calixarenes and calix(4)arene

This mini-review covers 25 fully functionalized facial calix[4]arene-based symmetrical and conical cyclic tetramers with significant (comparable to established therapeutic agents) anticancer and anti-infective activities. The main role of the calixarene scaffold in these calix[4]arene-based active pharmaceutical ingredients (calix[4]API-s) is to replicate embedded phenolic units in the cyclic tetramers. So, probably owing to the multivalency, facial, conical structures of calix[4]API-s and synergistic effect of their four replicated units, they can be considered as effective bioactive agents.

Topics: Animals; Anti-Infective Agents; Antineoplastic Agents; Calixarenes; Humans; Phenols

The present review is aimed at highlighting outlooks for cyclophanic 1,3-diketones as a new type of versatile ligands and building blocks of the nanomaterial for sensing and bioimaging. Thus, the main synthetic routes for achieving the structural diversity of cyclophanic 1,3-diketones are discussed. The structural diversity is demonstrated by variation of both cyclophanic backbones (calix[4]arene, calix[4]resorcinarene and thiacalix[4]arene) and embedding of different substituents onto lower or upper macrocyclic rims. The structural features of the cyclophanic 1,3-diketones are correlated with their ability to form lanthanide complexes exhibiting both lanthanide-centered luminescence and magnetic relaxivity parameters convenient for contrast effect in magnetic resonance imaging (MRI). The revealed structure-property relationships and the applicability of facile one-pot transformation of the complexes to hydrophilic nanoparticles demonstrates the advantages of 1,3-diketone calix[4]arene ligands and their complexes in developing of nanomaterials for sensing and bioimaging.

Topics: Calixarenes; Coordination Complexes; Ketones; Ligands; Molecular Structure; Nanoparticles; Particle Size; Phenols; Surface Properties

Chromium (III) salts are the most extensively used tanning agents due to the higher quality and stabilization ability to leather collagen. However, chromium (III) salts tanning agent has a strong impact on the environment owing to the pollution of wastewater and the solid waste containing chrome. In order to crosslink the collagen by a cleaner method, three kinds of sulfonated calix[4]arenes {sulfonated calix[4]arene (SC), sulfonated tetraphenyl calix[4]resorcinarene (STCR), and sulfonated tetramethylene tetraphenyl calix[4]resorcinarene(STTCR)} were prepared and utilized for the collagen crosslinking and leather tanning. The collagen crosslinking degree of sulfonated calix[4]arenes was investigated by fourier transform infrared (FTIR), thermogravimetric analysis (TG), differential scanning calorimetry (DSC), scanning electron micrograph (SEM), and X-ray photoelectron spectroscopy (XPS). The results show that the collagen can be crosslinked by phenol hydroxyl groups on sulfonated calix[4]arenes. Moreover, STCR shows better crosslinking effects than others because the number of phenol hydroxyl groups and the position of sulfonic groups on sulfonated calix[4]arenes play important roles in the crosslinking process. These results can be confirmed by sulfonated calix[4]arenes tanning processes, and STCR tanned leather shows the higher shrinkage temperature. This paper provides a promising chrome-free method to reduce the pollution of chromium tanning waste.

Topics: Calixarenes; Chromium Compounds; Collagen; Phenols

The design of biomimetic complexes for the modeling of metallo-enzyme active sites is a fruitful strategy for obtaining fundamental information and a better understanding of the molecular mechanisms at work in Nature's chemistry. The classical strategy for modeling metallo-sites relies on the synthesis of metal complexes with polydentate ligands that mimic the coordination environment encountered in the natural systems. However, it is well recognized that metal ion embedment in the proteic cavity has key roles not only in the recognition events but also in generating transient species and directing their reactivity. Hence, this review focuses on an important aspect common to enzymes, which is the presence of a pocket surrounding the metal ion reactive sites. Through selected examples, the following points are stressed: (i) the design of biomimetic cavity-based complexes, (ii) their corresponding host-guest chemistry, with a special focus on problems related to orientation and exchange mechanisms of the ligand within the host, (iii) cavity effects on the metal ion binding properties, including 1st, 2nd, and 3rd coordination spheres and hydrophobic effects and finally (iv) the impact these factors have on the reactivity of embedded metal ions. Important perspectives lie in the use of this knowledge for the development of selective and sensitive probes, new reactions, and green and efficient catalysts with bio-inspired systems.

Topics: Biomimetics; Calixarenes; Cations; Coordination Complexes; Cyclodextrins; Enzymes; Hydrophobic and Hydrophilic Interactions; Models, Molecular; Molecular Conformation; Phenols

Supramolecular chemistry has emerged as an important technique for the formation of biomaterials, including nano- and microparticles and hydrogels. One specific class of supramolecular chemistry is the direct association of guest-host pairs, which involves host macrocycles such as cyclodextrins and cucurbit[n]urils and a wide range of guest molecules, where association is typically driven by molecule size and hydrophobicity. These systems are of particular interest in the biomedical field due to their dynamic nature, chemical diversity, relative ease of synthesis, and ability to interact with biological or synthetic molecules. In this review, we discuss aspects of polymeric material assembly mediated by guest-host interactions, including the fundamentals of assembly into functional biomedical materials. Additionally, applications of biomaterials that utilize guest-host interactions are discussed with a focus on injectable material formulations, the sequestration and delivery of encapsulated cargo (i.e., drugs, biomolecules), and the investigation of cell-material interactions (i.e., adhesion, differentiation, and delivery). While methodologies for guest-host mediated assembly and biological interaction have rapidly evolved in recent years, they remain far from realizing their full potential in the biomaterials field.

Topics: Animals; Biocompatible Materials; Bridged-Ring Compounds; Calixarenes; Cyclodextrins; Drug Carriers; Drug Delivery Systems; Humans; Hydrogels; Imidazoles; Pharmaceutical Preparations; Phenols; Polymers; Quaternary Ammonium Compounds

The ion-coupled processes that occur in the plasma membrane regulate the cell machineries in all the living organisms. The details of the chemical events that allow ion transport in biological systems remain elusive. However, investigations of the structure and function of natural and artificial transporters has led to increasing insights about the conductance mechanisms. Since the publication of the first successful artificial system by Tabushi and co-workers in 1982, synthetic chemists have designed and constructed a variety of chemically diverse and effective low molecular weight ionophores. Despite their relative structural simplicity, ionophores must satisfy several requirements. They must partition in the membrane, interact specifically with ions, shield them from the hydrocarbon core of the phospholipid bilayer, and transport ions from one side of the membrane to the other. All these attributes require amphipathic molecules in which the polar donor set used for ion recognition (usually oxygens for cations and hydrogen bond donors for anions) is arranged on a lipophilic organic scaffold. Playing with these two structural motifs, donor atoms and scaffolds, researchers have constructed a variety of different ionophores, and we describe a subset of interesting examples in this Account. Despite the ample structural diversity, structure/activity relationships studies reveal common features. Even when they include different hydrophilic moieties (oxyethylene chains, free hydroxyl, etc.) and scaffolds (steroid derivatives, neutral or polar macrocycles, etc.), amphipathic molecules, that cannot span the entire phospholipid bilayer, generate defects in the contact zone between the ionophore and the lipids and increase the permeability in the bulk membrane. Therefore, topologically complex structures that span the entire membrane are needed to elicit channel-like and ion selective behaviors. In particular the alternate-calix[4]arene macrocycle proved to be a versatile platform to obtain 3D-structures that can form unimolecular channels in membranes. In these systems, the selection of proper donor groups allows us to control the ion selectivity of the process. We can switch from cation to anion transport by substituting protonated amines for the oxygen donors. Large and stable tubular structures with nanometric sized transmembrane nanopores that provide ample internal space represent a different approach for the preparation of synthetic ion channels. We used th

Topics: Calixarenes; Ion Transport; Ionophores; Lipid Bilayers; Metal Nanoparticles; Models, Biological; Molecular Structure; Phenols; Porosity

Topics: Amino Acids; Anions; Calixarenes; Cations; Coordination Complexes; Metals; Phenols; Stereoisomerism

This Account reviews the synthesis, conformations, and supramolecular properties of calixarenes endowed with alpha-amino acids or peptides (Peptidocalixarenes) and carbohydrate units (Glycocalixarenes), with a major emphasis on calix[4]arenes functionalized on the aromatic nuclei (upper or wide rim). Most properties of N-linked peptidocalix[4]arenes are found to be quite different from those of the corresponding C-linked derivatives. An interesting example is the tendency of C-linked peptidocalix[4]arenes to form self-assembled nanotubes in the solid state. In several cases the hydrogen bonding donor and acceptor groups of the amino acid residues and the cavity of cone calix[4]arenes act cooperatively in guest binding in nonpolar solvents but not in water, where hydrophobic interactions dominate. Upper-rim bridged peptidocalix[4]arenes act as vancomycin mimics being able to bind d-alanyl-d-alanine (d-Ala-d-Ala) residues. Glycocalix[4]arenes show the phenomenon of multivalency in their binding to specific lectins, and those bearing thiourea spacers between the calix[4]arene scaffold and the sugar units are able to bind aromatic carboxylates and phosphates, making them attractive as novel site specific drug delivery systems.

Topics: Alanine; Calixarenes; Crystallography, X-Ray; Glycosides; Hydrogen Bonding; Hydrophobic and Hydrophilic Interactions; Ionophores; Ligands; Macromolecular Substances; Models, Molecular; Molecular Conformation; Molecular Mimicry; Peptides; Phenols; Vancomycin

The effect of guest inclusion in the crystal structures of p-tert-butylcalix[4]arene complexes has been investigated through a combination of molecular-mechanics-based solid-state calculations and statistical analysis, with a procedure previously developed and used to study a variety of classes of organic compounds. The results indicate that the general trends in the behavior of calixarene crystals are very similar, irrespective of the presence or the absence of a guest encapsulated in the calixarene cavity, and are similar to those obtained for most other organics. Some differences arise only when a statistical analysis of several descriptors is performed. The investigation of the description of endo calix[4]arenes is extended by calculating the packing coefficient of the guest inside the calixarenes cavity, C(cavity), which shows that most of them are well accommodated inside the host and have coefficients that are similar to those found in the liquid phase. Further evaluation of the interaction energies between guest and host shows that the coefficients tend to be smaller than 30 kcal mol(-1). The combination of small C(cavity) and low interaction energies suggests that guest mobility in the solid could be rather common in endo complexes of calixarenes.

Topics: Binding Sites; Calixarenes; Crystallization; Models, Molecular; Molecular Structure; Phenols

A hydrophobic calix[4]arene derivative was investigated for its iodine (I

Topics: Calixarenes; Iodine; Povidone-Iodine; Spectrum Analysis

Calixarenes are hallmark molecules in supramolecular chemistry as hosts for small ligands. They have also conversely proved their interest as ligands toward assisted co-crystallization of proteins. These functionalized macrocycles target positively-charged residues, and notably surface-exposed lysines, with a site-selectivity finely characterized experimentally, but that remains to be assessed. Relying on a tailored molecular dynamics simulations protocol, we explore the association of

Topics: Antifungal Agents; Calixarenes; Ligands; Lysine; Proteins

Tumor selectivity is yet a challenge in chemotherapy-based cancer treatment. A series of calixarenes derivatized at the lower rim with 3-phenyl-1H-pyrazole units with variable upper-rim substituent and conformations of macrocyclic core, alkyl chain length between heterocycle and core, as well as phenolic monomer (5-(4-tert-butylphenyloxy)methoxy-3-phenyl-1H-pyrazole) have been synthesized and characterized in a range of therapeutically relevant cellular models (M-HeLa, MCF7, A-549, PC3, Chang liver, and Wi38) from different target organs/systems. Specific cytotoxicity for M-HeLa cells has been observed in tert-butylcalix[4]arene pyrazoles in 1,3-alternate (compound 7b) and partial cone (compound 7c) conformations with low mutagenicity and haemotoxicity and in vivo toxicity in mice. Compounds 7b,c have induced mitochondrial pathway of apoptosis of M-HeLa cells through caspase-9 activation preceded by the cell cycle arrest at G0/G1 phase. A concomitant overexpression of DNA damage markers in pyrazole-treated M-HeLa cells suggests that calixarene pyrazoles target DNA, which was supported by the presence of interactions between calixarenes and ctDNA at the air-water interface.

Topics: Animals; Calixarenes; HeLa Cells; Humans; Mice; Neoplasms; Porifera; Pyrazoles

Supramolecular carrier-mediated chemotherapy is a highly attractive strategy for targeted drug delivery. In this study, four novel biotin-linked calix[4]arenes BPCA1-BPCA4 have been rationally designed to construct nano-complex with doxorubicin. The

Topics: Biotin; Calixarenes; Cell Line, Tumor; Doxorubicin; Drug Carriers; Drug Delivery Systems; Micelles

Colorectal cancer (CRC) is a disease which is causing a high degree of mortality around the world. The present study reports the antiproliferative impact of the thioacetamide calix[4]arene, CAII receptor on a highly differentiated Caco-2 cell line. This statement is corroborated by the MTT assay results which revealed a reduction in the cell viability with an IC50 value of 19.02 ± 0.04 µM. Microscopic results indicated that at the starting amount of 10 µM of CAII, a decrease in cells confluency can already be observed in addition to changes in cells morphology. Cell metabolic pathway changes were also investigated.

Topics: Antineoplastic Agents; Caco-2 Cells; Calixarenes; Carbonic Anhydrase II; Cell Proliferation; Cell Survival; Colorectal Neoplasms; Humans; Phenols

Rolling resistance is one of the most important properties of a tire which is highly dependent on the viscoelastic properties of its rubber compounds. There are a lot of ways to reduce this parameter both in construction improvement of the tire and changing in rubber compound formulation especially in tire tread formulation. Rubber scientists have been trying to introduce new processing aid agents beyond the traditional tire components for reducing the rolling resistance. In this study, a unique structure of silica-supported calix[4]arene (SS-CSC[4]A) has been synthesized and applied as a processing aid agent in tire tread formulation. Fourier-transform infrared spectroscopy (FTIR), Nuclear Magnetic Resonance (1HNMR and 13CNMR), 29Si CP/MAS spectroscopy, thermal gravimetric analysis (TGA), elemental analysis, and acid-base titration were used to characterize its structure. Scanning Electron Microscopy (SEM) use to investigate the effect of prepared material on qualification of filler dispersion in the rubber matrix. The viscoelastic properties of the prepared rubber compound were measured by Dynamic Mechanical Thermal Analysis (DMTA) which showed the great decrease in rolling resistance of rubber compound based on SS-CSC[4]A as a processing aid agent. The mechanical and rheological properties of obtained tread rubber compound measured by tensometer and MDR rheometer showed no sensible changes in these properties.

Topics: Calixarenes; Phenols; Rubber; Silicon Dioxide

New fluorescent systems for photocatalysis, sensors, labeling, etc., are in great demand. Amphiphilic ones are of special interest since they can form functional colloidal systems that can be used in aqueous solutions. A new macrocycle platform for click chemistry and its adduct with o-propargylfluoresceine was synthesized and characterized using modern physical techniques. Nanosized solid lipid nanoparticles (SLNs) from the calixarene-fluoresceine adduct were synthesized through the solvent injection technique and well-characterized in the solution and in solid state using light-scattering and microscopy methods. The maximum fluorescence intensity of the SLNs was found to be in the pH range from 7 to 10. The Förster resonance energy transfer (FRET) efficiency from SLNs to rhodamine 6g was found to be 97.8%. Finally, pure SLNs and the FRET system SLNs-Rh6G were tested in model photocatalytic ipso oxidative hydroxylation of phenylboronic acid under blue LED light. The SLNs-Rh6G system was found to be the best, giving an almost qualitative phenol yield, which was shown by HPLC-UV analysis.

Topics: Calixarenes; Drug Carriers; Fluorescein; Lipids; Liposomes; Nanoparticles; Particle Size; Phenols

Diabetic retinopathy (DR) is a neurovascular disease characterized by the reduction of retina integrity and functionality, as a consequence of retinal pigment epithelial cell fibrosis. Although galectin-1 (a glycan-binding protein) has been associated with dysregulated retinal angiogenesis, no evidence has been reported about galectin-1 roles in DR-induced fibrosis. ARPE-19 cells were cultured in normal (5 mM) or high glucose (35 mM) for 3 days, then exposed to the selective galectin-1 inhibitor OTX008 (2.5-5-10 μM) for 6 days. The determination of cell viability and ROS content along with the analysis of specific proteins (by immunocytochemistry, Western blotting, and ELISA) or mRNAs (by real time-PCR) were performed. OTX008 5 μM and 10 μM improved cell viability and markedly reduced galectin-1 protein expression in cells exposed to high glucose. This was paralleled by a down-regulation of the TGF-β/, NF-kB p65 levels, and ROS content. Moreover, epithelial-mesenchymal transition markers were reduced by OTX008 5 μM and 10 μM. The inhibition of galectin-1 by OTX008 in DR may preserve retinal pigment epithelial cell integrity and functionality by reducing their pro-fibrotic phenotype and epithelial-mesenchymal transition phenomenon induced by diabetes.

Topics: Calixarenes; Diabetic Retinopathy; Epithelial Cells; Epithelial-Mesenchymal Transition; Fibrosis; Galectin 1; Glucose; Humans; Phenols; Reactive Oxygen Species; Retinal Pigment Epithelium; Retinal Pigments; Transforming Growth Factor beta

A preparative method for the synthesis of optically pure N-(1-phenylethyl)amides of inherently chiral (cR)- and (cS)-dibenzoyloxy-calix[4]arene acetic acids has been developed. Their absolute stereochemical configuration was determined by X-ray diffraction analysis.

Topics: Acetates; Amides; Calixarenes; Phenols; Stereoisomerism

Calix[4]arenes bearing photoactive α-ketophosphonic acid groups at the upper rim of the macrocycle were synthesized and evaluated as inhibitors of glutathione S-transferases. Irradiation at 365 nm increased the inhibition effects of some macrocyclic compounds on GSTP1-1 by more than two orders of magnitude. Calix[4]arene bis-α-ketophosphonic acids substituted at the lower rim by n-propyl or n-butyl groups showed IC

Topics: Animals; Calixarenes; Glutathione; Glutathione Transferase; Horses; Humans; Molecular Docking Simulation; Transferases

Artificial gene delivery systems are in great demand from both scientific and practical biomedical points of view. In this paper, we present the synthesis of a new click chemistry calix[4]arene precursor with free lower rim and new water-soluble calixarene triazoles with 12 amino-groups on the upper rim (one with free phenol hydroxyl groups and two another containing four butyl or tetradecyl fragments). Aggregation in the series of amino-triazole calixarenes of different lipophilicity (calixarene with free phenol hydroxyl groups or butyl and tetradecyl fragments on the lower rim) was studied using dynamic light scattering and fluorescent pyrene probe. It was found that calix[4]arene with a free lower rim, like alkyl-substituted butyl calix[4]arene, forms stable submicron aggregates 150-200 nm in size, while the more lipophilic tetradecyl -substituted calix[4]arene forms micellar aggregates19 nm in size. Using UV-Vis spectroscopy, fluorimetry and CD, it was shown that amino-triazole calix[4]arenes bind to calf thymus DNA by classical intercalation. According to DLS and TEM data, all studied macrocycles cause significant DNA compaction, forming stable nanoparticles 50-20 nm in size. Among all studied calix[4]arenes the most lipophilic tetradecyl one proved to be the best for both binding and compaction of DNA.

Topics: Calixarenes; DNA; Phenol; Polyamines; Triazoles

Fluorescent derivatives attract the attention of researchers for their use as sensors, photocatalysts and for the creation of functional materials. In order to create amphiphilic fluorescent derivatives of calixarenes, a fluorescein derivative containing oligoethylene glycol and propargyl groups was obtained. The resulting fluorescein derivative was introduced into three different (thia)calix[4]arene azide derivatives. For all synthesized compounds, the luminescence quantum yields have been established in different solvents. Using UV-visible spectroscopy, dynamic light scattering, as well as transmission and confocal microscopy, aggregation of macrocycles was studied. It was evaluated that calixarene derivatives with alkyl substituents form spherical aggregates, while symmetrical tetrafluorescein-containing thiacalix[4]arene forms extended worm-like aggregates. The macrocycle containing tetradecyl fragments was found to be the most efficient in photoredox ipso-oxidation of phenylboronic acid. In addition, it was shown that in a number of different electron donors (NEt

Topics: Calixarenes; Catalysis; Fluoresceins; Phenols; Water

In addition to a variety of viral-glycoprotein receptors (e.g., heparan sulfate, Niemann-Pick C1, etc.), dendritic cell-specific intercellular adhesion molecule-3-grabbing nonintegrin (DC-SIGN), from the C-type lectin receptor family, plays one of the most important pathogenic functions for a wide range of viruses (e.g., Ebola, human cytomegalovirus (HCMV), HIV-1, severe acute respiratory syndrome coronavirus 2, etc.) that invade host cells before replication; thus, its inhibition represents a relevant extracellular antiviral therapy. We report two novel

Topics: Antiviral Agents; Calixarenes; Cell Adhesion Molecules; Cell Line; Cytomegalovirus; Dendritic Cells; Ebolavirus; Glycoconjugates; Glycoproteins; Humans; Hydroxamic Acids; Jurkat Cells; Lectins, C-Type; Models, Biological; Phenols; Protein Binding; Receptors, Cell Surface; Recombinant Proteins; Viral Proteins

Carbohydrate-lectin interactions and glycol-molecule-driven self-assembly are powerful yet challenging strategies to create supramolecular nanostructures for biomedical applications. Herein, we develop a modular approach of micellization with a small molecular mannosylated-calix[4]arene synthetic core, CA

Topics: Calixarenes; Doxorubicin; Mannose Receptor; Micelles; Nanoparticle Drug Delivery System; Phenols

Calix[4]arene PTX008 is an angiostatic agent that inhibits tumor growth in mice by binding to galectin-1, a β-galactoside-binding lectin. To assess the affinity profile of PTX008 for galectins, we used

Topics: Binding Sites; Blood Proteins; Calixarenes; Dose-Response Relationship, Drug; Galectins; Humans; Magnetic Resonance Spectroscopy; Molecular Structure; Phenols; Polysaccharides; Structure-Activity Relationship

Calixarenes, with potential functionalization on the upper and lower rim, have been explored in recent years for the design and construction of anticancer agents in the field of drugs and pharmaceuticals. Herein, optimization of bis [N-(2-hydroxyethyl) aminocarbonylmethoxyl substituted calix [4] arene (CLX-4) using structure-based drug design and traditional medicinal chemistry led to the discovery of series of calix [4]arene carbonyl amide derivatives 5a-5t. Evaluation of the cytotoxicity of 5a-5t employing MTT assay in MCF-7, MDA-MB-231 (human breast cancer cells), HT29 (human colon carcinoma cells), HepG2 (human hepatocellular carcinoma cells), A549 (human lung adenocarcinoma cells) and HUVEC (Human Umbilical Vein Endothelial) cells demonstrated that the most promising compound 5h displayed the most superior inhibitory effect against A549 and MDA-MB-231 cells, which were 3.2 times and 6.8 times of CLX-4, respectively. In addition, the cell inhibition rate (at 10 μM) against normal HUVEC cells in vitro was only 9.6%, indicating the safty of compound 5h. Moreover, compound 5h could inhibit the migration of MDA-MB-231 cell in wound healing assay. Further mechanism studies significantly indicated that compound 5h could block MDA-MB-231 cell cycle arrest in G0/G1 phase by down regulating cyclin D1 and CDK4, and induce apoptosis by up-regulation of Bax, down-regulation of Caspase-3, PARP and Bcl-2 proteins, resulting in the reduction of DNA synthesis and cell division arrest. This work provides worthy of further exploration for the promising calixarene-based anticancer drugs.

Topics: Amides; Antineoplastic Agents; Calixarenes; Cell Cycle; Cell Proliferation; Cell Survival; Cells, Cultured; Dose-Response Relationship, Drug; Drug Design; Drug Screening Assays, Antitumor; Humans; Molecular Structure; Phenols; Structure-Activity Relationship; Wound Healing

We investigate the interaction between a molecule and a pore mouth-a critical step in adsorption processes-by characterizing the conformation of a macrocyclic calix[4]arene-Ti

Topics: Calixarenes; Density Functional Theory; Macrocyclic Compounds; Models, Molecular; Molecular Structure; Organometallic Compounds; Particle Size; Phenols; Porosity; Surface Properties; Titanium

Metal organic frameworks (MOFs) are hybrid organic inorganic materials with unique properties such as well-defined pore structure, extremely high surface area, excellent chemical-thermal stability. MOFs-based constructs have been extensively engineered and used for applications, such as enzyme immobilization for bio-catalysis. To obtained a zeolitic imidazole framework-8 (ZIF-8) for enzyme immobilization, Candida rugosa lipase (CRL) was pretreated with calix [4]arene tetracarboxylic acid (Calix) and reacted with Zn and imidazole by co-precipitation method. The prepared biocomposite was characterized by SEM, EDX, FT-IR, and XRD. The prepared CRL@Calix-ZIF-8 with high encapsulation efficiency showed improved resistance to alkali and thermal conditions. The CRL@Calix-ZIF-8 with the biocatalytic activity was 2-folds higher than that of the CRL@ZIF-8 (without Calix). The free lipase lost its catalytic activity completely at 60 °C after 100 min, while the CRL@Calix-ZIF-8 and CRL@ZIF-8 retained about 84% and 73%. It was found that CRL@Calix-ZIF-8 and CRL@ZIF-8 still retained ~83 and 67% of catalytic activity after its 6th use, respectively. The kinetic resolution of the immobilized lipases was examined for enantioselective hydrolysis of racemic naproxen methyl ester. CRL@Calix-ZIF-8 showed enantioselectivity against the racemic naproxen methyl ester, with E = 183 and 131 compared to the CRL@ZIF-8.

Topics: Biocatalysis; Calixarenes; Candida; Carboxylic Acids; Catalysis; Enzyme Stability; Enzymes; Enzymes, Immobilized; Esters; Hydrogen-Ion Concentration; Hydrolysis; Kinetics; Lipase; Metal-Organic Frameworks; Phenols; Spectroscopy, Fourier Transform Infrared; Stereoisomerism; Temperature

Effective protein adsorption by solid matrices from complex biological samples has attracted attention for broad application in biomedical field. Immobilization of calixarenes to solid supports is an essential process for their application in protein separation and purification. Silica is the most widely used support material in calixarene immobilization. With high concentration of polymer microspheres as templates, the large pore mesoporous silica microspheres with controllable, uniform size and structure were successfully synthesized and the resulting large pore mesoporous silica microspheres were modified with water-soluble tetrasulfonate calix[4]arene of unique hollow cavity-shaped structure. The tetrasulfonate calix[4]arene modified large pore mesoporous silica microspheres (SCLX4@LPMS) were characterized by diverse analytical techniques and their protein adsorption performance were also investigated. The obtained SCLX4@LPMS gave rise to an adsorption efficiency of >90% for cytochrome c and lysozyme within a wide pH range of 3.0-10.0 and possessed remarkably high adsorption capacity of cytochrome c (363.64 mg g

Topics: Adsorption; Calixarenes; Microspheres; Phenols; Porosity; Silicon Dioxide

Two solid phase extraction resins (SPER) were prepared by impregnating solutions of two diglycolamide-functionalized calix[4]arenes in 10% isodecanol in n-dodecane into Chromosorb W, as the stationary phase. While SPER-I contained n-propyl functionalized calix[4]arene, SPER-II contained the calix[4]arene with isopentyl groups at the carboxamide nitrogen atoms. The SPERs were characterized by SEM, TGA, FTIR, etc. and were used for the batch uptake of neptunium(IV) from nitric acid feed solutions. While the uptake of Np(IV) was extremely high with SPER-I (K

Topics: Adsorption; Calixarenes; Glycolates; Ions; Kinetics; Ligands; Neptunium; Nitric Acid; Phenols; Resins, Synthetic; Solid Phase Extraction; Spectroscopy, Fourier Transform Infrared; Temperature; Thermogravimetry; Time Factors

Alzheimer's disease (AD) is a progressive neurodegenerative condition affecting people in the elderly. Targeting aggregation of β-amyloid peptides (Aβ) is considered a promising approach for the therapeutic treatment of the disease. Peptide based inhibitors of β-amyloid fibrillation are emerging as safe drug candidates as well as interesting compounds for early diagnosis of AD. Peptide conjugation via covalent bond with functional moieties enables the resultant hybrid system to acquire desired functions. Here we report the synthesis, the structural characterization, and the Aβ

Topics: Aged; Alzheimer Disease; Amyloid beta-Peptides; Calixarenes; Humans; Neurons; Peptide Fragments; Phenols

It is crucial to determine and control the metronidazole (MET) ingredient in food and pharmaceuticals for human health and food safety. Even though many sensors have been previously reported to detect MET, there is still a need for a highly selective and sensitive, easy, fast, cost-effective sensor in this area. Herein, we report a fluorescent calix[4]arene derivative (PIMC) for highly selective and sensitive and facile and rapid MET detection based on fluorescence (FL) quenching. The highest FL quenching occurs when PIMC is exposed to MET solution at 400 nm (λ

Topics: Calixarenes; Fluorescent Dyes; Humans; Metronidazole; Phenols; Spectrometry, Fluorescence

The present work describes the reaction of triplet dioxygen with the porphyrinogenic calix[4]pyrrolato aluminates to alkylperoxido aluminates in high selectivity. Multiconfigurational quantum chemical computations disclose the mechanism for this spin-forbidden process. Despite a negligible spin-orbit coupling constant, the intersystem crossing (ISC) is facilitated by singlet and triplet state degeneracy and spin-vibronic coupling. The formed peroxides are stable toward external substrates but undergo an unprecedented oxidative pyrrole α-cleavage by ligand aromatization/dearomatization-initiated O-O σ-bond scission. A detailed comparison of the calix[4]pyrrolato aluminates with dioxygen-related enzymology provides insights into the ISC of metal- or cofactor-free enzymes. It substantiates the importance of structural constraint and element-ligand cooperativity for the functions of aerobic life.

Topics: Aluminum; Calixarenes; Density Functional Theory; Flavoproteins; Models, Molecular; Molecular Structure; Oxygen; Phenols; Pyrroles

Calixarenes, which have a great place in supramolecular chemistry, have become the most prominent macrocyclic compounds in synthetic organic chemistry due to their easy synthesis and functionalization. In this study, p-tert-butyl calix[4]arene dihydrazide derivative was synthesized and then reacted with 3-oxo-3,4-dihydro-2 H-benzo[b][1,4] thiazin-2-ylideneacetyl chloride to prepare new calixarene based chromophore compound 4. The structure of the synthesized compound was elucidated by spectroscopic methods such as

Topics: Calixarenes; Magnetic Resonance Spectroscopy; Phenols; Spectroscopy, Fourier Transform Infrared

Topics: Acetates; Amino Acids; Calixarenes; Chromatography, High Pressure Liquid; Phenols; Stereoisomerism

One of the possible ways of improving the activity and selectivity profile of anticancer agents is to design drug carrier systems employing nanomolecules. Calix[4]arene derivatives and chlorambucil and ibuprofen are important compounds that exhibit interesting anticancer properties.. The objective of this article is the synthesis of new calix[4]arene-derivative conjugates of chlorambucil or ibuprofen with potential anticancer activity.. Cytotoxicity assays were determined using the protein-binding dye sulforhodamine B (SRB) in microculture to measure cell growth as described [19, 20]. Conjugates of chlorambucil and resorcinarene-dendrimers were prepared in 2% DMSO and added into the culture medium immediately before use. Control cells were treated with 2% DMSO.. Thus, calix[4]arene-derivative conjugates of chlorambucil or ibuprofen showed good stability of the chemical link between drug and spacer. Evaluation of the cytotoxicity of the calix[4]arene chlorambucil or ibuprofen conjugates employing a sulforhodamine B (SRB) assay in K-562 (human chronic myelogenous leukemia cells) and U-251 (human glioblastoma cells) demonstrated that the conjugate was more potent as an antiproliferative agent than free chlorambucil and ibuprofen. The conjugates did not show any activity against the COS-7 African green monkey kidney fibroblast cell line.. In the paper, we report the synthesis and spectroscopic analyses of new calix[4]arene derivative conjugates of chlorambucil or ibuprofen. Cytotoxicity assays revealed that at 10 μM, the conjugates were very active against K-562 (human chronic myelogenous leukemia cells) and U- 251 (human glioblastoma cells) cancer cells' proliferation. In order to explain the molecular mechanisms involved in the anticancer activity of calix[4]arene chlorambucil or ibuprofen conjugates, our research will be continued.

Topics: Antineoplastic Agents; Calixarenes; Cell Proliferation; Chlorambucil; Drug Screening Assays, Antitumor; Humans; Ibuprofen; Molecular Structure; Phenols; Tumor Cells, Cultured

The unique conformational properties, functionality, low toxicity, and low cost make calixarene-based compounds a valuable candidate against cancer. The aim of the present study is the synthesis of the upper rim and lower rim-functionalized l-proline-based calix[4]arene derivatives and evaluation of their cytotoxic potential for human cancerous cells as well as to determine the death mechanism. Synthesized calix[4]arene (3, 8a, 8b 13a, and 13b) derivatives were characterized by different spectroscopic techniques such as

Topics: Antineoplastic Agents; Apoptosis; Calixarenes; Cell Line, Tumor; Drug Screening Assays, Antitumor; Humans; Phenols; Proline; Spectrum Analysis; Structure-Activity Relationship

Naringenin is considered as an important flavonoid in phytochemistry because of its important effect on cancer chemoprevention. Unfortunately its poor solubility has restricted its therapeutic applications. In this study, an efficient water-soluble fluorescent calix[4]arene (compound

Topics: Calixarenes; Flavanones; Humans; Phenols; Solubility; Water

Sulfonato-calix[n]arenes (sclxn) are promising tools to generate crystalline protein frameworks. We report, for the first time, a lower rim functionalised octa-anionic calix[4]arene (sclx4mc) in complex with proteins. Two crystal structures of sclx4mc bound to yeast or horse heart cytochrome c (cytc) are described. Highly porous honeycomb or tubular assemblies were obtained with yeast or horse cytc, respectively. Related frameworks were obtained previously with sclx8 and sclx6 but not with sclx4, suggesting that the ligand charge is a determining factor.

Topics: Animals; Anions; Calixarenes; Crystallization; Crystallography, X-Ray; Cytochromes c; Horses; Ligands; Molecular Structure; Phenols; Porosity; Proteins; Yeasts

Topics: Aquaporins; Calixarenes; Membranes, Artificial; Molecular Dynamics Simulation; Nanostructures; Peptides; Permeability; Phenols; Water

Topics: Adsorption; Alginates; Calixarenes; Hydroxides; Methylene Blue; Phenols; Water Purification

A calix[4]arene based compound incorporating amide and morpholine moieties has been synthesized and its ion recognition property towards metal ions and application of its metal complex towards sensing of amino acids has been investigated. The synthesized compound interacts with Cu

Topics: Calixarenes; Cations, Divalent; Colorimetry; Coloring Agents; Copper; Crystallography, X-Ray; Humans; Limit of Detection; Models, Molecular; Paper; Phenols; Reagent Strips; Saliva; Tyrosine; Water

In the search for soft and smart materials for nanomedicine, which is a present challenge, supramolecular nanohydrogels built on self-assembling low-molecular-weight building blocks attract interest for their structural, mechanical and functional properties. Herein, we describe a supramolecular nanohydrogel formed by a biofriendly micellar self-assembling choline-calix[4]arene derivative in the presence of curcumin, a natural and multitarget pharmacologically relevant drug. Morphology and mechanical properties of the nanohydrogel were investigated, and theoretical simulation performed to model the nanohydrogel structure. The self-healing and injectable nanohydrogel easily formed in PBS medium at physiologic pH, without using additives and organic solvents. The micellar nanohydrogel protected curcumin from rapid chemical and photochemical degradation, and slowly dissolved in curcumin-loaded micelles sustaining the drug release in a low rate. The nanohydrogel which combines the mechanical properties of a hydrogel and the benefits of a nanoscale micelle in drug delivery, appears a promising novel material for drug delivery.

Topics: Calixarenes; Computer Simulation; Curcumin; Drug Liberation; Drug Stability; Hydrogels; Injections; Micelles; Models, Molecular; Phenols; Rheology; Spectrophotometry, Ultraviolet; Viscosity

Two decades ago, halogen bonding attracted considerable attention as a new type of non-covalent interaction and has now emerged as an important supramolecular tool for crystal engineering, demonstrating its ability to self-assemble low affinity entities. Specific features of halogen bonds have been subsequently harnessed in biological and material sciences to give rise to elegant functional systems with a wide range of applications. In this highlight, we focused on new concepts in polymer science, electrochemistry, electronic and sensing materials. Recent findings on the use of halogenated compounds for transmembrane transport are also discussed, together with a short summary of the current understanding of the nature of the halogen bond, in the light of modern computational tools and energy decomposition.

Topics: Biological Transport; Calcium Compounds; Calixarenes; Catalysis; Electrochemical Techniques; Ferrous Compounds; Halogenation; Halogens; Metallocenes; Oxides; Phenols; Polymers; Semiconductors; Solar Energy; Thyroid Hormones; Titanium; Volatile Organic Compounds

Primary intracerebral hemorrhage (ICH) is a leading cause of long-term disability and death worldwide. Drug delivery vehicles to treat ICH are less than satisfactory because of their short circulation lives, lack of specific targeting to the hemorrhagic site, and poor control of drug release. To exploit the fact that metal ions such as Fe

Topics: Animals; Benzylisoquinolines; Blood-Brain Barrier; Calixarenes; Cerebral Hemorrhage; Disease Models, Animal; Drug Carriers; Humans; Interleukin-1beta; Ions; Male; Matrix Metalloproteinase 9; Metals; Mice; Mice, Inbred C57BL; Nanostructures; Neurons; Neuroprotective Agents; Organophosphonates; Phenols; Reactive Oxygen Species; Tetrahydroisoquinolines

A new topological design of fluorescent probes for sensing copper ion is disclosed. The calix[

Topics: Alkynes; Calixarenes; Cations, Divalent; Copper; Ethers, Cyclic; Fluorescence; Fluorescent Dyes; Molecular Structure; Phenols; Piperidines; Quantum Theory; Receptors, Artificial; Solutions

Curcumin (CUR) has shown remarkable efficacy in the treatment of skin diseases, but its effective transdermal delivery is still a major challenge and stimulates interest in the design of novel systems for CUR dispersion, preservation, and delivery facilitation to the deeper layers of the skin. The present work aimed to investigate the potential of a nanohydrogel, formed by a micellar choline-calix[4]arene amphiphile (CALIX) and CUR, in the treatment of skin diseases through an imiquimod (IMQ)-induced psoriasis model. Psoriasis plaques are associated with aberrant keratinization, abnormal distribution of tight junctions (TJs) proteins, and enhanced expression of inflammatory markers. The nanohydrogel restored the normal distribution of TJs proteins ZO1 and occludin and reduced the expression of TNF-α and inducible nitric oxide synthetase (iNOS) compared to the untreated IMQ group. The novelty lies in the calix[4]arene-based nanohydrogel as a potential new soft material for the topical skin delivery of CUR. The nanohydrogel, due to its physicochemical and mechanical properties, enhances the drug water-solubility, preserves CUR from rapid degradation, and eases the local skin administration and penetration.

Topics: Administration, Cutaneous; Animals; Anti-Inflammatory Agents, Non-Steroidal; Calixarenes; Choline; Curcumin; Disease Models, Animal; Drug Carriers; Hydrogels; Male; Mice; Mice, Inbred BALB C; Phenols; Psoriasis

A MoS2-supported-calix[4]arene (MoS2-CA4) nanocatalyst was used for efficient synthesis of 2,4,5-trisubstituted imidazole derivatives from 1-(4-nitrophenyl)-2-(4-(trifluoromethyl)phenyl)ethane-1,2-dione, aldehydes and ammonium acetate under solvent-free conditions. Reusability of the catalyst up to five cycles without any significant loss in the yields of the product is the unique feature of this heterogeneous solid catalysis. Furthermore, the noteworthy highlights of this method are safe reaction profiles, broad substrate scope, excellent yields, economical, solvent-free, and simple workup conditions. All synthesized compounds were evaluated for their in vitro antitubercular (TB) activity against

Topics: 3-Oxoacyl-(Acyl-Carrier-Protein) Reductase; Animals; Antitubercular Agents; Bacterial Proteins; Calixarenes; Catalysis; Chlorocebus aethiops; Disulfides; Drug Evaluation, Preclinical; Enzyme Inhibitors; Humans; Imidazoles; Microbial Sensitivity Tests; Molecular Docking Simulation; Molybdenum; Mycobacterium tuberculosis; Phenols; Protein Binding; Small Molecule Libraries; Structure-Activity Relationship; Vero Cells

In an attempt to circumvent the major pitfalls associated with conventional chemotherapy including drug resistance and off-target toxicity, we have adopted a strategy to simultaneously target both mitochondrial DNA (Mt-DNA) and nuclear DNA (n-DNA) with the aid of a targeted theranostic nanodelivery vehicle (TTNDV). Herein, folic acid-anchored

Topics: Animals; Antibiotics, Antineoplastic; Calixarenes; Cell Proliferation; Cell Survival; Cells, Cultured; DNA, Mitochondrial; DNA, Neoplasm; Doxorubicin; Drug Carriers; Drug Screening Assays, Antitumor; Folic Acid; Gold; Humans; Male; Metal Nanoparticles; Mice; Mice, Inbred BALB C; Neoplasms, Experimental; Particle Size; Phenols; Photochemotherapy; Photosensitizing Agents; Surface Properties; Temperature

Although alkaline earth metal cations play an important role in our daily life, little attention has been paid to the field of fast quantitative analysis of their content due to a lack of satisfactory precision and a fast and convenient means of detection. In this study, we have designed a set of molecular tweezers based on the calix[4]arene chemosensor

Topics: Animals; Barium; Calcium; Calixarenes; Cell Survival; HeLa Cells; Humans; Metals, Alkaline Earth; Optical Imaging; Organometallic Compounds; Phenols; Strontium; Tumor Cells, Cultured; Zebrafish

We recently identified completely monodisperse micelles whose aggregation number (N

Topics: Calixarenes; Cellobiose; Hydrogen-Ion Concentration; Hydrophobic and Hydrophilic Interactions; Micelles; Particle Size; Phenols; Surface Properties; Surface-Active Agents; Temperature

A reversible and easy assembled fluorescent sensor based on calix[4]arene and phenolphthalein (C4P) was developed for selective zinc ion (Zn

Topics: Cadmium; Calixarenes; Cell Line, Tumor; Cysteine; Fluorescent Dyes; Humans; Isomerism; Limit of Detection; Magnetic Resonance Spectroscopy; Molecular Imaging; Phenolphthalein; Phenols; Sensitivity and Specificity; Spectrometry, Fluorescence; Spectrophotometry, Ultraviolet; Zinc

A new water-soluble tetra-proline-modified calix[4]arene-bonded silica stationary phase was prepared straightforwardly by an indirect method and characterized by elemental analysis, energy dispersive Spectrometry, solid-state

Topics: Calixarenes; Chromatography, Reverse-Phase; Hydrophobic and Hydrophilic Interactions; Phenols; Proline; Silicon Dioxide

A novel nanocomposite of MGO-NGC, composed of magnetic Fe3O4 nanoparticles (M), graphene oxide (GO), and N-methyl-d-glucamine functionalized calix[4]arene (NGC), was synthesized and applied as an effective adsorbent for the removal of two selected pesticides, namely hexaconazole and chlorpyrifos from water samples. The adsorbent was characterized by FTIR, SEM, EDX, TEM, and XRD. The main parameters affecting the adsorption process such as adsorbent dosage, pH of sample solution, salt effect, pesticide concentration, and adsorption time were investigated. The data from kinetic studies fitted well to the pseudo-second order kinetic model with R2 > 0.99. Among the isotherm models of Langmuir, Freundlich, Temkin, and Dubinin-Radushkevich, the Langmuir isotherm fitted well to the adsorption process and demonstrated the monolayer adsorption pattern of the pesticides. Moreover, high adsorption capacities of 78.74 and 93.46 mg g-1 were obtained for chlorpyrifos and hexaconazole, respectively. Thermodynamic and free energy data indicated the physisorption mechanism for the adsorption process. The new adsorbent can be employed as an efficient, environment friendly, and highly reusable alternative for the removal of chlorinated pesticides from aqueous media.

Topics: Adsorption; Calixarenes; Graphite; Kinetics; Nanocomposites; Pesticides; Phenols; Thermodynamics; Water Pollutants, Chemical; Water Purification

Calix[4]arene derivative (1), bearing four α-l-C-fucosyl units linked via a flexible spacer, and a monomeric analogous (2) bearing a single moiety of fucose, were synthesized. Compounds 1 and 2 were assayed for antibiofilm activity against Pseudomonas aeruginosa (Gram-) and Staphylococcus epidermidis (Gram+). The macrocyclic compound 1 showed very high percentage of biofilm inhibition against two different bacterial strains while compound 2, which does not possess a macrocyclic structure, showed only moderate biofilm inhibition against P. aeruginosa and no biofilm inhibition against S. epidermidis. The fucose multivalent derivative could be a new broad-spectrum antibiofilm agent.

Topics: Anti-Bacterial Agents; Biofilms; Calixarenes; Chemistry Techniques, Synthetic; Fucose; Microbial Sensitivity Tests; Models, Molecular; Molecular Conformation; Phenols; Pseudomonas aeruginosa; Staphylococcus epidermidis

Two calix[4]resorcinarenes, which differ in the length of the alkyl chain on the methylene bridge between the aromatic rings, have been embedded in unilamellar liposomes prepared from 1-palmitoyl-2-oleoyl-sn-glycerol-3-phosphocholine in three host/guest ratios, following two different procedures. The effect of the insertion of the guests has been evaluated through the measurements of the viscosity and the kinetic stability of the liposomal systems by means of the fluorescent probes pyrene and 5(6)-carboxyfluorescein. The presence of the guests reduces the viscosity of the liposomes, suggesting a modification of the bilayer structure. However, this does not affect liposome stability. A calix[4]resorcinarene cavitand with a more rigid conformation compared to the parent resorcinarene, has been also synthetized and embedded in liposomes. The free energy of the insertion of the substrates in the lipid bilayer has been evaluated through Molecular Dynamics simulations.

Topics: Calixarenes; Kinetics; Lipid Bilayers; Liposomes; Molecular Dynamics Simulation; Phenols; Phenylalanine; Viscosity

Chemotherapy as an important tool for cancer treatment faces many obstacles such as multidrug resistance and adverse toxic effects on healthy tissues. Drug delivery systems has opened a new window to overcome these problems. There has been a strong interest development of new platform and system for delivof chemotherapeutic agents.. In the present study, a green synthesis method was chosen and performed for preparation of a novel amphoteric calix[4]arene (Calix) macrocycle with low toxicity to the human body.. The amphoteric Calix was coated on the surface of Fe. In vitro biological studies including hemolysis assay, erythrocytes sedimentation rate, red blood cells aggregation, cyto cellular internalization, and apoptosis evaluations were performed. Based on results, the developed nanocarrier has many advantages and capability for an efficient codelivery of DOX and MTX, which has a highly potent ability to kill cancer cells.. All these results persuade us, this nanocarrier could be effectively used for cancer therapy of MCF7 breast cancer cells and is suitable for use in further animal studies in future investigations.

Topics: Animals; Antineoplastic Agents; Apoptosis; Breast Neoplasms; Calixarenes; Calorimetry, Differential Scanning; Doxorubicin; Drug Carriers; Drug Delivery Systems; Drug Liberation; Drug Resistance, Multiple; Dynamic Light Scattering; Endocytosis; Female; Humans; Magnetite Nanoparticles; MCF-7 Cells; Methotrexate; Particle Size; Phenols; Spectroscopy, Fourier Transform Infrared

The low photostability of conventional organic dyes and the toxicity of cadmium-based luminescent quantum dots have prompted the development of novel probes for in vitro and in vivo labelling. Here, a new fluorescent lanthanide probe based on silica nanoparticles is fabricated and investigated for optically traceable in vitro translocator protein (TSPO) targeting. The targeting and detection of TSPO receptor, overexpressed in several pathological states, including neurodegenerative diseases and cancers, may provide valuable information for the early diagnosis and therapy of human disorders. Green fluorescent terbium(III)-calix[4]arene derivative complexes are encapsulated within silica nanoparticles and surface functionalized amine groups are conjugated with selective TSPO ligands based on a 2-phenylimidazo[1,2-a]pyridine acetamide structure containing derivatizable carboxylic groups. The photophysical properties of the terbium complex, promising for biological labelling, are demonstrated to be successfully conveyed to the realized nanoarchitectures. In addition, the high degree of biocompatibility, assessed by cell viability assay and the selectivity towards TSPO mitochondrial membrane receptors, proven by subcellular fractional studies, highlight targeting potential of this nanostructure for in vitro labelling of mitochondria.

Topics: Calixarenes; Cell Line, Tumor; Fluorescent Dyes; Humans; Ligands; Nanoparticles; Phenols; Protein Binding; Receptors, GABA; Silicon Dioxide; Terbium

Here we report template-free synthesis of imine-linked calix[4]arene hollow nanocapsules and their utility in the effective delivery of a poorly soluble cancer drug into tumor cells. These stimuli-responsive nanocapsules show high drug loading and release which resulted in a 40-fold higher cytotoxicity for breast cancer cell line over normal cells.

Topics: Antineoplastic Agents; Calixarenes; Camptothecin; Drug Carriers; Drug Liberation; Humans; Hydrogen-Ion Concentration; MCF-7 Cells; Nanocapsules; Phenols

This paper describes the synthesis of new chiral calix [4]arene derivative having (R)-2-phenylglycinol moiety (compound 6), and its chiral recognition studies for ascorbic acid (AA) enantiomers by using Quartz Crystal Microbalance (QCM). Initial experiments indicated that the outstanding selective chiral recognition (α) was observed as 2.61 for l-enantiomer of AA. The sensitivity (S) and the limit of detection (LOD) values for L-AA were calculated as 0.0226 Hz/μM and 0.63 μM, respectively. Furthermore, the sorption behavior and mechanism of AA onto compound 6 film were evaluated and the sorption data exhibited a good correlation with the Freundlich isotherm models. The maximum uptake of L-AA by the sensor was found as 5895.76 mg/g. In conclusion, chiral recognition of AA enantiomers as real-time, sensitive, selective and effective was performed by a calixarene derivative coated QCM sensor.

Topics: Ascorbic Acid; Biosensing Techniques; Calixarenes; Ethanolamines; Gold; Phenols; Quartz Crystal Microbalance Techniques; Stereoisomerism; Surface Properties

In this study a new calix[4]arene triazole 5 was successfully synthesized using click reaction and characterized through UV-visible, FT-IR,

Topics: Calixarenes; Cefuroxime; Drinking Water; Humans; In Vitro Techniques; Limit of Detection; Magnetic Resonance Spectroscopy; Phenols; Plasma; Spectroscopy, Fourier Transform Infrared; Triazoles; Water Pollutants, Chemical

Here we report a new chiral stationary phase (CSP) immobilized on silica gel based on cone calix[4]arene functionalized at the upper rim with two l-alanine units as new chiral selector that has been used in high-performance liquid chromatography. The CSP was prepared by covalently bonding the allyl groups at the lower rim of calix[4]arene to silica gel by thiol-ene click chemistry reaction. Elemental analysis of the CSP showed that 120 μmol of chiral selector bonded per gram of silica gel. 1-Hexene was used for end-capping of unreacted mercapto groups on silica gel. Since the CSP is chemically bonded to the silica, it can be used in the normal-phase and reversed-phase mode and with halogenated solvents as mobile phases, if desired. The chromatographic performance of the CSP was evaluated in the enantioseparation of the 3,5-dinitrobenzoyl derivatives of some amino acids, diclofop-methyl and dl-mandelic acid.

Topics: Alanine; Calixarenes; Chromatography, High Pressure Liquid; Dinitrobenzenes; Models, Chemical; Pharmaceutical Preparations; Phenols; Stereoisomerism

In the present work, a novel metal-organic framework (MOF) fluorescent probe was prepared by post-synthetic modification of MIL-53-NH

Topics: Calixarenes; Fluorescent Dyes; Hippurates; Humans; Limit of Detection; Metal-Organic Frameworks; Models, Molecular; Phenols; Reagent Strips; Spectrometry, Fluorescence; Toluene; Urinalysis

Carbon Quantum Dots (CDs) owing to its unique photophysical properties have attracted immense consideration of the researchers in last decade to explore its applications in the fields of bio-imaging and sensing. In the present work, we have developed a novel CDs functionalized with Calix[4]arene derivative by hydrothermal route to detect biologically pertinent Zn

Topics: Calixarenes; Carbon; Cells, Cultured; Escherichia coli; Fluorescence; Fluorescent Dyes; Ions; Molecular Structure; Optical Imaging; Particle Size; Phenols; Quantum Dots; Quantum Theory; Solutions; Spectrometry, Fluorescence; Surface Properties; Time Factors; Ultraviolet Rays; Water; Zinc

Targeting the intracellular "labile" iron pool is turned as a key modulator for cancer progression since the former is responsible for several pathological processes in tumor cells. Herein, we report a nonfluorescent calix[4]arene based triazole appended molecular probe (PTBC) for redox-specific detection of Fe

Topics: A549 Cells; Calixarenes; Cell Survival; Density Functional Theory; Dose-Response Relationship, Drug; Humans; Iron; Molecular Probes; Molecular Structure; Oxidation-Reduction; Phenols; Structure-Activity Relationship; Triazoles

A calix[4]arene-functionalized graphene oxide/polydopamine-coated cellulose acetate adsorbent was fabricated for the pre-concentration of aflatoxins. The highly porous developed adsorbent does not produce the high backpressure that normally occurs in particle-packed cartridges and its large surface area helps to improve adsorption. The highly efficient adsorption of aflatoxins by the hybrid adsorbent is facilitated via hydrogen bonding and hydrophobic and π-π interactions. Polymerization time, amount of calix[4]arene-functionalized graphene oxide, type and volume of desorption solvent, sample pH, sample volume, and sample flow rate were optimized. The linearity of aflatoxin B1 was in the range of 0.01-10.0 μg/kg, aflatoxin B2 was in the range of 0.02-10.0 μg/kg and aflatoxin G1 and aflatoxin G2 were in the range of 0.050-10.0 μg/kg. The limits of detection were 0.01 μg/kg for aflatoxin B1, 0.02 μg/kg for aflatoxin B2 and 0.05 μg/kg for aflatoxin G1 and aflatoxin G2. The developed calix[4]arene-functionalized graphene oxide/polydopamine-coated cellulose acetate adsorbent was successfully utilized for the analysis of aflatoxins from corn samples and the extraction efficiency was satisfactory with obtained recoveries from 83.0 to 106.7%. Moreover, fabricated adsorbent is easy to prepare, inexpensive, and can be reused.

Topics: Adsorption; Aflatoxins; Calixarenes; Cellulose; Graphite; Hydrogen-Ion Concentration; Indoles; Molecular Structure; Oxides; Particle Size; Phenols; Polymers; Solid Phase Extraction; Surface Properties; Zea mays

A promising strategy to design safer and more effective cationic lipids for gene delivery with inherent antibacterial properties is to covalently tether a lipophilic moiety with oligomeric aminoglycosides (AGs), a large family of Gram-negative-active antibiotics. Herein, we reported the development of a new class of multicationic-head AG-based amphiphiles built on the tetramino-tetrahexyloxycalix[4]arene (4A4Hex-calix-calix[4]) scaffold. Three different conjugates, namely 4A4Hex-calix-calix[4]-neomycin, -neamine, and -paromomycin, were synthesized and characterized. Due to the inherent multivalency of AGs and the amphiphilic behaviour, every 4A4Hex-calix-calix[4]-AG exhibited greater DNA binding ability than the gold standard transfectant 25 kDa bPEI and striking DNA packing ability. DNA/4A4Hex-calix-calix[4]-AG complexes at charge ratios (CRs, +/-) used for transfections displayed good colloidal stability, with a hydrodynamic diameters of ≈150 nm and an overall surface charges of ≈+30 mV. DNA/4A4Hex-calix[4]-AGs nanoassemblies, everyone tested at the optimal CR, invariably showed good transfection efficiency in two cell lines, along with low-to-negligible cytotoxicity. Besides, DNA/4A4Hex-calix-calix[4]-AG complexes exhibited appreciable antimicrobial activity against Gram-negative bacteria, even greater than uncomplexed 4A4Hex-calix-calix[4]-AGs. Altogether, these results disclose 4A4Hex-calix[4]-AGs as promising gene delivery tools with unique antibacterial properties.

Topics: Active Transport, Cell Nucleus; Anti-Bacterial Agents; Binding Sites; Calixarenes; DNA; Drug Design; Escherichia coli; Gene Expression Regulation; HeLa Cells; Humans; Molecular Structure; Nucleic Acid Conformation; Phenols; Sarcina; Structure-Activity Relationship; Surface Properties; Surface-Active Agents; Transfection

p- tert-Butyl-calix[4]arene was derivatized by integrating a benzooxadiazole fluorescent tag into its 1,3-arms at the lower rim to result in L and was characterized. L was titrated with 17 anions in THF and found selective for F

Topics: Calixarenes; Fluorescent Dyes; Fluorides; HeLa Cells; Humans; Microscopy, Confocal; Models, Molecular; Molecular Conformation; Oxadiazoles; Phenols; Solutions

The present study reports the preparation of novel alginate/calix[4]arenes modified graphene oxide nanocomposite beads (alginate/C4As-GOs) based on p-tert-butyl calix[4]arene and sodium p-sulfonatocalix[4]arene modified GO nanosheets (CGO and SGO). Different properties of alginate/GO and alginate/C4As-GOs nanocomposite beads were investigated by FTIR, XRD, TGA, SEM, and swelling ratio analysis. The alginate beads containing SGO nanosheets (ABSGO) showed a thin layered structure, high porosity, and high swelling ratio compared to other samples. Moreover, the batch adsorption studies on methylene blue exhibited that ABSGO beads act as a high-performance adsorbent among samples and can be introduced as a novel and efficient dye adsorbent. In the case of ABSGO adsorbent, the equilibrium adsorption data were modeled using the Langmuir and Freundlich isotherms. According to Langmuir isotherm equation, the maximum adsorption capacity of ABSGO was obtained 170.36 mg/g. The kinetic adsorption studies confirmed that the adsorption of MB onto ABSGO well obey the pseudo-second-order kinetic model.

Topics: Adsorption; Alginates; Calixarenes; Coloring Agents; Graphite; Hydrogen-Ion Concentration; Microspheres; Nanocomposites; Oxides; Phenols; Temperature; Water Pollutants, Chemical

Curcumin is an Indian spice with a wide spectrum of biological and pharmacological activities but poor aqueous solubility, rapid degradation, and low bioavailability that affect medical benefits. To overcome these limits in ophthalmic application, curcumin was entrapped in a polycationic calix[4]arene-based nanoaggregate by a simple and reproducible method. The calix[4]arene-curcumin supramolecular assembly (Calix-Cur) appeared as a clear colloidal solution consisting in micellar nanoaggregates with size, polydispersity index, surface potential, and drug loading percentage meeting the requirements for an ocular drug delivery system. The encapsulation in the calix[4]arene nanoassembly markedly enhanced the solubility, reduced the degradation, and improved the anti-inflammatory effects of curcumin compared to free curcumin in both in vitro and in vivo experiments. Calix-Cur did not compromise the viability of J774A.1 macrophages and suppressed pro-inflammatory marker expression in J774A.1 macrophages subjected to LPS-induced oxidative stress. Histological and immunohistochemical analyses showed that Calix-Cur reduced signs of inflammation in a rat model of LPS-induced uveitis when topically administrated in the eyes. Overall, the results supported the calix[4]arene nanoassembly as a promising nanocarrier for delivering curcumin to anterior ocular tissues.

Topics: Animals; Calixarenes; Cell Line; Curcumin; Drug Carriers; Inflammation; Macrophages; Ophthalmic Solutions; Phenols; Uveitis

Current approaches to lowering the pH of basic media rely on the addition of a proton source. An alternative approach is described herein that involves the liquid-liquid extraction-based removal of cesium salts, specifically CsOH and Cs

Topics: Binding Sites; Calixarenes; Carbonates; Cesium; Crystallography, X-Ray; Hydrogen-Ion Concentration; Hydroxides; Ions; Magnetic Resonance Spectroscopy; Mass Spectrometry; Molecular Conformation; Phenols

Polyglycosylated calixarenes are efficient and selective multivalent ligands for lectins. However, the chemical decoration of these macrocyclic scaffolds with saccharides of increasing complexity is hampered by the highly complex chemistry of carbohydrates. An alternative to the conventional approach is the enzymatic diversification of simple glycocluster-presented glycans. In this work, we present a highly efficient chemo-enzymatic approach to tetra-N-acetyl-lactosaminylcalix[4]arene via glycan extension catalyzed by a human β-1,4-galactosyltransferase. This demonstrates that calixarenes can be exhaustively processed by enzymatic glycosyl transfer despite the heavy steric crowding, paving the way to the design and achievement of multivalent ligands based on these macrocyclic scaffolds having complex branched glycans.

Topics: Calixarenes; Glycosylation; Humans; Molecular Conformation; N-Acetyllactosamine Synthase; Phenols

The synthesis and characterisation of a partially substituted calix[4]arene, namely, 5,11,17,23-tetra-tert-butyl,25,27-bis[aminoethoxy] 26,28-dihydroxycalix[4]arene are reported. Its interaction with commonly used pharmaceuticals (clofibric acid, diclofenac and aspirin) was investigated by spectroscopic (

Topics: Aspirin; Calixarenes; Calorimetry; Clofibric Acid; Diclofenac; Electric Conductivity; Models, Molecular; Phenols; Proton Magnetic Resonance Spectroscopy; Spectrophotometry, Ultraviolet; Thermodynamics

A new bimodal fluorescent cationic calix[4]arene (L

Topics: Calixarenes; Humans; Luminescent Proteins; Neoplasms; Phenols; Plasmids; Red Fluorescent Protein; Transfection; Water

A chemical sensor based on p-tert butyl calix[4]arene has been synthesized and characterized using an assortment of spectroscopic techniques such as (1)H NMR, (13)C NMR, and elemental analysis. For sensor application, organic nanoparticles (N1) of 1 have been primed by implementing re-precipitation technique, which were further employed for preparing organic-inorganic hybrid (H1) by decorating N1 with gold nanoparticles. Both N1 and H1 were characterized using UV-visible, fluorescence, and DLS studies. Photo-physical changes due to anion binding with H1 were scrutinized using UV-visible absorption spectrometer and found it to promptly and selectively recognize Cl(-) ions in aqueous media. Thus, H1 can be effectively used for recognition of Cl(-) ions in aqueous media over a wide pH range, in samples of real time importance with a detection limit of 2.84×10(-9) M with a linear detection range up to 50 μM.

Topics: Calixarenes; Chemistry Techniques, Analytical; Chlorides; Gold; Metal Nanoparticles; Nanocomposites; Phenols; Water; Water Pollutants, Chemical

In the present study, iron oxide magnetite nanoparticles, prepared through a co-precipitation method, were coated with phosphonic acid or iminodicarboxylic acid derivatives of calix[4]arene to modulate their surfaces with different acidic groups. Candida rugosa lipase was then directly immobilized onto the modified nanoparticles through sol-gel encapsulation. The catalytic activities and enantioselectivities of the two encapsulated lipases in the hydrolysis reaction of (R/S)-naproxen methyl ester and (R/S)-2-phenoxypropionic acid methyl ester were assessed. The results showed that the activity and enantioselectivity of the lipase were improved when the lipase was encapsulated in the presence of calixarene-based additives; the encapsulated lipase with the phosphonic acid derivative of calix[4]arene had an excellent rate of enantioselectivity against the (R/S)-naproxen methyl and (R/S)-2-phenoxypropionic acid methyl esters, with E=350 and 246, respectively, compared to the free enzyme. The encapsulated lipases (Fe-Calix-N(COOH)) and (Fe-Calix-P) showed good loading ability and little loss of enzyme activity, and the stability of the catalyst was very good; they only lost 6-11% of the enzyme's activity after five batches.

Topics: Biocatalysis; Calixarenes; Candida; Carboxylic Acids; Hydrolysis; Lipase; Magnetite Nanoparticles; Molecular Conformation; Phenols; Phosphorous Acids; Stereoisomerism

A phenylenediamine-capped conjugate of calix[4]arene (Lamino ) was synthesized by reducing its precursor, Limino , with sodium borohydride in methanol. The Lamino sample binds to anions due to the more flexible and bent conformation of the capped aminophenolic binding core, compared to the precursor Limino . The Lamino sample showed selectivity towards H2 PO4 (-) by exhibiting a ratiometric increase in emission by about 11-fold with a detection limit of (1.2±0.2) μm ((116±20) ppb) over 15 anions studied, including other phosphates, such as P2 O7 (4-) , adenosine monophosphate (AMP(2-) ), adenosine diphosphate (ADP(2-) ), and adenosine triphosphate (ATP(2-) ). The Lamino sample shows an increase in the absorbance at λ=315 nm in the presence of H2 PO4 (-) , CO3 (2-) , HCO3 (-) , CH3 CO2 (-) , and F(-) . The (1) H NMR spectroscopic titration of Lamino with H2 PO4 (-) , F(-) , and CH3 CO2 (-) showed major changes in the phenylene-capped and salicyl moieties, and thereby, confirming the aminophenolic region as the binding core. However, the binding strength of these anions followed the trend H2 PO4 (-) >F(-) ≫CH3 CO2 (-) >HSO4 (-) . The heat changes observed by isothermal titration calorimetry support this trend. The Lamino sample showed reversible sensing towards H2 PO4 (-) and F(-) in the presence of Mg(2+) and Ca(2+) , respectively. NOESY studies of Lamino , in comparison with its anionic complexes, revealed that major conformational changes occurred in the capping region to facilitate the binding of anion. ESI-MS and the Job's method revealed 1:1 stoichiometry between Lamino and H2 PO4 (-) or F(-) . In the SEM micrographs of Lamino , the spherical particles are converted into spherical aggregates and further form large agglomerates and even branched sheets in the presence of anions, depending upon their binding strength.

Topics: Adenosine Diphosphate; Adenosine Monophosphate; Adenosine Triphosphate; Anions; Borohydrides; Calixarenes; Calorimetry; Magnetic Resonance Spectroscopy; Methanol; Microscopy, Electron, Scanning; Phenols; Phenylenediamines; Phosphates; Spectrometry, Fluorescence; Spectrometry, Mass, Electrospray Ionization

A hydrophobic N-dodecyl-3-(trifluoromethyl)-4-nitrobenzenamine has been synthesized as a suitable NO photodonor and encapsulated in a nanocontainer based on a polycationic calix[4]arene derivative, leading to a supramolecular micellar-like nanoassembly ca. 45 nm in diameter. Visible light excitation of this nanoconstruct triggers NO generation with an efficiency remarkably higher than that observed for the free NO photoreleaser. This amplified NO release results in considerable antibacterial activity against Staphylococcus aureus (ATCC 6538) and Pseudomonas aeruginosa (ATCC 9027) as representative Gram positive and Gram negative bacteria, respectively.

Topics: Anti-Bacterial Agents; Calixarenes; Hydrophobic and Hydrophilic Interactions; Micelles; Nitric Oxide; Nitrobenzenes; Phenols; Photochemical Processes; Pseudomonas aeruginosa; Staphylococcus aureus

Topics: Calixarenes; Carbon-13 Magnetic Resonance Spectroscopy; DNA Topoisomerases, Type I; Humans; Hydrogen-Ion Concentration; Kinetics; Phenols; Phosphorus; Potentiometry; Proton Magnetic Resonance Spectroscopy; Spectrometry, Mass, Electrospray Ionization

Three cone-calix[4]arene-based sensitizers (Calix-1-Calix-3) with multiple donor-π-acceptor (D-π-A) moieties are designed, synthesized, and applied in dye-sensitized solar cells (DSSCs). Their photophysical and electrochemical properties are characterized by measuring UV/Vis absorption and emission spectra, cyclic voltammetry, and density functional theory (DFT) calculations. Calix-3 has excellent thermo- and photostability, as illustrated by thermogravimetric analysis (TGA) and dye-aging tests, respectively. Importantly, a DSSC using the Calix-3 dye displays a conversion efficiency of 5.48 % in under standard AM 1.5 Global solar illumination conditions, much better than corresponding DSSCs that use the rod-shaped dye M-3 with a single D-π-A chain (3.56 %). The dyes offer advantages in terms of higher molar extinction coefficients, longer electron lifetimes, better stability, and stronger binding ability to TiO2 film. This is the first example of calixarene-based sensitizers for efficient dye-sensitized solar cells.

Topics: Calixarenes; Coloring Agents; Electric Power Supplies; Electrochemistry; Models, Molecular; Molecular Conformation; Phenols; Solar Energy

A triazole-linked hydroxyethylimino conjugate of calix[4]arene () and its cadmium complex have been synthesized and characterized, and their structures have been established. In the complex, both the Cd(2+) centers are bound by an N2O4 core, and one of it is a distorted octahedral, whereas the other is a trigonal anti-prism. The fluorescence intensity of the di-nuclear Cd(ii) complex is quenched only in the presence of phosphates and not with other anions studied owing to their binding affinities and the nature of the interaction of the phosphates with Cd(2+). These are evident even from their absorption spectra. Different phosphates exhibit changes in both their fluorescence as well as absorption spectra to varying extents, suggesting their differential interactions. Among the six phosphates, H2PO4(-) has higher fluorescence quenching even at low equivalents of this ion, whereas P2O7(4-) shows only 50% quenching even at 10 equivalents. The fluorescence quenching is considerable even at 20 ppb (0.2 μM) of H2PO4(-), whereas all other phosphates require a concentration of 50-580 ppb to exhibit the same effect on fluorescence spectra. Thus, the interaction of H2PO4(-) is more effective by ∼30 fold as compared to that of P2O7(4-). Fluorescence quenching by phosphate is due to the release of from its original cadmium complex via the formation of a ternary species followed by the capture of Cd(2+) by the phosphate, as delineated based on the combination of spectral techniques, such as absorption, emission, (1)H NMR and ESI MS. The relative interactive abilities of the six phosphates differ from each other. The removal of Cd(2+) is demonstrated to be reversible by the repeated addition of the phosphate followed by Cd(2+). The characteristics of the ternary species formed in each of these six phosphates have been computationally modeled using molecular mechanics. The computational study revealed that the coordination between cadmium and -CH2-CH2-OH breaks and new coordination is established through the phosphate oxygens, and as a result the Cd(2+) center acquires a distorted octahedral geometry. The utility of the complex was demonstrated in HeLa cells.

Topics: Cadmium; Calixarenes; Coordination Complexes; Crystallography, X-Ray; HeLa Cells; Humans; Magnetic Resonance Spectroscopy; Microscopy, Fluorescence; Molecular Conformation; Phenols; Phosphates; Spectrometry, Fluorescence; Spectrometry, Mass, Electrospray Ionization

The macrocycle p-sulfonatocalix[4]arene (CX4) and the fluorescent dye lucigenin (LCG) form a stable host-guest complex, in which the dye fluorescence is quenched. Incubation of live V79 and CHO cells with the CX4/LCG chemosensing ensemble resulted in its spontaneous uptake. Subsequent addition of choline, acetylcholine, or protamine, which have a high affinity for CX4 and are capable of entering cells, resulted in a fluorescence switch-on response. This can be traced to the displacement of LCG from CX4 by the analytes. The results establish the principal functionality of indicator displacement assays with synthetic receptors for the detection of the uptake of bioorganic analytes by live cells.

Topics: Acetylcholine; Acridines; Animals; Calixarenes; Cell Line; CHO Cells; Choline; Cricetinae; Cricetulus; Fluorescent Dyes; Microscopy, Fluorescence; Phenols; Protamines

A facile synthesis of 1,3-diiodocalix[4]arene 6 has been achieved by copper-catalyzed iodination of the 1,3-bistriflate ester 2a of p-tert-butylcalix[4]arene. After protection of the hydroxy groups with iodomethane, diiodide 6 is subjected to halogen–lithium exchange with butyllithium, followed by carbonation with CO2 or formylation with N-formylpiperidine and subsequent deprotection of the hydroxy groups to give novel dicarboxylic acid 11 or dialdehyde 16 in practical yields. The iodo groups of diiodide 6 pass through the calixarene macrocycle; the activation free energy for the conversion of the more stable syn conformer 6syn to the less stable anti conformer 6anti is ΔG(⧧) = 104 kJ mol(–1) at 298 K. Dialdehyde 16 shows fast self-exchange between two equivalent species with a cone conformation, ΔG(⧧), being 63.2 kJ mol(–1). Dicarboxylic acid 11 adopts a cone conformation and forms a dimer in solution as suggested by 1H NMR and X-ray crystallographic analyses. The arrangement of the iodide groups of compound 6 can be fixed predominantly to anti (17a and 17b) by introducing bulky alkyl groups (e.g., propyl groups) onto the hydroxy groups. The stereospecific alkylation of the iodo groups of the resulting di-O-alkylated anti-1,3-diiodides provides access to the anti-1,3-dialkylcalixarenes 19, which is otherwise difficult to obtain.

Topics: Calixarenes; Crystallography, X-Ray; Halogenation; Magnetic Resonance Spectroscopy; Molecular Conformation; Phenols

In this work we have designed a novel system based on carbon dots prepared from chitosan gel capped with β-cyclodextrin and calix[4]arene-25,26,27,28-tetrol for sensitive and selective detection of fluoride ions in aqueous media. Fluorescent carbon dots prepared from chitosan gel when capped with β-cyclodextrin and calix[4]arene-25,26,27,28-tetrol results in quenching of its fluorescence intensity. Introduction of F(-) ions to carbon dots capped with β-cyclodextrin and calix[4]arene-25,26,27,28-tetrol system results in enhancement and restoration of fluorescence intensity leading to detection of F(-) ion. Minimum detection limit was determined to be ∼6.6 μM. The detection is selective as with other halide ions i.e. Cl(-), Br(-) and I(-) and hydroxyl ion (OH(-)), there is observed decrease of fluorescence intensity. A possible mechanism to justify the observation is also discussed in the paper.

Topics: beta-Cyclodextrins; Calixarenes; Carbon; Chitosan; Fatty Acids, Unsaturated; Fluorides; Gels; Limit of Detection; Phenols; Spectrometry, Fluorescence

In this work, three hydrosoluble azocalix[4]arene derivatives, 5-(o-methylphenylazo)-25,26,27-tris(carboxymethoxy)-28-hydroxycalix[4]arene (o-MAC-Calix), 5-(m-methylphenylazo)-25,26,27-tris(carboxymethoxy)-28-hydroxycalix[4]arene (m-MAC-Calix) and 5-(p-methylphenylazo)-25,26,27-tris(carboxymethoxy)-28-hydroxycalix[4]arene (p-MAC-Calix) were synthesized. Their structures were characterized by infrared spectrum (IR), nuclear magnetic resonance spectrum (1H NMR and 13C NMR) and mass spectrum (MS). The interactions between these compounds and bovine serum albumin (BSA) were studied by fluorescence spectroscopy, UV-vis spectrophotometry and circular dichroic spectroscopy. According to experimental results, three azocalix[4]arene derivatives can efficiently bind to BSA molecules and the o-MAC-Calix displays more efficient interactions with BSA molecules than m-MAC-Calix and p-MAC-Calix. Molecular docking showed that the o-MAC-Calix was embedded in the hydrophobic cavity of helical structure of BSA molecular and the tryptophan (Trp) residue of BSA molecular had strong interaction with o-MAC-Calix. The fluorescence quenching of BSA caused by azocalix[4]arene derivatives is attributed to the static quenching process. In addition, the synchronous fluorescence spectroscopy indicates that these azocalix[4]arene derivatives are more accessible to Trp residues of BSA molecules than the tyrosine (Tyr) residues. The circular dichroic spectroscopy further verified the binding of azocalix[4]arene derivatives and BSA.

Topics: Azo Compounds; Calixarenes; Phenols; Serum Albumin, Bovine; Solubility; Spectrum Analysis; Water

Topics: Calixarenes; Coloring Agents; Electric Power Supplies; Phenols; Solar Energy

A novel fluorescently labeled folate conjugate in which four folic acid units are covalently conjugated with a 7-nitro-benzofurazan fluorophore by means of a calix[4]arene platform was synthesized by using a Cu-catalyzed azide-alkyne cycloaddition reaction (click chemistry). The synthesized construct (FA-C4-NBD) was characterized by mass spectrometry, NMR and fluorescence spectroscopy. Confocal fluorescence microscopy experiments were carried out to evaluate the cell penetration ability of FA-C4-NBD on normal and cancer cells. The cellular uptake of FA-C4-NBD proceeds via folate receptor-mediated endocytosis. FA-C4-NBD is internalized into HeLa cancer cells which express high levels of folate receptors, whereas the uptake into fibroblast NIH3T3 cells which have very low expression levels of folate receptors is negligible. The involvement of the folate receptor was corroborated by competition tests with free folic acid. Co-localization analysis with different organelle markers indicated that FA-C4-NBD is not eliminated by recycling towards the outside of the cell, but accumulates intracellularly in the endo-lysosomal system.

Topics: Animals; Calixarenes; Cell Line, Tumor; Drug Design; Fluorescent Dyes; Folic Acid; HeLa Cells; Humans; Mice; Molecular Structure; Neoplasms; NIH 3T3 Cells; Phenols

In this publication, we design and report the synthesis of calix[4]arene-based β-diketo derivatives as novel HIV-1 integrase (IN) inhibitors. The target compounds were obtained using Claisen condensation, and their structures were characterized by NMR and ESI-MS. Preliminary bioassays showed that calix[4]arene-based β-diketo derivatives inhibit strand transfer (ST) with IC50 values between 5.9 and 21.2 µM. Docking studies revealed the predominant binding modes that were distinct from the binding modes of raltegravir, which suggests a novel binding region in the IN active site. Moreover, these compounds are predicted not to interact with some of the key amino acids (GLN148 and ASN155) implicated in viral resistance. Therefore, this series of compounds can further be investigated for a possible chemotype to circumvent resistance to clinical HIV-1 IN inhibitors.

Topics: Binding Sites; Calixarenes; Drug Design; Drug Resistance, Viral; HIV Integrase; HIV Integrase Inhibitors; HIV-1; Ketones; Molecular Docking Simulation; Molecular Structure; Phenols; Protein Binding; Structure-Activity Relationship

In the present study, azocalix[4]arenes were prepared by linking 4-methoxy, 4-methyl, 4-ethyl, 4-chloro, 4-bromo and 4-nitroaniline to calix[4]arene through a diazo-coupling reaction. A new family of azocalix[4]arene tetraester derivatives, (4a-f), have been prepared with the incorporation of ethyl ester units to azocalix[4]arene. Characterization of the synthesized azocalix[4]arenes was carried using elemental analyses, UV-vis, FT-IR and (1)H NMR spectroscopic techniques. The effect of varying pH levels and solvent types on the absorption ability of azocalix[n]arenes substituted with electron-donating and electron-withdrawing groups was examined. Thermal decomposition of azocalix[4]arene derivatives (4a-f) was investigated by means of thermogravimetry (TG), differential thermogravimetry (DTG) and differential thermal analysis (DTA) analyses. In conclusion of the examination of the extraction we found a selectivity characteristic of these compounds toward Ag(+), Hg(+) and Hg(2+) cations.

Topics: Azo Compounds; Calixarenes; Cations; Magnetic Resonance Spectroscopy; Mercury; Models, Molecular; Phenols; Silver; Solvents; Spectroscopy, Fourier Transform Infrared; Thermogravimetry

A calix[4]arene host equipped with two bis-[Zn(salphen)] complexes self-assembles into a capsular complex in the presence of a chiral diamine guest with an unexpected 2:1 ratio between the host and the guest. Effective chirality transfer from the diamine to the calix-salen hybrid host is observed by circular dichroism (CD) spectroscopy, and a high stability constant K2,1 of 1.59×10(11)  M(-2) for the assembled host-guest ensemble has been determined with a substantial cooperativity factor α of 6.4. Density functional calculations are used to investigate the origin of the stability of the host-guest system and the experimental CD spectrum compared with those calculated for both possible diastereoisomers showing that the M,M isomer is the one that is preferentially formed. The current system holds promise for the chirality determination of diamines, as evidenced by the investigated substrate scope and the linear relationship between the ee of the diamine and the amplitude of the observed Cotton effects.

Topics: Calixarenes; Coordination Complexes; Diamines; Models, Molecular; Phenols; Phenylenediamines; Zinc

Gels are interesting soft materials owing to their functional properties leading to potential applications. This paper deals with the synthesis of monocholesteryl derivatized calix[4]arene (G) and its instantaneous gelation at a minimum gelator concentration of 0.6% in 1:1 v/v THF/acetonitrile. The gel shows remarkable thermoreversibility by exhibiting Tgel→sol at ∼48 °C and is demonstrated for several cycles. The gel shows an organized network of nanobundles, while that of the sol shows spherical nanoaggregates in microscopy. A bundle with ∼12 nm diameter possessing hydrophobic pockets in itself is obtained from computationally modeled gel, and hence the gel is suitable for storage and release applications. The guest-entrapped gels exhibit the same microstructures as that observed with simple gels, while fluorescence spectra and molecular mechanics suggests that the drug molecules occupy the hydrophobic pockets. All the entrapped drug molecules are released into water, suggesting a complete recovery of the trapped species. The reusability of the gel for the storage and release of the drug into water is demonstrated for four consecutive cycles, and hence the gel formed from G acts as a functional material that finds application in drug delivery.

Topics: Antineoplastic Agents; Calixarenes; Coloring Agents; Curcumin; Diffusion; Doxorubicin; Gels; Materials Testing; Nanocapsules; Phenols; Temperature; Tocopherols

A cone-calix[4]arene derivative, featuring a guanidinium group and a Cu(II) ion ligated to a 1,4,7-triazacyclononane (TACN) ligand at the 1,3-distal positions of the upper rim, effectively catalyzes the cleavage of 2-hydroxypropyl p-nitrophenyl phosphate (HPNP) and a number of diribonucleoside 3',5'-monophosphates (NpN'). Kinetic and potentiometric measurements support the operation of a general-base/general-acid mechanism and demonstrate that the hydroxo form of the ligated Cu(II) ion is the sole catalytically active species. Rate enhancements relative to the background hydrolysis reaction at 1 mM catalyst concentration are 6 × 10(5)-fold for HPNP and cluster around 10(7)-fold with the most favorable catalyst-NpN' combinations.

Topics: Biochemical Phenomena; Calixarenes; Catalysis; Copper; Guanidine; Heterocyclic Compounds; Organometallic Compounds; Organophosphates; Phenols; Ribonucleases; Ribonucleosides

In order to enhance the cost-effectiveness practicability of enzymes in many industries such as pharmaceutical, food, medical and some other technological processes, there is great need to immobilize them onto a solid supports. In this study, a new and efficient immobilization of α-amylase from Saccharomyces cerevisiae has been developed by using the surface functionalization of calix[4]arene as support. A glutaraldehyde-containing amino group functionalized calix[4]arene was used to immobilize α-amylase covalently. In this procedure, imide bonds are formed between amino groups on the protein and aldehyde groups on the calix[4]arene surface. The surface modified support was characterized using Fourier transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM). The effect of various preparation conditions on the immobilized α-amylase process such as immobilization time, enzyme concentration, temperature and pH were investigated. The influence of pH and temperature on the activity of free and immobilized α-amylase was also studied using starch as substrate. The optimum reaction temperature and pH value for the enzymatic conversion catalyzed by the immobilized α-amylase were 25°C and 7, respectively. Compared to the free enzyme, the immobilized α-amylase retained 85% of its original activity and exhibited significant thermal stability than the free one and excellent durability.

Topics: alpha-Amylases; Calixarenes; Enzymes, Immobilized; Glutaral; Hydrogen-Ion Concentration; Industrial Microbiology; Phenols; Saccharomyces cerevisiae; Spectroscopy, Fourier Transform Infrared; Starch; Surface Properties; Temperature

Since amine compounds have been widespread pollutants in nature and they are extensively used in pharmaceutical industries and dye manufacturing, it is highly desirable to develop simple, effective and naked-eye available analytical methods for such aliphatic diamines determination. Calixarenes as macrocycles have drawn intensive interests for fields such as biomedicine, supramolecular chemistry and smart materials. Here, instead of the normal complicated modification strategy, a facile and efficient method for one-pot synthesis of calix[4]arene crown ether (CCE4) capped gold nanoparticles (AuNPs) is proposed. The as-prepared CCE4-AuNPs are not only high water dispersity and stability even after storage for 3 months, but also capable of host-guest recognition of diamines in aqueous systems. Size-selective encapsulation of amine group between CCE4 and diamines carry out the aggregation of CCE4-AuNPs. The determination of diamines such as hexamethylenediamine or spermine can be realized by the UV-vis absorbance change and visual color difference.

Topics: Calixarenes; Colorimetry; Crown Ethers; Diamines; Gold; Nanoparticles; Phenols; Spermine

A new naphthol-appended calix[4]arene (NOC4) has been synthesized and characterized. NOC4 is clicked onto a microstructured Au surface and exhibits selective macroscopic recognition of metolcarb (MC) via contact angle measurements. The proposed wettability sensing device displays remarkable specificity and is fast and easy to use, which should be suitable for the rapid detection of MC in environmental monitoring.

Topics: Calixarenes; Molecular Structure; Naphthols; Pesticides; Phenols

The thermodynamic property of the host-guest, inclusion complex formed between p-t-butyl calix(4)arene which is a supramolecule, and the antiseizure drug, carbamazepine was studied. p-t-Butyl calix(4)arene has been used as a host molecule and carbamazepine as a guest molecule. Optical absorption spectral studies were carried out to investigate the molecular recognition properties of p-t-butyl calix(4)arene with carbamazepine. The stochiometry of the host-guest complexes formed and the association constant were determined. An interesting 1:2 stochiometric host-guest complex was formed. Job's continuous method of variation and Benesi-Hildebrand expression were used for the determination of binding constant and the stochiometry of the host-guest complex formed. Molecular dimension of the host molecule plays a vital role in the formation of the host-guest stochiometric complexes.

Topics: Anticonvulsants; Calixarenes; Carbamazepine; Phenols; Spectrophotometry, Ultraviolet; Thermodynamics

The size, surface charge, and microstructure of lipoplexes comprising cationic lipids and nucleic acids are important factors for transfection efficiency. As these properties are largely determined by the cationic lipids used, a number of studies on the relationship between cationic lipids and the transfection efficiency have been reported. Among the many cationic lipids, lipids with multivalent cationic head groups are expected to be potent transfection reagents. Here, we prepared calix[4]arene-based lipids with different alkyl chain lengths from C3 to C15 and evaluated the relationship between the alkyl chain length and the transfection efficiency. C6 lipoplexes exhibited the highest transfection efficiency among all lipoplexes. The gene expression with C9 and C12 lipoplexes was slightly lower than that with C6 lipoplexes. C3 lipoplexes hardly induced gene expression, while C15 lipoplexes exhibited no complexation with plasmid DNA. Although all lipoplexes exhibited nearly identical characteristics, they exhibited different behaviours in terms of the interactions between the lipoplexes and anionic micelles comprising phosphatidylserine, a model of endosomal vehicle. After mixing with phosphatidylserine micelles, C6 lipoplexes released the bound plasmid DNA at pH 5 but not at pH 7, indicating that they can interact with the late endosomal membrane after being incorporated into cells. No plasmid DNA was released from C9 or C12 lipoplexes at either pH values. Thus, the alkyl chain length of cationic lipids is related to their interaction with the endosomal compartment and can provide a basis for the design of novel transfection reagents.

Topics: Alkanes; Anions; Calixarenes; DNA; Endosomes; Humans; Hydrogen-Ion Concentration; Indicators and Reagents; Lipids; Liposomes; Phenols; Plasmids; Transfection

A fluorescent calix[4]arene triazole-linked pyrene (CP) was carefully designed and synthesized via click chemistry. The modification of CP with graphene oxide (GO) by a simple non-covalent interaction strategy is presented. Further inspection by electrochemical impedance spectroscopy reveals that the CP-GO could exhibit a very high supramolecular recognition for carbaryl, in particular in serum samples with a nanomolar concentration detection. Additionally, it is easy to directly observe macroscopic recognition by the contact angle, and expand practical applications.

Topics: Calixarenes; Carbaryl; Chemistry Techniques, Analytical; Click Chemistry; Fluorescent Dyes; Graphite; Models, Molecular; Molecular Conformation; Phenols; Pyrenes; Triazoles

This approach disclose the selective fluorogenic ion sensing ability of 5,11,17,23-tetratertbutyl-25,27-bis((2hydroxynaphthylimino)1,2-ethylenediaminecarbonylmethoxy)-26,28 dihydroxycalix[4]arene (C4NSB). Binding property of receptor probed by using selected various cations and anions with conferring of results that demonstrates 'turn-off' fluorescence response and significantly high chromogenic selectivity toward Au(3+) and I(-). Furthermore, selective nature of receptor was investigated in the presence of different co-existing competing ions. The limit of detection (LOD) for Au(3+) and I(-) was determined as 1.5 × 10(-5) and 4.5 × 10(-6) M respectively. Receptor C4NSB form (1:1) stoichiometric complex with both ions and their binding constants were calculated as 8.0 × 10(2) for Au(3+) and 15.6 × 10(2) M(-1) for I(-). Complexes were also characterized through FT-IR spectroscopy.

Topics: Aldehydes; Calixarenes; Chemistry Techniques, Analytical; Fluorescent Dyes; Gold; Iodine; Models, Molecular; Molecular Conformation; Naphthalenes; Phenols; Schiff Bases

A phenylene diimine capped conjugate of 1,3-calix[4]arene (L) was synthesized and characterized, and its Mg(2+) complex has been isolated and characterized. The chemo sensing ensemble of Mg(2+) bound L provides distinguishable features of response toward phosphates, viz., HPO4(2-), P2O7(4-), and AMP(2-) (Set A) and H2PO4(-), ATP(2-), and ADP(2-) (Set B). While the Set A shows the formation of ternary complex, the Set B does not exhibit any intermediate complex, but both show the release of Mg(2+) and L at different equivalents. The structures of {L + Mg(2+)} and its phosphate bound ternary complexes have been established by computational calculations, and the corresponding results agree well with the experimental ones. The microscopy studies show an aggregation-disaggregation phenomenon in the presence of different equivalents of phosphates in both of the sets. Using the fluorescence data, an INHIBIT logic gate has been built.

Topics: Calixarenes; Magnesium; Microscopy; Models, Molecular; Molecular Conformation; Organometallic Compounds; Phenols; Phosphates; Spectrometry, Fluorescence

Post-translational modification of histone tails plays critical roles in gene regulation. Thus, molecules recognizing histone tails and controlling their epigenetic modification are desirable as biochemical tools to elucidate regulatory mechanisms. There are, however, only a few synthetic ligands that bind to histone tails with substantial affinity. We report CA2 and CA3, which exhibited sub-micromolar affinity to histone tails (especially tails with a trimethylated lysine). Multivalent display of trisulfonated calix[4]arene was important for strong binding. CA2 was applicable not only to synthetic tail peptides but also to endogenous histone proteins, and was successfully used to pull-down endogenous histones from nuclear extract. These findings indicate the utility of these supramolecular ligands as biochemical tools for studying chromatin regulator protein and as a targeting motif in ligand-directed catalysis to control epigenetic modifications.

Topics: Amino Acid Sequence; Biotin; Calixarenes; HeLa Cells; Histones; Humans; Kinetics; Ligands; Molecular Sequence Data; Phenols; Protein Binding; Surface Plasmon Resonance

Two new chiral calix[4]arene-salen ligands 1a,b, based on calix[4]arene platforms in 1,3-alternate conformation, have been prepared by a new general synthetic pathway. Their Mn(III) complexes, 3a,b have shown fairly good efficiency in the asymmetric epoxidation of styrene and substituted styrenes, whereas excellent catalytic activity and selectivity were observed with rigid bicyclic alkenes, namely 1,2-dihydro-naphthalene and substituted 2,2'-dimethyl-chromene. The higher catalytic properties of 3a may be ascribed to the more rigid and inherently chiral structure as proved by molecular modelling, NMR spectroscopy and X-ray data of the similarly structured UO2 complexes 2a,b.

Topics: Alkenes; Calixarenes; Catalysis; Coordination Complexes; Epoxy Compounds; Manganese; Molecular Conformation; Phenols; Stereoisomerism; X-Ray Diffraction

A new type of 4-isopropylcalix[4]arene-capped (3-(2-O-β-cyclodextrin)-2-hydroxypropoxy)propylsilyl-appended silica particles (IPC4CD-HPS) has been prepared by treatment of bromoacetate-substituted (3-(2-O-β-cyclodextrin)-2-hydroxypropoxy)propylsilyl-appended silica particles (BACD-HPS) with 4-isopropylcalix[4]arene oxyanions in anhydrous N-methyl-2-pyrrolidone. The bonded silica IPC4CD-HPS has been successfully used as chiral stationary phase (CSP) in high-performance liquid chromatography (HPLC) for the first time. The synthetic stationary phase was characterized by means of elemental analysis and Fourier transform infrared spectroscopy. This new CSP has a chiral selector with two anchored functional moieties: 4-isopropylcalix[4]arene and β-cyclodextrin. The chromatographic performance of IPC4CD-HPS was investigated by separation of positional isomers of several disubstituted benzenes and enantiomers of some chiral drug compounds under reversed-phase conditions. The results showed that IPC4CD-HPS had excellent selectivity for the separation of aromatic positional isomers and enantiomers of chiral compounds due to the cooperative functioning of the anchored 4-isopropylcalix[4]arenes and β-cyclodextrins.

Topics: Benzene; beta-Cyclodextrins; Calixarenes; Chromatography, High Pressure Liquid; Phenols; Silicon Dioxide; Stereoisomerism

The ability of a calix[4]arene derivative (CX-1), bearing four protonated NH3(+) groups located in the upper rim and aliphatic tails in the lower rim, to interact with a 1,2-dioleoyl-sn-glycero-3-phosphocholine (DOPC) model bilayer and promote transmembrane chloride transport was investigated by molecular dynamics (MD) simulations. Unconstrained MD simulations show that the interaction of CX-1 with DOPC occurs via the NH3(+) groups, which are able to establish electrostatic interactions and multiple hydrogen bonds with the DOPC phosphate groups, while the aliphatic tails point towards the water phase (when CX-1 starts from the water phase) or to the membrane (when CX-1 is initially positioned within the bilayer). The interaction does not induce any relevant perturbation on the biophysical properties of the bilayer system (area per lipid, thickness, and hydration) apart from a systematic increase in the order parameter of the C2 carbon atom of the sn-1 lipid tail, meaning that the bilayer conserves its integrity. Since total internalization of CX-1 was not observed in the unconstrained MD time-scale, constant velocity steered molecular dynamics (SMD) simulations were performed in order to simulate the CX-1 permeation across the bilayer. At pulling velocities lower than 0.0075 nmps(-1), chloride transport was observed. The Potential of Mean Force (PMF), calculated with the weighted histogram analysis method, indicates a barrier of ca. 58kJmol(-1) for this mobile carrier to cross the membrane.

Topics: Calixarenes; Cell Membrane; Chlorides; Ion Transport; Lipid Bilayers; Models, Molecular; Molecular Dynamics Simulation; Phenols; Phosphatidylcholines

A series of polycyclic aromatic hydrocarbons (PAHs) of different size and shape has been used to characterize the chromatographic behavior of five calix[4]arene stationary phases in 1,3-alternate conformation synthesized in our laboratory. The selection of linear, four-ring nonlinear, and five-ring PAHs gave data on selectivity changes across range of the calix[4]arene columns. Retention of the 12 aromatic solutes has been evaluated at various methanol contents in the mobile phase (70-100% v/v) and column temperatures (20-45°C). The thermodynamic parameters underlying the retention mechanisms revealed that each of the five calix[4]arene columns exhibited variation in selectivity and retention of PAHs caused by enthalpy and entropy effects. The calixarene stationary phases substituted with electron-withdrawing groups exhibit enhanced selectivity toward PAHs in comparison to the rest of the investigated columns. The observed divergences are due to differences in solute-stationary phase interactions and originate in π-π and π-electron transfer specific to the analytes and the type of calix[4]arene functionalization at the upper rim, as well as steric and sorption phenomena.

Topics: Calixarenes; Chromatography, Liquid; Phenols; Polycyclic Aromatic Hydrocarbons; Silicon Dioxide; Thermodynamics

25,27-Bis{1'-N-(1-pyrenyl)-aminocarbonylmethyl-1H-[1',2',3']tri-azolyl-4'-methoxy}-26,28-dihydroxycalix[4]arene, 4, is synthesized as a fluorescent chemosensor for the selective detection of both anions and ion pairs in MeCN. Sensor 4 uses bis-triazoles as ligands to bind a metal ion, bis-amides and bis-triazoles as the sites to recognize anions, and pyrenes as fluorophores. Among eight anions screened, chemosensor 4 showed a marked fluorescence change toward F(-), H2PO4(-) and AcO(-), but 4 responded to each anion in a distinct way. In the presence of F(-) at low concentrations, the dynamic excimer emission of compound 4 at λ(max) 482 nm was quenched, but an emission at λ(max) 472 nm appeared at large doses of F(-). A control compound 6 showed very similar red shifts in the UV-vis and excitation spectra as 4 did, and its 472 nm emission band grew as the fluoride doses increased. Thus, the growth of the 472 nm emission of 4 and 6 in the presence of excess F(-) may be because strong H-bonding interactions of amido protons with F(-) favoured the formation of pyrene dimers in the ground state with charge transfer characteristics. The addition of H2PO4(-), unlike F(-), to a solution of 4 showed an enhanced monomer emission but a decreased excimer emission (λ(max) 482 nm). Adding AcO(-) to 4 produced a systematic change from a dynamic excimer (λ(max) 482 nm) to λ(max) 472 nm but with very little change in the UV-vis spectrum. Time-resolved fluorescence measurements on compound 6 with F(-) and AcO(-) confirmed that the 472 nm emission band mainly came from static excimers for the former, but was partly from a dynamic excimer for the latter because it contained a growth component in the fluorescence decay traces. Without pre-treatment with an anion, chemosensor 4 showed recognition of only metal ions Cu(2+), Hg(2+) and Cr(3+), but it became sensitive to Ag(+) when it was pretreated with fluoride.

Topics: Acetates; Amides; Calixarenes; Chemistry Techniques, Analytical; Electron Transport; Fluorides; Phenols; Spectrometry, Fluorescence

Adaptation of Ugi-4CR for the narrow-rim modification of calix[4]arene toward the synthesis of a series of tripeptoid and tetrapeptoid calix[4]arenes is described. The metal ion/organic cation binding properties of the newly synthesized peptoid calix[4]arenes were also investigated.

Topics: Aldehydes; Calixarenes; Magnetic Resonance Spectroscopy; Peptoids; Phenols

The silica gel modified with benzothiazole calix[4]arene (APS-L1) via Schiff's base reaction was applied as a sorbent in an online system for preconcentration and determination of silver ion by flame atomic absorption spectrometry (FAAS). APS-L1 was used as an effective sorbent for solid phase extraction (SPE) of silver(I) ion in both batch and column methods. The optimum experimental parameters such as pH, eluent type, sample flow rate, eluent volume and eluent flow rate including the effect of interfering ions were investigated. Silver(I) ion was determined at pH 6-7. The capacity of APS-L1 sorbent was found to be 12.2 mg/g of sorbent. The high affinity was obtained without interference from the interfering ions. The optimum conditions of the online flow injection preconcentration coupled with the FAAS (FI-FAAS system) were evaluated. The sample flow rate was 3.0 mL min(-1) using sample volume of 5-10 mL. Elution was performed with 250 μL of 0.1 mol L(-1) thiosulfate at the flow rate of 1.5 mL min(-1). The analytical characteristics and performance of the FI-FAAS system were studied under optimum conditions using a solution spiked with standard silver(I) ion at 20 and 50 μg L(-1). The detection limit of 0.44 μg L(-1) was obtained. The accuracy of the proposed method was evaluated and percentages of recovery at 20 and 50 μg L(-1) were 100.2 and 99.5%, respectively. The percent relative standard deviations (%RSD) at 20 and 50 μg L(-1) were 6.1 and 3.3%, respectively. The developed method was successfully applied to determine trace silver(I) ion in drinking and tap water samples.

Topics: Benzothiazoles; Calixarenes; Flow Injection Analysis; Hydrogen-Ion Concentration; Ions; Phenols; Silicon Dioxide; Silver; Solid Phase Extraction; Spectrophotometry, Atomic

We report here a supramolecular strategy to directly assemble the small molecular antipsychotic drug chlorpromazine (CPZ) into nanostructures, induced by p-sulfonatocalix[4]arene (SC4A) and p-sulfonatocalix[4]arene tetraheptyl ether (SC4AH), with high drug loading efficiencies of 61% and 46%, respectively. The binary host-guest assembly process was monitored using optical transmittance measurements, and the size and morphology of these two kinds of supra-amphiphilic assemblies were identified using a combination of light scattering and high-resolution transmission electron microscopy, which showed solid spherical micelles. This strategy presents new opportunities for the development of high loading drug-containing carriers with easy processability for drug delivery.

Topics: Antipsychotic Agents; Calixarenes; Chlorpromazine; Drug Carriers; Hydrogen-Ion Concentration; Micelles; Nanostructures; Phenols; Temperature; Water

A photoreversible switch based on a photoresponsive host-guest system consisting of dimethylamino calix[4]arene L and 4-(phenylazo)benzoic acid (O) is reported. The host L exhibited selective binding and release of O on UV and visible irradiation at 450 and 365 nm, respectively. Moreover, the photoresponsive host-guest complex was applied as a photocontrolled wettability switch on a functional micro/nanostructured silicon surface, and is thus promising for applications in sensors and microfluidic devices.

Topics: Azo Compounds; Benzoates; Calixarenes; Click Chemistry; Models, Molecular; Molecular Structure; Phenols; Photochemical Processes; Wettability

The development of antibacterial and antifungal drugs has been the target of several pharmaceutical and chemical industries mainly due to the lack of effective drugs with low or no side effect. In this work, studies were conducted both in vitro and in vivo with 8-oxyquinolinepropoxycalix[4]arene (A) and 5-Cl-8-oxyquinolinepropoxycalix[4]arene (B) ligands, showing fairly good results. Cytotoxicity and fungicidal actions of compounds A and B were determined in Wistar male rats and peritoneal macrophages of mice. A slight change in the total of leukocytes and erythrocytes was observed on the hematologic assays, showing almost no inflammation after using both compounds in Wistar male rats. We have also noted some, but not significant, alteration in liver enzymes representing modest hepatotoxicity. Cytotoxicity of peritoneal macrophages, in the presence of compound A or B, showed 50% of survival of macrophages. On the other hand, macrophages previously infected with Candida albicans and treated with substance A or B exhibited an increased cytokine IL-10 at 24h incubation. By checking the effect of substance A or B on growing C. albicans, the results pointed that these substances revealed antifungal activity against C. albicans, in 24h culture with a reduction of yeast cells.

Topics: Animals; Antifungal Agents; Calixarenes; Candida albicans; Cell Line; Cell Survival; Cytokines; Macrophages; Male; Mice; Mice, Inbred BALB C; Oxyquinoline; Phenols; Rats; Rats, Wistar

In the present paper, a new calix[4]arene derivatized chitosan bonded stationary phase (CCS4) for high performance liquid chromatography (HPLC) was synthesized and characterized. Its chromatographic performance and retention mechanism were evaluated in reversed-phase mode compared with ODS using different solute probes including mono-substituted benzenes, phenols and nucleosides. The results showed that CCS4 stationary phase could provide various interactions with solutes, such as hydrophobic, hydrophilic, π-π, and inclusion interactions. It could perform the mixed-mode separation including RP and HILIC.

Topics: Calixarenes; Chitosan; Chromatography, High Pressure Liquid; Hydrophobic and Hydrophilic Interactions; Organic Chemicals; Phenols; Silica Gel

A phenylene-diimine-capped conjugate of lower rim 1,3-calix[4]arene (L) was synthesized, characterized, and shown to selectively bind to Mg(2+) using its capped arms. This results in a selective recognition of Mg(2+) through eliciting fluorescence enhancement of ∼70 fold with a detection limit of 40 ± 5 ppb. However, in the presence of blood serum, the lowest detection limit is 209 ± 10 ppb (0.2 μM). The binding of Mg(2+) to L is authenticated by absorption and (1)H NMR data. The Job's plot derived on the basis of the absorption data showed 1:1 stoichiometry between the receptor and Mg(2+). The 1:1 species was further confirmed through ESI MS, that is, being supported by the isotope peak pattern authenticating the presence of Mg(2+) in the complex. The L binds Mg(2+) octahedrally using the tetradentate L(2-) and two additional acetic acid moieties by bringing conformational changes as studied on the basis of MM computations. The conformational changes that occur in the capped arms upon Mg(2+) binding were supported experimentally by NOESY. AFM and SEM studies showed that spherical particles of L are modified into flower and chain type aggregates upon complexation with Mg(2+), confirming the supramolecular behavior of the species formed.

Topics: Calixarenes; Imines; Magnesium; Magnetic Resonance Spectroscopy; Phenols; Spectrometry, Fluorescence

For all microhelices on aromatic rings of inherently chiral calix[4]arene, an expression was derived from one approximation and one hypothesis on the basis of the electron-on-a-helix model of Tinoco and Woody as follows: 1/E = μ(H - KΔα2), where μ = 1 for the right-handed microhelix and μ = -1 for the left-handed microhelix; and H and K are constant and greater than zero. The expression correlates microhelical electronic energy (E) with the atom polarizability difference (Δα) on both microhelix ends, which intuitively and clearly shows the impact of helical substituent polarizability on helical electronic energy. The case analysis almost entirely proves that the qualitative analysis of the helical electronic energy of inherently chiral calix[4]arenes with the expression is scientific and can be used to effectively assign their absolute configuration.

Topics: Calixarenes; Electrons; Models, Molecular; Molecular Conformation; Phenols; Stereoisomerism

The supramolecular compound calix[4]arene C-90 (5,11,17,23-tetra(trifluoro)methyl(phenylsulfonylimino)-methylamino-25,26,27,28-tetrapropoxycalix[4]arene) is shown to efficiently inhibit the ATP hydrolase activity of Ca2+,Mg2+-ATPase in the myometrium cell plasma membrane fraction and also in a preparation of the purified enzyme solubilized from this subcellular fraction. The inhibition coefficient I0.5 values were 20.2 ± 0.5 and 58.5 ± 6.4 µM for the membrane fraction and the solubilized enzyme, respectively. The inhibitory effect of calix[4]arene C-90 was selective comparatively to other ATPases localized in the plasma membrane: calix[4]arene C-90 did not influence the activities of Na+,K+-ATPase and "basal" Mg2+-ATPase. The inhibitory effect of calix[4]arene C-90 on the Ca2+,Mg2+-ATPase activity was associated with the cooperative action of four trifluoromethylphenylsulfonylimine (sulfonylamidine) groups oriented similarly on the upper rim of the calix[4]arene macrocycle (the calix[4]arene "bowl"). The experimental findings seem to be of importance for studies, using calix[4]arene C-90, of membrane mechanisms of regulation of calcium homeostasis in smooth muscle cells and also for investigation of the participation of the plasma membrane Ca2+-pump in control of electro- and pharmacomechanical coupling in myocytes.

Topics: Animals; Ca(2+) Mg(2+)-ATPase; Calixarenes; Cell Membrane; Female; Kinetics; Myocytes, Smooth Muscle; Myometrium; Phenols; Protein Binding; Swine

The tremendous therapeutic potential of curcumin as a chemopreventive, antineoplastic and chemosensitizing agent has failed to progress towards clinical development and commercialization due to its unfavorable physicochemical properties, low aqueous solubility, chemical instability, and pharmacokinetics. The present contribution is focused on the feasibility of using PEGylated calixarene, in particular polyoxyethylene-derivatized tert-butylcalix[4]arene, to prepare various platforms for delivery of curcumin such as inclusion complex, supramolecular aggregates, and hybrid liposomal systems. The inclusion complex is characterized by UV-vis and FT-IR spectroscopy as well as thermal gravimetrical analysis and differential scanning calorimetry. At concentrations exceeding the critical micellization concentration of PEGylated calixarene, the tremendous solubility enhancement of curcumin is attributed to additional solubilization and hydrophobic non-covalent interactions of the drug with supramolecular aggregates. A hybrid liposomal system is created via encapsulation of the inclusion complex in dipalmitoylphosphatidylcholine:cholesterol liposomes. Bare and liposomal curcumin:BEC-X inclusion complexes, as well as free curcumin were additionally investigated for cytotoxicity and apoptogenic activity against human tumor cell lines.

Topics: 1,2-Dipalmitoylphosphatidylcholine; Antineoplastic Agents; Apoptosis; Calixarenes; Cell Cycle; Cell Line, Tumor; Cell Survival; Cholesterol; Curcumin; Drug Delivery Systems; Humans; Liposomes; Phenols; Polyethylene Glycols; Solubility

A biomimetic, ion-regulated molecular receptor was synthesized via the Weak-Link Approach (WLA). This structure features both a calix[4]arene moiety which serves as a molecular recognition unit and an activity regulator composed of hemilabile phosphine alkyl thioether ligands (P,S) chelated to a Pt(II) center. The host-guest properties of the ion-regulated receptor were found to be highly dependent upon the coordination of the Pt(II) center, which is controlled through the reversible coordination of small molecule effectors. The environment at the regulatory site dictates the charge and the structural conformation of the entire assembly resulting in three accessible binding configurations: one closed, inactive state and two open, active states. One of the active states, the semiopen state, recognizes a neutral guest molecule, while the other, the fully open state, recognizes a cationic guest molecule. Job plots and (1)H NMR spectroscopy titrations were used to study the formation of these inclusion complexes, the receptor binding modes, and the receptor binding affinities (Ka) in solution. Single crystal X-ray diffraction studies provided insight into the solid-state structures of the receptor when complexed with each guest molecule. The dipole moments and electrostatic potential maps of the structures were generated via DFT calculations at the B97D/LANL2DZ level of theory. Finally, we describe the reversible capture and release of guests by switching the receptor between the closed and semiopen configurations via elemental anion and small molecule effectors.

Topics: Allosteric Regulation; Allosteric Site; Biomimetics; Calixarenes; Coordination Complexes; Ligands; Models, Molecular; Phenols; Platinum; Thermodynamics

Improved methods for quickly identifying neutral organic compounds and differentiation of analytes with similar chemical structures are widely needed. We report a new approach to effectively "fingerprint" neutral organic molecules by using (19)F NMR and molecular containers. The encapsulation of analytes induces characteristic up- or downfield shifts of (19)F resonances that can be used as multidimensional parameters to fingerprint each analyte. The strategy can be achieved either with an array of fluorinated receptors or by incorporating multiple nonequivalent fluorine atoms in a single receptor. Spatial proximity of the analyte to the (19)F is important to induce the most pronounced NMR shifts and is crucial in the differentiation of analytes with similar structures. This new scheme allows for the precise and simultaneous identification of multiple analytes in a complex mixture.

Topics: Calixarenes; Coordination Complexes; Fluorine; Magnetic Resonance Spectroscopy; Models, Molecular; Organic Chemicals; Phenols; Tungsten

A crystal structure of lysozyme in complex with p-sulfonato-calix[4]arene (sclx4) reveals a linear assembly of protein tetramers glued together by protein-calixarene interactions. One interaction involves encapsulation of the highly exposed C-terminal Arg128. The other involves an intricate protein-bound complex of sclx4, Mg(2+) and a fragment of polyethylene glycol.

Topics: Binding Sites; Calixarenes; Crystallography, X-Ray; Molecular Dynamics Simulation; Muramidase; Phenols; Polyethylene Glycols; Protein Binding; Protein Structure, Quaternary; Sulfonic Acids

A novel photoinduced electron transfer (PET) based substituted calix[4]arene fluoroionophore has been used for the selective recognition of tryptophan (L-Trp) and histidine (L-His) by emission spectroscopy. The detection limit of the synthesized receptor was found to be 0.00826 nM for L-Trp and 0.00158 nM for L-His. Moreover, this probe has been applied for the recognition of L-Trp and L-His from blood serum.

Topics: Biosensing Techniques; Calixarenes; Fluorescent Dyes; Histidine; Phenols; Protons; Spectrometry, Fluorescence; Tryptophan

Notwithstanding its small dimensions, the narrow cavity of p-tert-butylcalix[4]arene macrocycle is still able to host alkylammonium guests in the presence of the tetrakis[3,5-bis(trifluoromethyl)phenyl]borate (TFPB(-)) weakly coordinating (or "superweak") anion. As an artificial analogue of biological receptors, cone-shaped calix[4]arene 1d is able to recognize a n-BuNH3(+) guest mainly through a 4-fold cation-π interaction aided by a weak H-bonding interaction. This recognition motif can be used to assembly a 2:1 capsular architecture with a linear diammonium axle.

Topics: Anions; Borates; Calixarenes; Hydrocarbons, Fluorinated; Hydrogen Bonding; Molecular Structure; Phenols; Tetraethylammonium

The synthesis and characterization of a triazole linked quinoline appended calix[4]arene conjugate, L, and its fluorescence turn on receptor property for Fe(3+) have been demonstrated. The selective and sensitive discrimination of Fe(3+) has been shown using fluorescence and absorption titration experiments. The Fe(3+) binding to L has been further shown by ITC and ESI MS. The mode of binding of Fe(3+) by calix[4]arene conjugate has been shown by absorption, (1)H NMR and visual color change and the species were modeled based on DFT computations. The {L + Fe(3+)} has been shown to label cells with fluorescence imaging. Moreover the utility of this conjugate has been demonstrated by the combination logic gate system.

Topics: Calixarenes; Cell Line; Fluorescence; Fluorescent Dyes; Humans; Iron; Microscopy, Fluorescence; Models, Molecular; Phenols; Quantum Theory; Quinolines; Spectrometry, Mass, Electrospray Ionization

A readily available chromionophore 5,11,17,23-tetra-tert-butyl-25,27-bis(hydrazidecarbonylmethoxy)-26,28-dihydroxycalix[4]arene (HCC4) was employed as a chromogenic sensing probe selective for Pb(II) and Cr2O7(2-) ions among a series of various ions such as Li(I), Na(I), K(I), Rb(I), Ba(II), Sr(II), Al(III), Cd(II), Co(II), Cu(II), Hg(II), Ni(II), Pb(II) and Zn(II) as well as Cr2O7(2-), CH3CO2(-), Br(-), Cl(-), F(-), I(-), ClO4(-) and NO3(-) that have been examined by UV-visible and fluorescence spectroscopic techniques. The HCC4 in DCM-MeCN system forms 2:1 (ligand-metal) complex with Pb(II). It also shows 2:1 stoichiometry with Cr2O7(2-). The complexation phenomenon has been confirmed by FTIR spectroscopy that favors the selective nature of HCC4 with Pb(II) and Cr2O7(2-). Thermal gravimetric analysis (TGA) also supports its utility in drastic conditions.

Topics: Calixarenes; Chemistry Techniques, Analytical; Chromates; Color; Hydrazines; Lead; Liquid-Liquid Extraction; Phenols; Solvents; Spectroscopy, Fourier Transform Infrared

A biscalix[4]arene ( capable of spontaneous self-assembly into nanoparticles and microspheres in CH3CN was serendipitously observed, and it eventually formed stable blue-light emitting supramolecular organogels.

Topics: Acetonitriles; Calixarenes; Gels; Microspheres; Nanospheres; Phenols; Spectrophotometry; Temperature

We developed a new, advanced, simple and non enzymatic approach for the colorimetric detection of glucose based on calix[4]arene/phenyl boronic acid (CX-PBA)functionalized gold nanoparticles (AuNPs). This molecular receptor proficiently and selectively recognizes glucose due to its ability to reversibly bind diol-containing compounds. The assembly was characterized by transmission electron micrograph (TEM), dynamic light scattering (DLS), UV-Vis, FT-IR, ESI-MS and (1)H NMR spectrometry, which demonstrates the binding affinity for glucose via a boronic acid-diol interaction. The linear range for glucose was found to be 5-100 nM with phosphate buffer pH 10, with a lower detection limit of 4.3 nM. Interference by other saccharides was negligible. The biosensor has been successfully applied to estimate the glucose in human blood serum samples and the results compared well to an automatic analyzer. With the advantages of high sensitivity, selectivity and low sample volume, this method is potentially suitable for the on-site monitoring of glucose.

Topics: Biosensing Techniques; Blood Glucose; Boronic Acids; Calixarenes; Colorimetry; Gold; Humans; Limit of Detection; Metal Nanoparticles; Phenols; Serum

A novel PET with ICT based substituted calix[4]arene fluroionophore was synthesized and used for detection of Cu(2+) and F(-) by emission spectra. The detection limit of the synthesized receptor was found to be 4.16 nM for Cu(2+) and 2.15 nM for F(-). Moreover, this probe has been applied for recognition of Cu(2+) in blood serum and F(-) from waste water.

Topics: Anions; Calixarenes; Cations, Divalent; Copper; Fluorescent Dyes; Fluorine; Humans; Industrial Waste; Phenols; Quinolines; Spectrometry, Fluorescence; Wastewater; Water Pollutants, Chemical

Cell-penetrating peptides are widely used as molecular transporters for the internalization inside cells of various cargo, including proteins and nucleic acids. A special role is played by arginine-rich peptides and oligoarginines covalently linked or simply mixed with the cargo. Here we report cell-penetrating agents in which arginine units are clustered on a macrocyclic scaffold. Instead of using long peptides, four single arginine units were covalently attached to either the upper or lower rim of a calix[4]arene, kept in the cone conformation building a 'parallel' cyclic array. These new macrocyclic carriers show high efficiency in DNA delivery and transfection in a variety of cell lines.

Topics: Animals; Arginine; Calixarenes; DNA; Humans; Macrocyclic Compounds; Phenols; Transfection

Four calix[4]arene derivatives containing various donor atoms and different topology (L1-L4) have been synthesized and used as neutral ionophores to fabricate silver ion selective electrodes (Ag-ISEs) which were characterized in terms of their potentiometric selectivities and complex formation constants. The ionophore L2 having two nitrogen and two sulfur donors showed stronger interactions with Ag(+) and the highest selectivity coefficient towards Ag(+). The best membrane electrode was prepared from L2 and used to fabricate silver ion selective microelectrodes (Ag-ISμEs) which could detect silver ions in 1000 μL samples with detection limit around 1 μM using sodium ion microelectrodes as a pseudo reference electrode. Such potentiometric measurement was then applied to detect DNA hybridization on a gold substrate, employing immobilized lipoic acid-modified pyrrolidinyl PNA (Lip-acpcPNA) as a probe. The hybridization between the neutral Lip-acpcPNA probe and DNA target led to a negatively charged surface that could bind positively charged silver nanoparticles (AgNPs(+)) via electrostatic interactions. The hybridization signal was observed by dissolution of the electrostatically adsorbed AgNPs(+) with hydrogen peroxide. Excellent discrimination of complementary from single mismatched and non-complementary DNA targets was achieved under non-stringent conditions. The detection limit of DNA was 0.2 μM in 1000 μL samples.

Topics: Base Sequence; Calixarenes; DNA; Electrodes; Membranes, Artificial; Microscopy, Electron, Transmission; Nucleic Acid Hybridization; Phenols; Polymers; Silver

Four upper rim bis-monopyrrolotetrathiafulvalene-calix[4]arene conjugates 2a,b and 3a,b have been efficiently synthesized using a modular construction approach. The new compounds feature a molecular tweezer architecture with a quasi-parallel arrangement of redox-active tetrathiafulvalene (TTF) arms, which serve as the guest binding centers. Complexation studies using UV/vis binding titrations revealed a high affinity of the calixarene-TTF receptors for planar electron-deficient guests, leading to formation of deeply colored charge-transfer complexes in solution. The binding efficiency of the receptors depends on the flexibility of the calixarene scaffolds and the electronic nature of the TTF arms: the highest binding efficiency is shown by receptor 2b, featuring a highly preorganized molecular structure and an electron-rich TTF moiety.

Topics: Calixarenes; Electrons; Heterocyclic Compounds; Models, Molecular; Molecular Structure; Phenols

Four Ag(I) ions are linked by four 5-phenyl-1H-tetrazole (Hptz) units to form a molecular crown [Ag4(ptz)4] as a structural analogue of calix[4]arene, which are further supported by Keggin anions to build a 2D layer containing two kinds of cycles, [Ag8(ptz)4(HPW(V)2W(VI)10O40)]·2H2O (1).

Topics: Anions; Calixarenes; Models, Molecular; Molecular Structure; Organometallic Compounds; Phenols; Silver

The two t-butylcalix[4]arene attached ruthenium(II)-bipyridine complexes (Rubc2 and Rubc3) has been synthesized and the anion recognition studies have been carried out using emission techniques. The binding of anions, which are sensed by the complexes, are studied by UV-visible and emission techniques. The complex Rubc2 recognizes the Cl(-), H2PO4 (-) and AcO(-) anions. The complex Rubc3 recognizes the Br(-) and AcO(-) anions. The AcO(-) quenches the emission intensity of both two complexes but the other anion increases the emission intensity of the complexes. The excited state lifetime and transient absorption studies were carried out the AcO(-) facilitates non radiative pathway. The other anions stabilize the excited state and facilitate the radiative pathway.

Topics: 2,2'-Dipyridyl; Anions; Calixarenes; Luminescent Measurements; Molecular Structure; Optical Phenomena; Organometallic Compounds; Phenols; Ruthenium; Spectrophotometry, Ultraviolet

A novel colorimetric and fluorometric calix[4]arene probe (CTP) bearing triphenylamine units was synthesized in good yield and characterized by combination of (1)H, (13)C, APT, COSY, FTIR, HRMS, and UV-vis spectral data. Ion-binding studies of CTP were investigated in acetonitrile with a wide range of cations and anions and the recognition process was monitored by luminescence, UV-vis and (1)H NMR spectral changes. CTP exhibited naked eye detection for Hg(2+) ion. Also it showed a significant fluorescence quenching towards F(-) ion.

Topics: Amines; Calixarenes; Cations, Divalent; Colorimetry; Fluorescent Dyes; Luminescent Measurements; Magnetic Resonance Spectroscopy; Mercury; Models, Molecular; Phenols; Spectrophotometry, Ultraviolet

The synthesis, characterization and inclusion in liposomes of a glucosylated bolaamphiphile built on a calix[4]arene scaffold are described. The new glucocalixarene bolaamphiphile destabilizes bilayers of saturated lipids whereas it rigidifies those of unsaturated lipids, thus reducing leakage of calcein from the liposome internal aqueous compartment. Moreover, from fluorescence and turbidimetry experiments it was found that the glucose units of bolaamphiphile 1 functionalised liposomes allow a specific multivalent interaction with the tetrameric glucose binding protein Concanavalin A. These results therefore represent a novel strategy to functionalise liposomes with saccharides, exploiting multivalent glycosylated ligands to be used in the preparation of drug delivery systems potentially able to target specific lectins.

Topics: Calixarenes; Concanavalin A; Drug Delivery Systems; Furans; Glucose; Lectins; Lipid Bilayers; Liposomes; Models, Molecular; Molecular Structure; Phenols; Pyridones

The article describes preparation of new calixarene biopolymers consisting of the immobilization of convenience calixarene derivative onto cellulose and chitosan biopolymers, and the encapsulation of these calixarene biopolymers with Candida rugosa lipase within a chemical inert sol-gel supported by polycondensation with tetraethoxysilane and octyltriethoxysilane. The catalytic properties of immobilized lipase were evaluated into model reactions employing the hydrolysis of p-nitrophenylpalmitate and the enantioselective hydrolysis of naproxen methyl esters from racemic prodrugs in aqueous buffer solution/isooctane reaction system. The resolution studies using sol-gel support have observed more improvement in the enantioselectivity of naproxen E = 300 with Cel-Calix-E than with encapsulated lipase without calixarene-based materials. Furthermore, the encapsulated lipase (Cel-Calix-E) was still retained about 39 % of their conversion ratios after the fifth reuse in the enantioselective reaction.

Topics: Biopolymers; Calixarenes; Catalysis; Enzyme Activation; Enzyme Stability; Enzymes, Immobilized; Fungal Proteins; Gels; Lipase; Phase Transition; Phenols

Topics: Calixarenes; Electric Power Supplies; Electrodes; Electrolytes; Gels; Ions; Lithium; Molecular Structure; Particle Size; Phenols; Polymers; Quinones; Surface Properties

In this paper, the interaction of safranine T (ST) and calix[4]arene (4,10,16,22-tetramethoxylresorcinarene carboxylic acid derivatives (TRCA)) was investigated with fluorescence spectroscopy. The results was shown that the fluorescence intensity of TRCA could be quenched by ST, and the fluorescence quenching (ΔF=FTRCA-FST-TRCA) was sensitised in cetyltrimethyl ammonium bromide (CTAB). Under the optimal conditions, the linear range of calibration curve for the determination of ST was 0.10-4.00 μg/mL. The detection limit and RSD was 0.034 μg/mL, 2.30% (n=3). The quantum yield (Yu) of ST was approximately 2.0 times higher in the presence of CTAB than that in the absence of CTAB. The method has been applied for the determination of ST in food samples with satisfactory results.

Topics: Calixarenes; Cetrimonium; Cetrimonium Compounds; Fluorescence; Food Analysis; Limit of Detection; Phenazines; Phenols; Spectrometry, Fluorescence

We investigate the synthesis of accessible calix[4]arene-bound gold clusters consisting of open "coordinatively unsaturated" active sites, using a comparative approach that relies on calix[4]arene ligands with various upper- and lower-rim substituents. In contrast with a reported Au(I)-tert-butyl-calixarene phosphine complex, which exhibits a single cone conformer in solution, the H upper-rim analog exhibits multiple conformers in solution. This contrasts with observations of the tert-butyl upper-rim analog, which exhibits a single cone conformer in solution under similar conditions. In the solid state, as determined by single-crystal X-ray diffraction, both H and tert-butyl upper-rim analogs exhibit exclusively cone conformer. A detailed structural analysis of these two solid-state structures highlights a CH-π interaction involving a methoxy lower-rim substituent and phenyl substituent on P as the key feature that enforces a tight configuration of Au(I) atoms on the same side of the calix[4]arene lower-rim plane. We hypothesize that such a configuration promotes chelation of the ligand to a gold surface and facilitates the synthesis of small Au11-sized clusters after reduction of both complexes. The new cluster, like the one reported with the tert-butyl analog, has an extraordinary 25% of surface atoms that are open and accessible to a 2-NT (2-naphthalenethiol) probe in solution. We also investigated the effect of calix[4]arene lower-rim substituents that coordinate to the metal, by using N-heterocyclic carbene (NHC) functional groups rather than phosphines. Four small (<1.6 nm diameter) calix[4]arene NHC-bound gold clusters were synthesized, including three using novel calix[4]arene NHC ligands. The smallest calix[4]arene NHC-bound Au cluster consisted of a 1.2 nm gold core, and its number density of accessible and open surface sites was measured. This required development of a new titration method for open sites on gold clusters, using a SAMSA fluorescein dye molecule, which excites and emits at lower energy relative to the previously used 2-NT probe. The number density of open sites on the new calix[4]arene NHC-bound gold cluster measured by the SAMSA fluorescein probe strongly supports the generality of a mechanical model of accessibility, which does not depend on the functional group involved in binding to the gold surface and rather depends on the relative radii of curvature of bound ligands and the gold cluster core.

Topics: Calixarenes; Gold; Heterocyclic Compounds; Ligands; Methane; Models, Molecular; Molecular Structure; Organogold Compounds; Phenols; Phosphines

Amphiphilic calix[4]arenes were designed as phospholipid mimics by incorporating PO3H2 or NMe3(+) head groups. Using PC12 cells and three stressors (H2O2, menadione and glutamate), we established safe calix[4]arene levels that are able not only to deliver antioxidant payloads of curcumin, but intriguingly also have inherent antioxidant properties. The calix[4]arenes appear to be potent synthetic antioxidants that could be used as nano-carriers for drug delivery.

Topics: Animals; Antioxidants; Calixarenes; Drug Delivery Systems; Glutamic Acid; Hydrogen Peroxide; Micelles; Molecular Structure; PC12 Cells; Phenols; Phospholipids; Rats; Reactive Oxygen Species; Surface-Active Agents; Vitamin K 3

Mesoporous silica nanoparticles (MSNs) have been surface-functionalized with choline moieties encircled by sulfonatocalix[4]arenes. Two enzyme cleavable sites are incorporated in the stalks for specific enzymes to regulate the release of loaded cargos from MSNs. These gated materials show a clear enzymatic response and proven orthogonality.

Topics: Biocompatible Materials; Calixarenes; Choline; Enzymes; Esterases; Hydrogen-Ion Concentration; Nanoparticles; Phenols; Porosity; Rhodamines; Rotaxanes; Silicon Dioxide; Sulfonic Acids; Surface Properties

Сalix[4]arenes bearing methylenebisphosphonic or hydroxymethylenebisphosphonic acid fragments at the wide rim of the macrocycle were studied as inhibitors of PTP1B. Some of the inhibitors showed IC50 values in the micromolar range and good selectivity in comparison with other protein tyrosine phosphatases such as TC-PTP, PTPβ, LAR, and CD45. Kinetic studies indicated that the calix[4]arene derivatives influence PTP1B activity as slow-binding inhibitors. Based on molecular docking results, the binding modes of the macrocyclic bisphosphonates in the active centre of PTP1B are discussed.

Topics: Binding Sites; Calixarenes; Diphosphonates; Enzyme Inhibitors; Humans; Kinetics; Molecular Docking Simulation; Phenols; Protein Binding; Protein Structure, Tertiary; Protein Tyrosine Phosphatase, Non-Receptor Type 1

Post-translational modifications act as 'on' or 'off' switches causing downstream changes in gene transcription. Modifications such as trimethylation of lysine 27 on histone H3 (H3K27me3) cause repression of transcription and stable gene silencing, and its presence is associated with aggressive cancers of many types. We report here macrocyclic host-type compounds that can bind H3K27me3 preferentially over unmethylated H3K27, and characterize their binding affinities and selectivities using a convenient dye-displacement method. We also show that they can disrupt the protein-protein interaction of H3K27me3 with the chromobox homolog 7 (CBX7), a methyllysine reader protein, using fluorescence polarization. These results show that sub-micromolar potencies are achievable with this family of host compounds, and suggest the possibility of their use as new tools to induce the disruption of methyllysine-mediated protein-protein interactions and to report on lysine methylation in vitro.

Topics: Calixarenes; Fluorescence Polarization; Histones; Humans; Kinetics; Methylation; Phenols; Polycomb Repressive Complex 1; Protein Interaction Domains and Motifs; Protein Processing, Post-Translational; Receptors, Artificial

A novel calix[4]arene amphiphilic molecule, denoted by CCaL3, was synthesized and found to form a spherical micelle consisting of 12 molecules at low pH in aqueous solution. Furthermore, uniform Au nanoparticles with 2.0 nm in diameter were synthesized in aqueous solution on the template consisting of the four cysteines of the upper rim of CCaL3. Asymmetric field flow fractionation coupled with light scattering showed that there was no dispersity in the CCaL3 micellar aggregation number. When AuCl4(-) ions were added into the CCaL3 micelle solution, induced circular dichroism (ICD) appeared, indicating appearance of the structural chirality of the CCaL3/AuCl4(-) complex. A combination of electron microscopy and small-angle X-ray scattering showed that helically coiled bilayer sheets were formed upon addition of AuCl4(-). Subsequent reduction with the amine of cysteine moieties led to uniform Au nanoparticles formation with 2.0 nm in diameter on the micellar plate surface. The nanoparticle size was almost equal to the size of cavity constructed by the four cysteines on the calix[4]arene upper rim, indicating that the growth of Au nanoparticles was spatially controlled by the host-guest interaction between the cysteines and Au.

Topics: Calixarenes; Cysteine; Gold; Hydrophobic and Hydrophilic Interactions; Metal Nanoparticles; Micelles; Models, Molecular; Molecular Conformation; Phenols

Glass-transition behaviors concerning the quadruple proton/deuteron rearrangements in the crystalline p-tert-butylcalix[4]arene-toluene (BC4A·T) host-guest compound were studied by adiabatic calorimetry. The glass-transition temperatures (Tg's) of the hydrated BC4A·T-h and deuterated BC4A·T-d were found to be around 90 and 181 K, respectively. The difference of 90 K is too big to be recognized as the ordinary isotope effect, which is about 5 K in classical thermal activation processes. The temperature interval over which the enthalpy relaxation effect was observed was beyond 50 K, being too wide, in BC4A·T-h, while it was 20-30 K in BC4A·T-d; the latter is the one ordinarily observed in the classical processes. The associated equilibration rate in BC4A·T-h was evaluated from the enthalpy relaxation curve observed at 62 K to evidence the non-Arrhenius nature of the temperature dependence. The relaxation effect was detected even at 20 K. These are quite the same behaviors as observed in calix[4]arene, and the quantum tunneling rate in the quadruple proton rearrangement was concluded to be only a little affected by the substitution of the tert-butyl group at the para-position of each phenol moiety.

Topics: Calixarenes; Phenols; Protons; Quantum Theory; Thermodynamics; Toluene; Transition Temperature

The recognition of the mercury(II) ion (Hg(2+)) is essential because of its extreme toxicity in the environment and food. Hence we reported a novel cysteine (Cys) complex of piperidine-calix[4]arene (L) as a convenient and effective dual-signal responsive switch for Hg(2+). This switch system exhibited excellent selectivity toward Hg(2+) by fluorescence (FL), (1)H NMR spectroscopy and the atomic force microscopy (AFM). More importantly, the Hg(2+)-responsive switch had an important and potential application by water contact angle (CA) on a functional micro-nano silicon surface, including intelligent microfluidic and laboratory-on-chip devices, controllable drug delivery, and self-cleaning surfaces.

Topics: Calixarenes; Click Chemistry; Cysteine; Fluorescence; Magnetic Resonance Spectroscopy; Mercury; Models, Molecular; Molecular Structure; Particle Size; Phenols; Piperidines; Protons; Silicon; Surface Properties; Wettability

A new benzimidazole-functionalized calix[4]arene receptor (R) was synthesized and characterized. The receptor R shows better selectivity toward trinitrotoluene (TNT) compared to the other nitro explosives in solution, which also retains its effectiveness for solid-phase detection. The chemical interactions of the molecule with different nitro explosive analytes were studied by fluorescence spectroscopy and by a molecular dynamics approach. The molecular dynamics studies show a 1:3 complex between R and TNT, and hence high sensitivity was imparted by fluorescence studies. The detection of explosive vapors in ambient conditions was tested by using a sensitive coating layer of R on an SU-8/CB-based piezoresistive cantilever surface. The developed device showed large sensitivity toward TNT compared to cyclotrimethylenetrinitramine (RDX) and pentaerythritol tetranitrate (PETN) in the solid state at their respective vapor pressures at room temperature. The detection sensitivity of the device was estimated to be 35 mV for TNT at ambient conditions. Moreover, the sensor does not show a response when exposed to humidity. These results demonstrate that R can be used as one of the coating materials for a cantilever for the detection of TNT using piezoresistivity measurement. R can also detect the explosives in solution with high sensitivity and selectivity by fluorescence spectroscopy.

Topics: Benzimidazoles; Calixarenes; Epoxy Compounds; Explosive Agents; Molecular Dynamics Simulation; Nanostructures; Phenols; Polymers; Spectrometry, Fluorescence; Surface Properties; Temperature; Trinitrotoluene

Topics: Calixarenes; Capsules; Delayed-Action Preparations; Dimerization; Drug Carriers; Drug Design; Drug Stability; Models, Molecular; Molecular Conformation; Phenols

The structures of three novel compounds prepared from the reaction of the lower-rim 1,3-diacid calix[4]arene (LH(2)) with lithium carbonate (1), t-butyl-lithium (2) and zinc acetate (3) are reported.

Topics: Calixarenes; Crystallography, X-Ray; Hydrogen Bonding; Lithium Carbonate; Molecular Conformation; Organometallic Compounds; Phenols; Zinc Acetate

A piperidine-modified calix[4]arene derivative was synthesized and its structure was confirmed with X-ray diffraction data. UV-visible spectroscopy was used to study its molecular recognition of rare earth ions. The results revealed the calix[4]arene derivative could separate tight metal picrate ion pairs by complexation with the rare earth metal ions in tetrahydrofuran. Resolution of the UV-visible spectra with chemometric methods revealed that the derivative and the rare earth ions Eu(3+), Dy(3+), and Tb(3+) formed ML(2) complexes with stability constants of 10(8.26), 10(8.29), and 10(7.41) respectively.

Topics: Calixarenes; Coordination Complexes; Crystallography, X-Ray; Furans; Metals, Rare Earth; Models, Molecular; Phenols; Piperidines; Spectrophotometry, Ultraviolet

The article depicts a detailed study regarding copper selective chemosensing and complexation nature of 5,11,17,23-tetrakis[(N,N-diphenylamino)methyl]-25,26,27,28-tetrahydroxycalix[4]arene (PAC4). Its photophysical characteristics in various solvents of different polarities along with the influence of acid and base on its spectral properties in these solvents are also discussed. The complexation affinity of PAC4 with regard to its latent applications as Cu(II) selective colorimetric and fluorescent sensor among the selected series of various cations such as Li(I), Na(I), K(I), Rb(I), Ba(II), Sr(II), Al(III), Fe(III), Cd(II), Co(II), Hg(II), Mn(II), Ni(II), Pb(II) and Zn(II) was examined by UV-visible and fluorescence emission spectroscopy in dichloromethane:acetonitrile (DCM:MeCN) solvent system. In addition, the process of complexation has been investigated through Job's plot and it has been observed that the complex between PAC4 and Cu(II) is formed in 1:1 stoichiometric ratio. The complex formation between PAC4 and Cu(II) has also been confirmed by FT-IR spectroscopy and thermal gravimetric analysis (TGA).

Topics: Calixarenes; Colorimetry; Coordination Complexes; Copper; Phenols; Sensitivity and Specificity; Spectrometry, Fluorescence; Spectrophotometry, Ultraviolet

In this study, BODIPY-appended calix[4]arene was chosen as a fluorescent probe for intracellular pH. The compound with cell permeability can monitor the minor pH change near neutrality inside the cell and is the first BODIPY-derived probe reported for cytosolic pH. Owing to a high level of cell retention and minor cytotoxicity of the probe, stable fluorescence is provided in the cells for 24h, facilitating the precise observation of intracellular pH. A model of cell apoptosis was designed by exposure of the cells to a low concentration of hydrogen peroxide. An increase in the fluorescence of the cells confirmed that BODIPY-appended calix[4]arene sensed the fluctuation of the cellular pH during early cell apoptosis. The developed fluorescent pH probe will be useful for the study of cell apoptosis.

Topics: Apoptosis; Boron Compounds; Calixarenes; Fluorescent Dyes; HeLa Cells; Humans; Hydrogen Peroxide; Hydrogen-Ion Concentration; Microscopy, Fluorescence; Phenols

An approach for the control and understanding of supported molecular catalysts is demonstrated with the design and synthesis of open and closed variants of a grafted Lewis acid active site, consisting of Al(III)-calix[4]arene complexes on the surface of silica. The calixarene acts as a molecular template that enforces open and closed resting-state coordination geometries surrounding the metal active sites, due to its lower-rim substituents as well as site isolation by virtue of its steric bulk. These sites are characterized and used to elucidate mechanistic details and connectivity requirements for reactions involving hydride and oxo transfer. The consequence of controlling open versus closed configurations of the grafted Lewis acid site is demonstrated by the complete lack of observed activity of the closed site for Meerwein-Ponndorf-Verley (MPV) reduction; whereas, the open variant of this catalyst has an MPV reduction activity that is virtually identical to previously reported soluble molecular Al(III)-calix[4]arene catalysts. In contrast, for olefin epoxidation using tert-butyl-hydroperoxide as oxidant, the open and closed catalysts exhibit similar activity. This observation suggests that for olefin epoxidation catalysis using Lewis acids as catalyst and organic hydroperoxide as oxidant, covalent binding of the hydroperoxide is not required, and instead dative coordination to the Lewis acid center is sufficient for catalytic oxo transfer. This latter result is supported by density functional theory calculations of the transition state for olefin epoxidation catalysis, using molecular analogs of the open and closed catalysts.

Topics: Alkenes; Aluminum Compounds; Calixarenes; Catalysis; Catalytic Domain; Lewis Acids; Magnetic Resonance Spectroscopy; Models, Molecular; Molecular Structure; Oxidation-Reduction; Phenols; Spectrometry, Mass, Electrospray Ionization

Diglycolamide-functionalized calix[4]arenes (C4DGAs) with varying structural modifications were evaluated for actinide complexation from their extraction behavior toward actinide ions such as UO2(2+), Pu(4+), PuO2(2+), and Am(3+) in the room temperature ionic liquid (RTIL) 1-n-octyl-3-methylimidazolium bis(trifluoromethane)sulfonamide (C8mimNTf2). The formation constants were calculated for Am(3+) which showed a significant role of ligand structure, nature of substituents, and spacer length. Although the alkyl substituents on the amidic nitrogen increase the extraction efficiency of americium at lower acidity because of the inductive effect of the alkyl groups, at higher acidity the steric crowding around the ligating site determines the extraction efficiency. All C4DGAs formed 1:1 complexes with Am(3+) while for the analogous Eu(3+) complexes no inner sphere water molecules were detected and the asymmetry of the metal ligand complex differed from one another as proved by time-resolved laser induced fluorescence spectroscopy (TRLIFS). Thermodynamic studies indicated that the extraction process, predominant by the Am(3+)-C4DGA complexation reaction, is exothermic. The unique role of the medium on Am(3+) complexation with the C4DGA molecules with varying spacer length, L-IV and L-V, was noticed for the first time with a reversal in the trend observed in the RTIL compared to that seen in a nonpolar molecular diluent like n-dodecane. Various factors leading to a more preorganized structure were responsible for favorable metal ion complexation. The solvent systems show promise to be employed for nuclear waste remediation, and sustainability options were evaluated from radiolytic stability as well as stripping studies.

Topics: Actinoid Series Elements; Calixarenes; Glycolates; Ionic Liquids; Ions; Lasers; Ligands; Molecular Structure; Phenols; Radiation Monitoring; Spectrometry, Fluorescence; Thermodynamics

A series of calix[4]arene-supported Ln(III)(6) clusters have been synthesised under facile bench top conditions. The magnetic and structural properties of these clusters are reported, the latter suggesting that the Ln(III)-calix[4]arene moiety may be used for the construction of other assemblies in a manner akin to that for the Mn(III)-calix[4]arene analogue.

Topics: Calixarenes; Crystallography, X-Ray; Lanthanoid Series Elements; Models, Molecular; Organometallic Compounds; Phenols

A new calix[4]arene 1 with tetrathiafulvalene (TTF), quinone, and crown ether units in the lower rim was designed and synthesized with the aim to investigate the possibility to tune the metal-ion promoted electron transfer by coordination of the crown ether unit with additional metal ions. Both absorption and electron spin resonance (ESR) spectroscopic studies clearly indicate that electron transfer occurs efficiently from TTF to the quinone units in the presence of Sc(3+)/Pb(2+)/Zn(2+). Moreover, the intramolecular electron transfer within 1 induced by Zn(2+) can be switched off by addition of Na(+) and further turned on by addition of either Sc(3+) or Pb(2+).

Topics: Calixarenes; Cations; Crown Ethers; Electron Transport; Heterocyclic Compounds; Ions; Metals, Heavy; Molecular Structure; Phenols; Quinones; Sodium

An amphiphilic calix[4]arene bearing branched 3,4,5-tris(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)benzamide groups at the upper rim was synthesized and could increase the solubility of naproxen and ibuprofen in water through hydrogen bonding and π-π stacking interactions. The interactions between amphiphilic calix[4]arene and carboxylic acids such as naproxen and ibuprofen could reverse the direction of the branched substituents and change the shape and size of calixarene micelles from solid to hollow or linear ones.

Topics: Anti-Inflammatory Agents, Non-Steroidal; Calixarenes; Carboxylic Acids; Hydrogen Bonding; Ibuprofen; Micelles; Naproxen; Phenols; Solubility; Surface-Active Agents; Water

Vanadyl bearing calix[4]arene ligands have undergone evaluation against several cell lines, and show varying degrees of toxicity. For vanadyl complexed to a sulfonylcalix[4]arene, monitoring of the strong blue fluorescence revealed slow uptake kinetics. The complex is exclusively found in the cytoplasm of the cells and uptake is not due to active endocytotic mechanisms.

Topics: Animals; Biological Transport; Calixarenes; Cell Line; Cell Survival; Fluorescent Dyes; Humans; Models, Molecular; Molecular Conformation; Organometallic Compounds; Phenols; Vanadium

Carboxamidoquinoline appended calix[4]arene-1,3-di-conjugate (L) has been synthesized and characterized and its single crystal XRD structure has been established. L has been shown to act as selective ratiometric turn-on fluorescence sensor for Zn(2+) up to a lowest concentration of 183 ± 18 ppb (2.82 μM) with a nine-fold enhancement by exhibiting blue-green emission. The coordination features of the species of recognition have been computationally evaluated by DFT methods and found to have distorted tetrahedral Zn(2+) center in an N(4) core. The spherical nano-structural features observed for L in TEM are being transformed into the Koosh nano-flower like structure when complexed with Zn(2+) and hence these two can be easily differentiated. Even the features observed in AFM can distinctly differentiate L from its Zn(2+) complex.

Topics: Amides; Calixarenes; Colorimetry; Crystallography, X-Ray; Models, Molecular; Nanostructures; Phenols; Quinolines; Sensitivity and Specificity; Spectrometry, Fluorescence; Zinc

The structurally characterized lower rim 1,3-di{4-antipyrine}amide conjugate of calix[4]arene (L) exhibits high selectivity toward Hg(2+) among other biologically important metal ions, viz., Na(+), K(+), Ca(2+), Mg(2+), Mn(2+), Fe(2+), Co(2+), Ni(2+), Cu(2+), Zn(2+), Cd(2+), Hg(2+), Pb(2+), and Ag(+) as studied by fluorescence, absorption, and ESI MS. L acts as a sensor for Hg(2+) by switch-off fluorescence and exhibits a lowest detectable concentration of 1.87 ± 0.1 ppm. The complex formed between L and Hg(2+) is found to be 1:1 on the basis of absorption and fluorescence titrations and was confirmed by ESI MS. The coordination features of the mercury complex of L were derived on the basis of DFT computations and found that the Hg(2+) is bound through an N(2)O(2) extending from both the arms to result in a distorted octahedral geometry with two vacant sites. The nanostructural features such as shape and size obtained using AFM and TEM distinguishes L from its Hg(2+) complex and were different from those of the simple mercuric perchlorate. L is also suited to sense pyrimidine bases by fluorescence quenching with a minimum detection limit of 1.15 ± 0.1 ppm in the case of cytosine. The nature of interaction of pyrimidine bases with L has been further studied by DFT computational calculations and found to have interactions through a hydrogen bonding and NH-π interaction between the host and the guest.

Topics: Absorption; Amides; Aminopyrine; Antipyrine; Calixarenes; Chemistry Techniques, Synthetic; Mercury; Methanol; Models, Molecular; Molecular Conformation; Nanostructures; Phenols; Pyrimidines; Spectrometry, Fluorescence; Substrate Specificity

Various polycharged calix[4]arenes were assayed as anti-mycobacterial agents against Mycobacterium tuberculosis, H(37)Rv strain. The sulfonate, carboxylate and phosphonate anionic species displayed no activity. Cationic derivatives integrating four aminoethyl groups at the upper rim and two 6,6'-dimethyl-2,2'-bipyridyl- or 4,4'-dimethyl-2,2'-bithiazolyl subunits at the lower rim were also found inactive against M. tuberculosis, while the unsubstituded and the 5,5'-dimethyl-2,2'-bipyridyl-analogues exhibited MIC values of 3.2 and 0.8μM respectively. Introduction of guanidinoethyl groups at the upper rim resulted, except for the 6,6'-dimethyl-2,2'-bipyridyl-derivative, in high anti-mycobacterial activities for the unsubstituted, the 5,5'-dimethyl-2,2'-bipyridyl- and the 4,4'-dimethyl-2,2'-bithiazolyl analogues, with MIC values of 0.8, 0.8 and 1.6μM, respectively, similar to those of current commercial anti-tuberculosis agents. The five more active substances were also evaluated against the isoniazid-resistant strain MYC5165, resulting in highly interesting micromolar or sub-micromolar MIC and IC(50), ca. 4-125 times more active than isoniazid. These preliminary results are attractive for the development of new anti-TB agents.

Topics: 2,2'-Dipyridyl; Anions; Antitubercular Agents; Calixarenes; Guanidine; Humans; Inhibitory Concentration 50; Microbial Sensitivity Tests; Mycobacterium tuberculosis; Phenols; Quaternary Ammonium Compounds; Tuberculosis

Calix[4]arene derivatives, blocked in the cone conformation and functionalized with two to four guanidinium units at the upper rim were synthesized and investigated as catalysts in the cleavage of the RNA model compound 2-hydroxypropyl p-nitrophenyl phosphate. When compared with the behavior of a monofunctional model compound, the catalytic superiority of the calix[4]arene derivatives points to a high level of cooperation between catalytic groups. Combination of acidity measurements with the pH dependence of catalytic rates unequivocally shows that a necessary requisite for effective catalysis is the simultaneous presence, on the same molecular framework, of a neutral guanidine acting as a general base and a protonated guanidine acting as an electrophilic activator. The additional guanidinium (guanidine) group in the diprotonated (monoprotonated) trifunctional calix[4]arene acts as a more or less innocent spectator. This is not the case with the tetrasubstituted calix[4]arene, whose mono-, di-, and triprotonated forms are slightly less effective than the corresponding di- and triguanidinocalix[4]arene derivatives, most likely on account of a steric interference with HPNP caused by overcrowding.

Topics: Calixarenes; Catalysis; Guanidine; Hydrogen-Ion Concentration; Molecular Conformation; Molecular Structure; Phenols; Phosphoric Diester Hydrolases; RNA; Stereoisomerism

A calix[4]arene acetylene (C4AE)-modified gold surface is successfully constructed in situ via click chemistry. The functionalized surface is used for selective recognition of paraquat by a wettability switch. Impedance measurements showed that the surface also expresses recognition for paraquat with a high sensitivity of 10 pM. The recognition mode, based on host-guest inclusion, is studied by computational calculations and the possible mechanism is analyzed.

Topics: Acetylene; Calixarenes; Click Chemistry; Electric Impedance; Electrochemical Techniques; Gold; Herbicides; Paraquat; Phenols; Sensitivity and Specificity; Surface Properties; Wettability

Guanidinium groups were introduced through a spacer at the lower rim of calix[4]arenes in the cone conformation to give new potential nonviral vectors for gene delivery. Several structural modifications were explored, such as the presence or absence of a macrocyclic scaffold, lipophilicity of the backbone, length of the spacer, and nature of the charged groups, in order to better understand the factors which affect the DNA condensation ability and transfection efficiency of these derivatives. The most interesting compound was a calix[4]arene unsubstituted at the upper rim and having four guanidinium groups linked at the lower rim through a three carbon atom spacer. This compound, when formulated with DOPE, showed low toxicity and transfection efficiency higher than the commercially available lipofectamine LTX in the treatment of human Rhabdomiosarcoma and Vero cells. Most of the investigated compounds showed a tendency to self-aggregate in pure water or in the presence of salts, as evidenced by NMR and AFM studies, and it was found that the ability to condense DNA plasmids in nanometric globules is a necessary but not sufficient condition for transfection. The superiority of macrocyclic vectors over linear Gemini-type analogues and of guanidinium compared to other ammonium head groups in determining the biological activity of the vectors was also ascertained.

Topics: Animals; Calixarenes; Cell Line, Tumor; Chlorocebus aethiops; DNA; Guanidine; Humans; Phenols; Plasmids; Solubility; Transfection; Vero Cells

Pyridyl-based triazole-linked calix[4]arene conjugates, viz. L(1) and L(2), were synthesized and characterized. These two conjugates were shown to be selective and sensitive for Zn(2+) among the 12 metal ions studied in HEPES buffer medium by fluorescence, absorption, and visual color change with the detection limit of ~31 and ~112 ppb, respectively, by L(1) and L(2). Moreover, the utility of the conjugates L(1) and L(2) in showing the zinc recognition in live cells has also been demonstrated using HeLa cells as monitored by fluorescence imaging. The zinc complexes of L(1) and L(2) were isolated, and the structure of [ZnL(1)] has been established by single-crystal XRD and that of [ZnL(2)] by DFT calculations. TDDFT calculations were performed in order to demonstrate the electronic properties of receptors and their zinc complexes. The isolated zinc complexes, viz. [ZnL(1)] and [ZnL(2)], have been used as molecular tools for the recognition of anions on the basis of their binding affinities toward Zn(2+). [ZnL(2)] was found to be sensitive and selective toward phosphate-bearing ions and molecules and in particular to pyrophosphate (PPi) and ATP among the other 18 anions studied; however, [ZnL(1)] was not sensitive toward any of the anions studied. The selectivity has been shown on the basis of the changes observed in the emission and absorption spectral studies through the removal of Zn(2+) from [ZnL(2)] by PPi. Thus, [ZnL(2)] has been shown to detect PPi up to 278 ± 10 ppb at pH 7.4 in aqueous methanolic (1/2 v/v) HEPES buffer.

Topics: Absorption; Adenosine Triphosphate; Calixarenes; Chemistry Techniques, Analytical; Diphosphates; HeLa Cells; Humans; Imines; Intracellular Space; Models, Molecular; Molecular Conformation; Organometallic Compounds; Phenols; Pyridines; Quantum Theory; Solutions; Spectrometry, Fluorescence; Zinc

The calix[4]arene secondary-amide derivative L was synthesized, and its complexation with alkali-metal cations in acetonitrile (MeCN) was studied by means of spectrophotometric, NMR, conductometric, and microcalorimetric titrations at 25 °C. The stability constants of the 1:1 (metal/ligand) complexes determined by different methods were in excellent agreement. For the complexation of M(+) (M = Li, Na, K) with L, both enthalpic and entropic contributions were favorable, with their values and mutual relations being quite strongly dependent on the cation. The enthalpic and overall stability was the largest in the case of the sodium complex. Molecular and crystal structures of free L, its methanol and MeCN solvates, the sodium complex, and its MeCN solvate were determined by single-crystal X-ray diffraction. The inclusion of a MeCN molecule in the calixarene hydrophobic cavity was observed both in solution and in the solid state. This specific interaction was found to be stronger in the case of metal complexes compared to the free ligand because of the better preorganization of the hydrophobic cone to accept the solvent molecule. Density functional theory calculations showed that the flattened cone conformation (C(2) point group) of L was generally more favorable than the square cone conformation (C(4) point group). In the complex with Na(+), L was in square cone conformation, whereas in its adduct with MeCN, the conformation was slightly distorted from the full symmetry. These conformations were in agreement with those observed in the solid state. The classical molecular dynamics simulations indicated that the MeCN molecule enters the L hydrophobic cavity of both the free ligand and its alkali-metal complexes. The inclusion of MeCN in the cone of free L was accompanied by the conformational change from C(2) to C(4) symmetry. As in solution studies, in the case of ML(+) complexes, an allosteric effect was observed: the ligand was already in the appropriate square cone conformation to bind the solvent molecule, allowing it to more easily and faster enter the calixarene cavity.

Topics: Acetonitriles; Amides; Calixarenes; Calorimetry; Cations; Coordination Complexes; Crystallography, X-Ray; Magnetic Resonance Spectroscopy; Metals, Alkali; Models, Molecular; Phenols; Spectrophotometry; Thermodynamics

The carrier activity of calix[4]arene containing imidazole groups towards the facilitated transport of palladium(II) through dichloromethane bulk liquid membrane has been studied. The optimum transport conditions were established by the studies on the effect of pH, feed concentration, carrier concentration, receiver phase concentration and transport time. A solution of 1M hydrochloric acid (HCl) served as receiving phase for maximum transport of the metal ion. Maximum transport efficiency was observed for Pd(II) ion when it was present in the concentration of 10(-3)M and the transport efficiency after 24h was found as 95%.

Topics: Calixarenes; Equipment Design; Imidazoles; Industrial Waste; Kinetics; Membranes, Artificial; Models, Chemical; Molecular Structure; Palladium; Phenols; Solvents; Waste Management

Small molecules that recognize protein surfaces are important tools for modifying protein interaction properties. Since the 1980s, several thousand studies concerning calixarenes and host-guest interactions have been published. Although there is growing interest in protein-calixarene interactions, only limited structural information has been available to date. We now report the crystal structure of a protein-calixarene complex. The water-soluble p-sulfonatocalix[4]arene is shown to bind the lysine-rich cytochrome c at three different sites. Binding curves obtained from NMR titrations reveal an interaction process that involves two or more binding sites. Together, the data indicate a dynamic complex in which the calixarene explores the surface of cytochrome c. In addition to providing valuable information on protein recognition, the data also indicate that the calixarene is a mediator of protein-protein interactions, with potential applications in generating assemblies and promoting crystallization.

Topics: Binding Sites; Calixarenes; Crystallography, X-Ray; Cytochromes c; Phenols; Protein Interaction Mapping; Protein Structure, Tertiary; Solvents; Static Electricity

A chiral 1,1-bi-2-naphthol-derived calix[4]arene (1) was synthesized via a click reaction. Fluorescence spectra and dynamic light-scattering revealed that Cu(II)-1 complexes were generated in situ and exhibited remarkable enantioselectivity toward mandelic acid. Using this dynamic light-scattering technique, the detection sensitivity was improved almost 100-fold, with a detection limit of 2.0 × 10(-7) M, compared with fluorescent methods.

Topics: Calixarenes; Click Chemistry; Fluorescence; Magnetic Resonance Spectroscopy; Mandelic Acids; Molecular Structure; Naphthols; Phenols

A highly fluorescent Zn(2+) complex of the triazole linked salicyl-imino-thiophenyl conjugate of calix[4]arene, [ZnL] has been demonstrated to be a chemo-sensing ensemble for the recognition of His and Cys among the naturally occurring amino acids in HEPES buffer milieu. The recognition behaviour of the [ZnL] towards these amino acids has been shown on the basis of fluorescence, absorption and visual fluorescent colour changes. The species of recognition were shown by ESI MS titrations, AFM & TEM microscopy and cell studies.

Topics: Buffers; Calixarenes; Cysteine; HeLa Cells; HEPES; Histidine; Humans; Microscopy, Fluorescence; Phenols; Triazoles; Zinc

An N,N-Dimethylamine ethylimino-appended triazole-linked calix[4]arene conjugate, L, has been synthesized and characterized, and its Cd(2+) complex has been isolated and characterized. The structure of [CdL] was established by computational calculation using B3LYP/LANL2DZ. Time-dependent density functional theory calculations were performed to demonstrate the electronic properties of [CdL]. This highly fluorescing [CdL] has been used to recognize Cys selectively among the 20 naturally occurring amino acids. [CdL] exhibits a minimum detection limit of 58 ppb for Cys, with reusability and reversibility being imparted to the system during sensing. Thus, the sensing of Cys was well demonstrated using various techniques, viz., fluorescence, absorption, visual color change, electrospray ionization MS, (1)H NMR, and live cell imaging experiments.

Topics: Cadmium; Calixarenes; Coordination Complexes; Cysteine; Humans; Ions; Magnetic Resonance Spectroscopy; MCF-7 Cells; Microscopy, Fluorescence; Phenols; Spectrometry, Fluorescence; Spectrometry, Mass, Electrospray Ionization; Triazoles

A benzimidazole appended triazole linked 1,3-diconjugate of calix[4]arene (L) has been synthesized and characterized. The conjugate L has been found to recognize Cu(2+) among the thirteen different metal ions studied by exhibiting ratiometric fluorescence changes through newly generated excimer band at ∼380 nm. Fluorescence off-on-off behavior has been clearly demonstrated on the basis of the binding variability of Cu(2+) to L. The binding has been elicited through the changes observed in the fluorescence, ESI MS and (1)H NMR titrations. All the other metal ions studied do not show any new band and further do not interfere with the recognition of Cu(2+) by L, even when these are present in the same medium. The structural features of both the mono- and di-nuclear complexes were established by DFT computational calculations and found to display highly distorted geometry about the copper centers that deviate from both the tetrahedral and the square planar.

Topics: Benzimidazoles; Buffers; Calixarenes; Copper; Crystallography, X-Ray; Ions; Molecular Conformation; Phenols; Spectrometry, Fluorescence; Triazoles

In this communication we report a p-sulfonatocalix[4]arene coated ZnS quantum dots "cup type" highly stable optical probe for the detection and determination of menadione (VK(3)) with high sensitivity and selectivity. The detection of VK(3) depends on supramolecular host-guest chemistry.

Topics: Calixarenes; Osmolar Concentration; Phenols; Quantum Dots; Spectrometry, Fluorescence; Sulfides; Vitamin K 3; Zinc Compounds

The triazole linked o-imino phenol appended calix[4]arene conjugate (L) has been synthesized and characterized. The structure of L has been established based on single crystal XRD. The binding and recognition behavior of conjugate, L toward the transition metal ions, such as Mn(2+), Fe(2+), Co(2+), Ni(2+), Cu(2+), and Zn(2+), has been demonstrated using fluorescence, absorption and ESI-MS techniques. The in situ prepared complexes of these metal ions, namely, [Mn(2)L], [Fe(2)L], [Co(2)L], [Ni(2)L], [Cu(2)L], and [Zn(2)L] have shown recognition toward Glu, Asp, His and Cys. Hence L provides a multiple sensing molecular tool where the response for the recognition of biologically active amino acids of metalloproteins is elicited by the presence of specific metal ion.

Topics: Aspartic Acid; Calixarenes; Cysteine; Glutamic Acid; Histidine; Imines; Models, Molecular; Molecular Structure; Organometallic Compounds; Phenols; Spectrometry, Fluorescence; Spectrometry, Mass, Electrospray Ionization; Transition Elements; Triazoles

Due to their potential applicability as selective receptors in electrochemical or optical sensors, a bis(azophenol)calix[4]arene derivative H(2)L has been investigated. The complexation properties of this molecule towards Ni(2+) and Co(2+) metal ions has been studied. It is revealed that this ligand exhibits tetradentate with N(2)O(2) core when bound to Ni (II) or Co (II) metal ion. The optical response of azo groups of H(2)L towards Ni(2+), Co(2+), Cu(2+), Pb(2+) and Hg(2+) metal ions has been investigated in DMSO by UV-vis spectroscopy. The absorption spectra of calix[4]arene with cations show marked changes, especially for Co(2+) ion. Furthermore, Job's plot indicate 1:1 binding-stiochiometry for calix[4]arene with Co(2+) ion and Benson-Hilderbrand plot is used for the determination of its association constant. The investigation of UV-vis spectra of chromogenic calix[4]arene in different solvents shows that cis-trans isomerization of azo groups probably depends on kind of solvent. Also the different between the polarity and viscosity of organic solvents used is likely responsible for the changes of the band shape of the spectra.

Topics: Calixarenes; Cations, Divalent; Cobalt; Coordination Complexes; Copper; Lead; Mercury; Metals; Nickel; Phenols; Spectrophotometry, Infrared; Spectrophotometry, Ultraviolet

The present paper describes the spectroscopic and theoretical insights on non-covalent interaction of a calix[4]arene molecule, namely, 4-iso-propyl-calix[4]arene (1) with chromophore appended fullerenes, namely, tert-butyl-(1,2-methanofullerene)-61-carboxylate (2) and [6,6]-phenyl-C(71)- butyric acid methyl ester (3) in solvents having varying polarity, viz., toluene and benzonitrile. Absorption spectrophotometric studies reveal appreciable ground state interaction between fullerenes and 1. The most fascinating feature of the present study is that 1 binds very effectively with both 2 and 3 as obtained from binding constant (K) data of such complexes; i.e., K(2-1) and K(3-1) exhibit value of 4.53 × 10(5) dm(3) mol(-1) (7.95 × 10(5) dm(3) mol(-1)) and 13.35 × 10(5) dm(3) mol(-1) (27.62 × 10(5) dm(3) mol(-1)) in toluene (benzonitrile), respectively. The effect of solvent over the complexation between fullerenes and 1 is clearly observed from the trend in the K values. Estimation of solvent reorganization energy (R(S)) evokes that both 2-1 and 3-1 complexes are stabilized more in toluene compared to benzonitrile. Molecular mechanics force field (MMMF) calculations in vacuo evoke geometrical structures of the 2-1 and 3-1 complexes and reveal interesting feature regarding binding pattern of fullerenes toward 1 in terms of heat of formation value of the respective complexes.

Topics: Calixarenes; Coloring Agents; Fullerenes; Models, Molecular; Phenols; Solvents; Spectrophotometry, Ultraviolet

An amphiphilic calix[4]arene derivative bearing four guanidino moieties at the upper rim and four dodecyl chains at the lower rim was shown to form stable solid lipid nanoparticles (SLNs) in water. The study of the interactions of these cationic SLNs with DNA revealed a sequence-dependent groove binding mechanism.

Topics: Base Sequence; Calixarenes; DNA; Lipids; Nanoparticles; Phenols; Static Electricity

Complexes [bzimAlR(2)](4) [bzim = benzimidazolate; R = Et (2), (i)Bu (3)], [mbzimAlR(2)](4) [mbzim = 2-methylbenzimidazolate; R = Et (6), (i)Bu (7)], [dmbzimAlR(2)](4) [dmbzim = 5,6-dimethylbenzimidazolate; R = Me (9), Et (10), (i)Bu (11)], and [tmbzimAlR(2)](4) [tmbzim = 2,5,6-trimethylbenzimidazolate; R = Me (12), Et (13), (i)Bu (14)] have been prepared via alkane elimination and coordinative self-assembly upon the reaction of benzimidazole ligands with aluminum alkyls in benzene, toluene, or xylene. Characterization of the complexes was achieved by spectroscopic methods, microanalysis, and X-ray crystallography of 2, 7, 10, 11, 13, and 14. The complexes reported herein and the aluminum and gallium analogues 1, 4, 5, and 8 reported in a previous paper (1) are predominantly tetranuclear aggregates related to calix[4]arenes in which the benzimidazolyl ligands bind two metal atoms in a η(1):η(1) fashion. X-ray crystallography demonstrates that modulation of the conformation adopted by these metallacalix[4]arenes is achieved by proper substitution on the C atom at the 2 position of the benzimidazolyl ligand. An H substituent for 1, 2, 4, 10, and 11 favors a chair conformation with a small cavity and approximate C(2h) symmetry, while a CH(3) substituent for 5, 7, 8, 13, and 14 introduces enough repulsion to switch the conformation to a 1,3-alternate or double cone with a concomitant larger cavity and approximate C(2v) symmetry.

Topics: Aluminum; Benzimidazoles; Calixarenes; Crystallography, X-Ray; Gallium; Ligands; Models, Molecular; Molecular Conformation; Organometallic Compounds; Phenols

Proton rearrangement rates in hydrogen bond networks are dominated by classical activation and quantum tunneling at higher and lower temperatures, respectively. Calix[4]arene (C4A) has a square-ring network composed of four hydroxyl groups with the O···O length of ~0.265 nm. Calorimetry and dielectric relaxation measurements were applied to determination of the rates in the crystals of C4A and its deuteron analogue (C4A-d). The rearrangement rates in C4A-d exhibited Arrhenius dependence in the measured temperature range. On the other hand, the rates in C4A showed the same dependence as those in C4A-d above 200 K, deviated from this dependence at around 180 K, and became independent of temperature at around 10(-4) s(-1) below 100 K. This evidenced that the tunneling in the quadruple proton rearrangement proceeds at a very slow rate of 10(-4) s(-1). This is the first determination by calorimetry of the proton tunneling rate.

Topics: Calixarenes; Hydrogen Bonding; Hydroxyl Radical; Molecular Structure; Phenols; Protons; Quantum Theory; Temperature

This work reports a new method to covalently attach calix[4]arene derivatives onto MCM-41, using a diisocyanate as a linker. The modified mesoporous silicates were characterized by fourier transform infrared spectroscopy (FTIR), thermal analysis (TGA) and elemental analysis. The FTIR spectra and TGA analysis verified that the calix[4]arene derivates are covalently attached to the mesoporous silica. The preservation of the MCM-41 channel system was checked by X-ray diffraction and nitrogen adsorption analysis.

Topics: Calixarenes; Phenols; Porosity; Silicon Dioxide; Spectroscopy, Fourier Transform Infrared; Thermogravimetry; X-Ray Diffraction

Cell cycle progression is dependent on the intracellular iron level and chelators can lead to iron depletion and decrease cell proliferation. This antiproliferative effect can be inhibited by exogenous iron. In this work, we present the synthesis of some new synthetic calix[4]arene podands bearing diamino-tetraesters, diamino-tetraalcohols, diamino-tetraacid and tetraaryloxypentoxy groups at the lower rim, designed as potential iron chelators. We report their effect on cell proliferation, in comparison with the new oral chelator ICL670A (4-[3,5-bis-(2-hydroxyphenyl)-1,2,4-triazol-1-yl]-benzoic acid). The antiproliferative effect of these new compounds was studied in the human hepatocarcinoma HepaRG cell cultures using cell nuclei counting after staining with the DNA intercalating fluorescence dye, Hoechst 33342. Their cytotoxicity was evaluated by the extracellular LDH activity. Preliminary results indicated that their antiproliferative effect was mainly due to their cytotoxicity. The efficiency of these compounds, being comparable to that of ICL670, was independent of iron depletion. This effect remains to be further explored. Moreover, it also shows that the new substituted calix[4]arenes could open the way to valuable new approaches for medicinal chemistry scaffolding.

Topics: Antineoplastic Agents; Calixarenes; Cell Line, Tumor; Cell Proliferation; Cells, Cultured; Female; Hepatocytes; Humans; Liver; Molecular Structure; Phenols; Solubility

The fluorescence quenching effect of Ni(2+) on the derivatives of p-tert- butyl-calix[4]arene with o-phenanthroline(TBCP) was studied in cetyltrimethyl- ammonium bromide (CTAB) medium. Ni(2+) reacted with the TBCP to form inclusion complex. The fluorescence quenching was sensitized in CTAB. The linear range of calibration curve for the determination of Ni(2+) was 0.050 μg/mL ~ 1.00 μg/mL. The detection limit estimated (S/N = 3) was 5.3 ng/mL. It has been applied for the determination of Ni(II) in samples with satisfactory results.

Topics: Calibration; Calixarenes; Cetrimonium; Cetrimonium Compounds; Hydrogen-Ion Concentration; Limit of Detection; Nickel; Phenols; Spectrometry, Fluorescence; Surface-Active Agents

Two armed chiral calix[4]arenes 8-16 functionalized at the lower rim with chiral aminonaphthol units have been prepared and the structures of these receptors characterized by FTIR, (1)H, and (13)C, DEPT and COSY NMR spectroscopy and elemental analysis. The enantioselective recognition of these receptors with various carboxylic acids has been studied by (1)H NMR and UV/Vis spectroscopy. The receptors exhibited different chiral recognition abilities towards the enantiomers of racemic materials and formed 2 : 1 or 1 : 1 complexes between host and guest. It was also demonstrated that chiral calix[4]arenes 9 and 16 could be used as chiral NMR solvating agents to determine the enantiomeric purity of mandelic acid.

Topics: Amines; Calixarenes; Carboxylic Acids; Molecular Structure; Naphthols; Phenols; Stereoisomerism

Lower rim 1,3-diamido conjugates of calix[4]arene have been synthesized and characterized, and the structures of some of these have been established by single crystal XRD. The amido-calix conjugates possessing a terminal -COOH moiety have been shown to exhibit recognition toward guest molecules possessing -COOH moiety, viz., Asp, Glu, and reduced and oxidized glutathione (GSH, GSSG), by switch-on fluorescence in aqueous acetonitrile and methanol solutions when compared to the control molecules via forming a 1:1 complex. The complex formed has been shown by mass spectrometry, and the structural features of the complexes were derived on the basis of DFT computations. The association constants observed for the recognition of Asp/Glu by Phe-calix conjugate, viz., 532/676 M(-1), are higher than that reported for the recognition of Val, Leu, Phe, His, and Trp (16-63 M(-1)) by a water-soluble calixarene (Arena, G., et al. Tetrahedron Lett. 1999, 40, 1597). For this recognition, there should be a free -COOH moiety from the guest molecule. AFM, SEM, and DLS data exhibited spherical particles with a hundred-fold reduction in the size of the complexes when compared to the particles of the precursors. These spherical particles have been computationally modeled to possess hexameric species reminiscent of the hexameric micellar structures shown for a Ag(+) complex of a calix[6]arene reported in the literature (Houmadi, S., et al. Langmuir 2007, 23, 4849). Both AFM and TEM studies demonstrated the formation of nanospheres in the case of GSH-capped Ag nanoparticles in interaction with the amido-calix conjugate that possesses terminal -COOH moiety. The AFM studies demonstrated in this paper have been very well applied to albumin proteins to differentiate the aggregational behavior and nanostructural features exhibited by the complexes of proteins from those of the uncomplexed ones. To our knowledge, this is the first report wherein a amido-calix[4]arene conjugate and its amino acid/peptide/protein complexes have been differentiated on the basis of spectroscopy and microscopy studies followed by species modeling by computations.

Topics: Amino Acids; Calixarenes; Computers, Molecular; Crystallography, X-Ray; Magnetic Resonance Spectroscopy; Microscopy; Models, Molecular; Phenols; Protein Binding; Proteins

A thiacalix[4]arene based chemosensor 3 bearing two pyrene groups has been synthesized which demonstrates ratiometric sensing with Ag(+) and fluorescence quenching with Fe(3+) ions in mixed aqueous media. The 'in situ' prepared Ag(+) and Fe(3+) complexes showed high selectivity toward cysteine. The molecular switching between three chemical inputs (Ag(+), Fe(3+), cysteine) results in various molecular logic gates which have been integrated sequentially to generate a sequential information processing device.

Topics: Calixarenes; Cysteine; Ferric Compounds; Molecular Structure; Organometallic Compounds; Phenols; Pyrenes; Silver; Spectrometry, Fluorescence

Two new cone- and 1,3-alternate-calix[4]arenes (cone-1 and 1,3-alt-1), bearing four modified TTF (tetrathiafulvalene) substituents on the upper rim, have been synthesized. The binding ability of these two sets of conformers for various anions, including F(-), Cl(-), Br(-), I(-), PF6(-), ClO4(-), HSO4(-), CH3COO(-), H2PO4(-), and HP2O7(3-), was tested in organic media by monitoring the changes in their UV/vis and (1)H NMR spectra as a function of added anion, as well as via cyclovoltammetry (CV) (all anions studied as their respective TBA salts). On the basis of the present findings, we propose that incorporation of four TTF units within an overall calix[4]arene-based recognition framework produces a preorganized receptor system that displays a modest preference for the pyrophosphate (HP2O7(3-)) anion.

Topics: Anions; Calixarenes; Heterocyclic Compounds; Magnetic Resonance Spectroscopy; Molecular Conformation; Molecular Structure; Phenols

The present work explores sorption behavior of calix[4]arene based silica resin to remove α and β endosulfan isomers from aqueous solution. The efficiency of resin was checked through both batch and column sorption methods. In both methods, the sorption parameters, i.e. pH, equilibrium time, shaking speed and sorbent dosage were optimized as 2, 60 min, 125 rpm and 50 mg, respectively. Freundlich and Langmuir sorption isotherm models were applied to validate the sorption process. The data obtained in both models reveal that the sorption is favorable. Column sorption data were analyzed through Thomas model to calculate kinetic coefficient k(TH) and maximum sorption capacity q(o) of the resin, which were found to be 6.18 and 5.83 cm(3) mg(-1) min(-1) as well as 1.11 and 1.08 mg g(-1) for α and β endosulfan, respectively. Kinetics of sorption shows that it follows pseudo second order rate equation. The optimized method has also been applied to real water samples and the results show that calix[4]arene based silica resin is an effective sorbent to remove endosulfan from waste waters.

Topics: Adsorption; Algorithms; Calixarenes; Endosulfan; Hydrogen-Ion Concentration; Indicators and Reagents; Insecticides; Microscopy, Electron, Scanning; Models, Chemical; Phenols; Silicon Dioxide; Spectroscopy, Fourier Transform Infrared; Thermodynamics; Water Purification

The uptake of a fluorescently labeled cationic calix[4] (NBDCalAm) in live, nonfixed cells has been investigated. The compound is taken into the cells rapidly and shows distinct endosomal distribution after 2 hours. This distribution pattern shows colocalization with lysosomal staining. The uptake is not altered by inhibition of clathrin or caveolae dependent pathways nor by depletion of the cellular ATP-pool. Immediately after uptake the probe is localized in the Golgi and brefeldin A treatment prevents transport to lysosomes. Pulse chase experiments with bafilomycin A1, monensin, and sodium azide showed that accumulation and retention of the probe in lysosomes is primarily driven by the activity of vacuolar ATPases. The NBD labeled calix[4]arene provides a very stable and sensitive marker for lysosomes, and has a considerable advantage over some commercially available lysosomal markers in so far that the fluorescent signal is stable even when the cells are incubated in dye-free medium after staining.

Topics: Animals; Biological Transport; Brefeldin A; Calixarenes; Caveolae; CHO Cells; Clathrin; Cricetinae; Cricetulus; Endosomes; Fluorescent Dyes; Golgi Apparatus; HeLa Cells; Humans; Lysosomes; Macrolides; Monensin; Phenols; Sodium Azide; Tumor Cells, Cultured; Vacuolar Proton-Translocating ATPases

The present article describes the solvatochromic effect including solvent system selection, time study and a detailed complexation study along with exploration of extraction properties of 5,11,17,23-tetrakis[(diethylamino)methyl]-25,26,27,28-tetrahydroxycalix[4]arene (4) that bears nitrogen atom as a donor group available for chelating metal ions. Complexation properties of 4 toward selected transition metal ions have been investigated by UV-visible and fluorescence spectroscopies. The% efficiency of 4 toward selected transition metal ions was found in order Cu(2+)>Ni(2+)>Hg(2+)>Zn(2+)>Co(2+)>Cd(2+)>Pb(2+). It has been noticed that 4 is not only proved to be an efficient Cu(2+) selective chromoionophore but also possesses an effective extraction property for transferring Cu(2+) ions from an aqueous to dichloromethane layer. The FT-IR spectroscopic method has also been applied for further confirmation of the complexation phenomenon of 4 with Cu(2+) ion and found adequate.

Topics: Calixarenes; Copper; Fluorescence; Molecular Structure; Organometallic Compounds; Phenols; Spectrometry, Fluorescence; Spectrophotometry, Ultraviolet; Spectroscopy, Fourier Transform Infrared

The pyrimidine (pym) nucleobase cytosine (H(2)C) forms cyclic ring structures ("metallacalix[n]arenes") when treated with square-planar cis-a(2)M(II) entities (M=Pt, Pd; a=NH(3) or a(2)=diamine). The number of possible linkage isomers for a given n and the number of possible rotamers can be substantially reduced if a "directed" approach is pursued. Hence, two cytosine ligands are bonded in a defined way to a kinetically robust platinum corner stone. In the accompanying paper (Part I: A. Khutia, P. J. Sanz Miguel, B. Lippert, Chem. Eur. J. 2010, 17, DOI: 10.1002/chem.2010002722) we have demonstrated this principle by allowing cis-[Pta(2)(H(2)C-N3)(2)](2+) to react with (en)Pd(II) to give cycles of (N1,N3⋅N3,N1▪)(x) (with x=2 or 3; ⋅ represents Pt(II) and ▪ represents Pd(II)). In an extension of this work we have now prepared cis-[Pta(2)(HC-N1)(2)] (1; HC=monoanion of cytosine) and treated it with (bpy)Pd(II) (bpy=2,2'-bipyridine) to give the Pt(2) Pd(2) cycle cis-[{Pt(NH(3))(2)(N1-HC-N3)(2)Pd(bpy)}(2)](NO(3))(4) ⋅13H(2)O (5) with the coordination sites of the metals inverted; hence, platinum is bonded to N1 and palladium is bonded to N3 sites. Again, not only the expected single linkage isomer is formed, but at the same time the solid-state structure and (1)H NMR spectroscopy reveal the preferential occurrence of a single rotamer (1,3-alternate). The addition of (bpy)Pd(II) to 5 led to the formation of Pd(6) Pt(2) complex 6 in which the exocyclic N4H(2) groups of the cytosine ligands have undergone deprotonation and chelate four more (bpy)Pd(II) entities through the O2 and N4H sites. With a large excess of (bpy)Pd(II) over 5 (4:1), cis-(NH(3))(2) Pt(II) is eventually substituted by (bpy)Pd(II) to give the Pd(8) complex 7. In both 6 and 7 stacks of three (bpy)Pd(II) entities occur. The linkage isomer of 5,cis-[{Pt(NH(3))(2)(N3-HC-N1)(2)Pd(bpy)}(2)](NO(3))(4) ⋅9H(2)O (8), has been structurally characterized and the two complexes compared. The acid/base properties of cis-[Pt(NH(3))(2)(H(2)C-N1)(2)] (1) have been determined and compared with those of the corresponding N3 isomer. The complexation of AgCl by 1 is reported.

Topics: Calixarenes; Cytosine; Heterocyclic Compounds; Isomerism; Ligands; Magnetic Resonance Spectroscopy; Metals; Models, Molecular; Molecular Structure; Palladium; Phenols; Platinum; Pyrimidines

Tetrazoles and acyl sulfonamides are functional groups that are common in medicinal chemistry but virtually unexplored as recognition elements in supramolecular chemistry. We report here on the anion binding properties of these highly acidic N-H functional groups. We have prepared two new calixarene-based tetrazole-containing hosts, as well as new acetyl sulfonamide and benzoyl sulfonamide hosts. We also report on analogous hosts bearing the better-known aryl sulfonamide functional group as a point of comparison. We find that these hosts are competent anion binders and that the recognition of anions by these groups is highly dependent on their conformational preferences. We also report in detail on the preferred molecular shape of each acid bioisostere as determined by calculations and structural database surveys, and discuss how these shapes impact binding in the context of the reported hosts.

Topics: Calixarenes; Carboxylic Acids; Models, Molecular; Molecular Conformation; Phenols; Sulfonamides; Tetrazoles

Hexabromocalix[4]arene derivatives (3a and 3b) possessing pairs of dibromomethylene and bromomethylene groups located at distal or proximal positions of the calix scaffold were prepared via photochemical bromination of tetramethoxycalix[4]arene. The dibromomethylene groups undergo hydrolysis to afford calix[4]arenes possessing pairs of carbonyl groups and bromomethylene groups located at distal or proximal bridges (4a and 4b, respectively). The bromomethylene groups of 4 undergo reactions with nucleophiles under S(N)1 conditions to afford a wide array of derivatives possessing two different chemical modifications at the bridges.

Topics: Alkylating Agents; Azides; Calixarenes; Carboxylic Acids; Halogenation; Molecular Conformation; Phenols

The bridge-substituted calix[4]arene carboxylic acid, 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetramethoxy-calix[4]arene-2-carboxylic acid (1), can be readily converted to various esters 2-4 and reduced to the alcohol 5, which reacts with methyl iodide to give the ether 6. The alcohol can be dansylated to give 7, the fluorescence of which is selectively quenched by Cu(II) in acetonitrile. An attempt to convert the acid 1 to an amide resulted unexpectedly in the formation of a lactone 8. The conformational characteristics of 1-8 have been studied in solution and, in the cases of 2 and 4, in the solid state by determination of their single-crystal X-ray structures. With the exception of 8, in all these compounds the bridge substituent adopts an equatorial (lateral) orientation.

Topics: Calixarenes; Crystallography, X-Ray; Models, Molecular; Molecular Conformation; Phenols; Stereoisomerism

A novel 1,3-alternate calix-[4]arene L, containing two different cationic binding sites of bis-triazoles and bis-enaminone groups, was synthesized and shown to be a homobinuclear ditopic fluorescent chemosensor for Ag(+) ions. The fluorescence intensity of L was selectively enhanced by binding with Ag(+) ions in methanol/chloroform (49:1, v/v) cosolvent. In the presence of most competing metal ions, L retains its selectivity toward Ag(+) ion. The binding constants K(1) and K(2) of the successive complexation of L with the first and second Ag(+) ions were calculated to be 4.46×10(3) and 9.20×10(4) M(-1), respectively. The higher K(2) value revealed that a positive allosteric effect participated in the complexation of L with the second equivalent of Ag(+). Based on (1)H NMR titration results, we inferred that the two distal bis-enaminone and bis-triazole groups on L cooperatively coordinated to Ag(+) ions with the help of cation-π interactions from the phenoxy rings. Furthermore, the ESI-MS spectrometry clearly proved the formation of the homobinuclear complex L·(Ag(+))(2), because a base peak at m/z of 750.1701 was detected and its isotope pattern was in excellent agreement with the calculated one.

Topics: Binding Sites; Calixarenes; Crystallography, X-Ray; Fluorescent Dyes; Ions; Models, Molecular; Molecular Structure; Phenols; Silver

Candida rugosa lipase (CRL) was encapsulated within a chemically inert sol-gel support prepared by polycondensation with tetraethoxysilane (TEOS) and octyltriethoxysilane (OTES) in the presence of N-methylglucamine based calix[4]arene magnetic nanoparticles. The results indicate that the magnetic calix[4]arene based encapsulated lipase particularly has shown high conversion and enantioselectivity. It has also been noticed that the magnetic calix[4]arene based encapsulated lipase has excellent enantioselectivity (E = 460) as compared to the free enzyme (E = 166) with an ee value of >98% for S-Naproxen.

Topics: Biocatalysis; Calixarenes; Candida; Ferric Compounds; Gels; Lipase; Magnetics; Molecular Structure; Nanoparticles; Particle Size; Phenols; Stereoisomerism; Surface Properties

Solution-phase and solid-state structural studies indicate that the remarkable hydrogelation properties of a proline-functionalised calix[4]arene emerge as a result of extended helical structures formed via inclusion of a proline moiety in a neighbouring calixarene cavity.

Topics: Calixarenes; Crystallography, X-Ray; Hydrogels; Lanthanoid Series Elements; Microscopy, Atomic Force; Molecular Conformation; Phenols; Proline

A supramolecular drug delivery system has been developed via the self-assembly of a supramolecular amphiphilic polymer, which is constructed by the host-guest interaction of hydrophilic PEGylated calix[4]arene and hydrophobic photosensitizer chlorin e6. It provides a new strategy for the preparation of supramolecular polymeric micelles, and plays an important role in biological applications.

Topics: Calixarenes; Chlorophyllides; Female; HeLa Cells; Humans; Micelles; Phenols; Photochemotherapy; Polyethylene Glycols; Porphyrins; Uterine Cervical Neoplasms

This paper deals with the design, synthesis, and evaluation of a new series of receptors for protein surface recognition. The design of these agents is based around the attachment of four constrained dipeptide chains onto a central resorc[4]arene scaffold. By varying the sequence, nature, and stereochemistry of the chains we prepared anionically functionalized N-linked peptidoresorc[4]arenes 12, 13, and 17 by Pd/C-catalyzed hydrogenation of the corresponding benzyl esters 10, 11, and 16. From this family of receptors we have identified noncompetitive inhibitors of α-chymotrypsin (ChT), which function by binding to the surface of the enzyme in the neighborhood of the active site cleft (K(i) values ranging from 12.4 ± 5.1 μM for free carboxylic acid (+)-12b to 0.76 ± 0.14 μM for benzyl ester (-)-16a). For anionically functionalized receptors 12, 13, and 17 the ChT inhibition is based essentially on electrostatic interaction, and the bound enzyme can be released from the resorcarene surface by increasing the ionic strength, with its activity almost completely restored. For receptors with terminal benzyl ester groups (10 and 16) a hydrophobic network can be suggested.

Topics: Animals; Calixarenes; Catalytic Domain; Cattle; Chymotrypsin; Drug Evaluation, Preclinical; Humans; Models, Molecular; Nitrogen; Osmolar Concentration; Peptides, Cyclic; Phenols; Protease Inhibitors; Serum Albumin; Stereoisomerism; Substrate Specificity

1,3-Alternate calix[4]arene with para-phenylene spacers connecting nitroxide monoradicals and high-spin (S = 1) diradicals provides tetraradical and octaradical scaffolds that possess conformations with slow electron spin relaxation rates (1/T(1)). Such scaffolds may facilitate tuning of relaxation rates that are more favorable for MRI or DNP applications.

Topics: Calixarenes; Electron Spin Resonance Spectroscopy; Magnetic Resonance Spectroscopy; Nitric Oxide; Phenols; Quantum Theory

Twelve molecules of β-carbonyl-para-octyl-calix[4]arene assemble in an aggregate containing two types of cavities filled by water molecules and they pack in a cubic structure. Both the aggregates and the packing resemble that observed for inverse micelles.

Topics: Calixarenes; Hydrogen Bonding; Micelles; Molecular Conformation; Phenols; Water

This highlight examines recent advances in the development of synthetic membrane transporters for anions, highlighting the underlying principles of transporter design and the promising applications of such transporters to biological systems including potential future treatments for diseases like cystic fibrosis which is caused by dysregulation of chloride transport across epithelial cell membranes.

Topics: Anions; Calixarenes; Hydrogen Bonding; Hydrogen-Ion Concentration; Ion Transport; Lipid Bilayers; Phenols; Prodigiosin

The recognition of protein surfaces by designed ligands has become an attractive approach in drug discovery. However, the variable nature and irregular behavior of protein surfaces defy this new area of research. The easy to understand "lock-and-key" model is far from being the ideal paradigm in biomolecular interactions and, hence, any new finding on how proteins and ligands behave in recognition events paves a step of the way. Herein, we illustrate a clear example on how an increase in flexibility of both protein and ligand can result in an increase in the stability of the macromolecular complex. The biophysical study of the interaction between a designed flexible tetraguanidinium-calix[4]arene and the tetramerization domain of protein p53 (p53TD) and its natural mutant p53TD-R337H shows how the floppy mutant domain interacts more tightly with the ligand than the well-packed wild-type protein. Moreover, the flexible calixarene ligand interacts with higher affinity to both wild-type and mutated protein domains than a conformationally rigid calixarene analog previously reported. These findings underscore the crucial role of flexibility in molecular recognition processes, for both small ligands and large biomolecular surfaces.

Topics: Calixarenes; Calorimetry, Differential Scanning; Hydrophobic and Hydrophilic Interactions; Ligands; Mutation; Phenols; Protein Binding; Protein Structure, Tertiary; Tumor Suppressor Protein p53

Self-assembly and characterization of novel heterodimeric diphosphine capsules formed by multiple ionic interactions and composed of one tetracationic diphosphine ligand and one complementary tetraanionic calix[4]arene are described. Encapsulation of a palladium atom within a diphosphine capsule is achieved successfully by using the metal complex of the tetracationic diphosphine ligand for the assembly process. In this templated approach to metal encapsulation, the transition-metal complex is an integrated part of the capsule with the transition metal located inside the capsule and is not involved in the assembly process. We present two approaches for capsule assembly by mixing solutions of the precharged building blocks in methanol and mixing solutions of the neutral building blocks in methanol. The scope of the diphosphine capsules and the metallodiphosphine capsules is easily extended by applying tetracationic diphosphine ligands with different backbones (ethylene, diphenyl ether, and xanthene) and cationic binding motifs (p-C(6)H(4)-CH(2)-ammonium, m-C(6)H(4)-ammonium, and m-C(6)H(4)-guanidinium). These tetracationic building blocks with different flexibilities and shapes readily associate into capsules with the proper capsular structure, as is indicated by (1)H NMR spectroscopy, 1D NOESY, ESI-MS, and modeling studies.

Topics: Calixarenes; Capsules; Catalysis; Coordination Complexes; Palladium; Phenols; Phosphines; Transition Elements

A calix[4]arene conjugate bearing salicylyl imine having dibenzyl moiety (L) has been synthesized and characterized, and its ability to recognize three most important essential elements of human system, viz., iron, copper, and zinc, has been addressed by colorimetry and fluorescence techniques. L acts as a sensor for Cu(2+) and Fe(2+) by exhibiting visual color change and for Zn(2+) based on fluorescence spectroscopy. L shows a minimum detection limit of 3.96 ± 0.42 and 4.51 ± 0.53 ppm and 45 ± 4 ppb, respectively, toward Fe(2+), Cu(2+), and Zn(2+). The in situ prepared [ZnL] exhibits phosphate sensing among 14 anions studied with a detection limit of 247 ± 25 ppb. The complexes of Zn(2+), Cu(2+), and Fe(2+) of L have been synthesized and characterized by different techniques. The crystalline nature of the zinc and copper complexes and the noncrystalline nature of simple L and its iron complex have been demonstrated by powder XRD. The structures of Cu(2+) and Zn(2+) complexes have been established by single crystal XRD wherein these were found to be 1:1 monomeric and 2:2 dimeric, respectively, using N(2)O(2) as binding core. The geometries exhibited by the Zn(2+) and the Cu(2+) complexes were found to be distorted tetrahedral and distorted square planar, respectively. The iron complex of L exists in 1:1 stoichiometry as evident from the mass spectrometry and elemental analysis.

Topics: Absorption; Amines; Calixarenes; Chemistry Techniques, Analytical; Color; Copper; Crystallography, X-Ray; Humans; Imines; Iron; Models, Molecular; Molecular Conformation; Organometallic Compounds; Phenols; Phosphates; Spectrometry, Fluorescence; Zinc

Self-assembly and characterization of heterodimeric diphosphine capsules formed by multiple ionic interactions are described. The first type of capsules is composed of one novel tetrasulfonato-xantphos ligand and one complementary tetraammonium calix[4]arene. Encapsulation of a transition metal is achieved by self-assembly of a rhodium complex containing the tetraanionic diphosphine ligand and a tetracationic calix[4]arene. The second type of capsules is composed of two oppositely charged diphosphine ligands: one tetrasulfonato-xantphos and one tetraammonium-diphosphine (of the xantphos-, DPEphos-, and 1,2-bis(diphenylphosphino)ethane (dppe)-type). Bis(metallo) capsules, that is, simultaneous encapsulation of two different transition metals, are created by self-assembly of a palladium or platinum complex containing a tetracationic ligand and a rhodium complex containing a tetraanionic ligand. Diphosphine ligands with different flexibilities and shapes assemble into metallocapsules with a proper capsular structure, as is indicated by (1)H NMR and 1D-NOESY spectroscopy, ESIMS, and modeling studies.

Topics: Calixarenes; Capsules; Ligands; Palladium; Phenols; Phosphines; Platinum; Rhodium; Transition Elements

A bis-alkynyl calix[4]arene Au(I) isocyanide complex has been synthesized and demonstrated to be a selective ion probe for Al(3+) based on Au(I)Au(I) interactions.

Topics: Aluminum; Calixarenes; Coordination Complexes; Cyanides; Gold; Hydrogen Bonding; Ions; Phenols

Atomic force microscopy reveals that Pseudomonas aeruginosa LecA (PA-IL) and a tetra-galactosylated 1,3-alternate calix[4]arene-based glycocluster self-assemble according to an aggregative chelate binding mode to create monodimensional filaments. Lectin oligomers are identified along the filaments and defects in chelate binding generate branches and bifurcations. A molecular model with alternate 90° orientation of LecA tetramers is proposed to describe the organisation of lectins and glycoclusters in the filaments.

Topics: Adhesins, Bacterial; Binding Sites; Calixarenes; Glycosylation; Microscopy, Atomic Force; Phenols; Pseudomonas aeruginosa

A series of novel calix[4]arene enones (5-7) and cinnamates (12-14) have been synthesized and evaluated for ensuring protection from ultraviolet radiation (UVR). Spectroscopic analyses has revealed that compound 6 absorbs ultraviolet radiations between 280 and 350 nm with an absorption maximum at 312 nm. Its molar absorption coefficient (ε) (>5 × 10(4)M(-1)cm(-1)) and bandwidth are larger than those for the commercially used sun protectants (oxybenzone (OB), 2-ethylhexyl 4-methoxycinnamate (OMC) and avobenzone). The in vitro Sun Protection Factor (SPF) measurement revealed an SPF of 5.2 at 2% concentration of 6 in home made emulsion formulations while combination of 2% each of 6 and OMC gave an SPF of 8.8. Lower sun protection seems to be compensated by significant protection from more harmful UVA radiations (UVA/UVB absorbance ratio of 0.62).

Topics: Calixarenes; Cinnamates; Humans; Isomerism; Phenols; Skin; Spectrophotometry, Ultraviolet; Sunscreening Agents; Ultraviolet Rays

The first example of a folate-calix[4]arene conjugate was designed and synthesized via microwave-assisted click chemistry. In PBS medium at physiological pH, the conjugate formed soluble aggregates and showed the capability to improve the water-solubility of a hydrophobic drug model, such as indomethacin.

Topics: Calixarenes; Chemistry Techniques, Synthetic; Click Chemistry; Drug Design; Folic Acid; Indomethacin; Microwaves; Molecular Structure; Phenols; Solubility; Stereoisomerism

The complexation of nucleosides and nucleotides by hybrid nanoparticles capped by para-sulfonato-calix[4]arene shows clear discrimination between purine and pyrimidine based molecules. For the pyrimidine nucleotides there is appearance of a new absorption band around 550 nm, and a colour change from yellow to orange red and pink.

Topics: Calixarenes; Colorimetry; Metal Nanoparticles; Nucleosides; Nucleotides; Phenols; Silver; Spectrophotometry

The complexes between the host calix[4]arene (C4A) and various guest molecules such as NH(3), N(2), CH(4), and C(2)H(2) have been investigated via experimental and theoretical methods. The S(1)-S(0) electronic spectra of these guest-host complexes are observed by mass-selected resonant two-photon ionization (R2PI) and laser-induced fluorescence (LIF) spectroscopy. The IR spectra of the complexes formed in molecular beams are obtained by IR-UV double resonance (IR-UV DR) and IR photodissociation (IRPD) spectroscopy. The supramolecular structures of the complexes are investigated by electronic structure methods (density functional and second order perturbation theory). The current results for the various molecular guests are put in perspective with the previously reported ones for the C4A-rare gas (Rg) (Phys. Chem. Chem. Phys. 2007, 126, 141101) and C4A-H(2)O complexes (J. Phys. Chem. A, 2010, 114, 2967). The electronic spectra of the complexes of C4A with N(2), CH(4), and C(2)H(2) exhibit red-shifts of similar magnitudes with the ones observed for the C4A-Rg complexes, whereas the complexes of C4A with H(2)O and NH(3) show much larger red-shifts. Most of the IR-UV DR spectra of the complexes, except for C4A-C(2)H(2), show a broad hydrogen-bonded OH stretching band with a peak at ~3160 cm(-1). The analysis of the experimental results, in agreement with the ones resulting from the electronic structure calculations, suggest that C4A preferentially forms endo-complexes (guests inside the host calizarene cavity) with all the guest species reported in this study. We discuss the similarities and differences of the structures, binding energies, and the nature of the interaction between the C4A host and the various guest species.

Topics: Acetylene; Ammonia; Calixarenes; Hydrogen Bonding; Lasers; Methane; Nitrogen; Phenols; Quantum Theory; Spectrometry, Fluorescence; Spectrophotometry, Infrared

The calix[4]arene-imidazolium salts 5-(3-butyl-1-imidazolylium)-25,26,27,28-tetrabenzyloxy-calix[4]arene bromide (cone) (2), and 5,11-bis(3-alkyl-1-imidazolylium)-25,26,27,28-tetrabenzyloxycalix[4]arene diiodide (cone) (R = methyl, 3a; R = n-butyl, 3b) have been synthesised. Reaction of 2 in dioxane with PdCl(2) in the presence of CsCO(3) and KBr (80 °C, 24 h) gives the carbene complex trans-[PdBr(2)(calix-monocarbene)(2)] (14), containing two N-heterocyclic carbene ligands derived from 2 (yield: 63%). Repeating the reaction in pyridine instead of dioxane gives the mixed pyridine-carbene complex trans-[PdBr(2)(calix-carbene)(pyridine)] (15) in 75% yield. Treatment of the bis-imidazolium salt 3a with [Pd(OAc)(2)] affords a chelate complex, trans-[PdI(2){calix-bis(carbene)}] (16), in which a metallo-(bis-carbene) fragment caps the upper rim of the calixarene basket. Complex 16, as well as its analogue 17, obtained from 3b, display apparent C(s)-symmetry in solution. This is not the case in the solid state, a single X-ray diffraction study carried out for 16 revealing a pinced cone structure for the calixarene skeleton, which reduces the symmetry to C(1). The chelate complex 17 shows poor activity in Suzuki-Miyaura cross-coupling of phenyl boronic acid and p-tolyl halides, an observation that suggests the presence of a strained metallocyclic unit preventing easy stereochemical rearrangement to an active species. Unlike 17, complexes 14 and 15 show good activities in cross-coupling. A comparative study using the carbene precursor 1-butyl-3-(2,6-diisopropylphenyl)imidazolium bromide (18), which is devoid of the receptor fragment, strongly suggests that the carbene ligands of 14 and 15 operate typically as bulky NHC-ligands.

Topics: Calixarenes; Coordination Complexes; Crystallography, X-Ray; Heterocyclic Compounds; Imidazoles; Methane; Models, Molecular; Molecular Conformation; Palladium; Phenols; Stereoisomerism

Reactions of [H(4)L][PF(6)](4) with 4 equiv. of Mn(OAc)(2)·4H(2)O in the presence of air gave rise to a mononuclear Mn(III)-superoxo complex [Mn(III)L(O(2))(H(2)O)](PF(6))(2), which contains a bowl-shaped cationic structure with a D(4d) symmetry. It has an unprecedented linear end-on Mn(III)-O(2) unit and exhibited good efficiency and selectivity in the catalytic oxidation of alkenes with O(2) plus isobutyraldehyde under mild conditions.

Topics: Alkenes; Calixarenes; Catalysis; Electron Transport; Epoxy Compounds; Manganese; Organometallic Compounds; Oxygen; Phenols

A new 1,3-di-capped calix[4]arene conjugate of salicylidene (L) has been synthesized, characterized and the structure has been established by single crystal XRD. L shows selectivity towards Hg(2+) in ethanol by turn-on fluorescence among the biologically important metal ions studied. The species of recognition has been modeled by DFT computational calculations to result in conformational changes in the arms that support the turn-on fluorescence behaviour.

Topics: Calixarenes; Environmental Monitoring; Environmental Pollutants; Fluorescence; Magnetic Resonance Spectroscopy; Mercury; Molecular Conformation; Phenols; Schiff Bases; Spectroscopy, Fourier Transform Infrared; X-Ray Diffraction

Topics: Calixarenes; Cross-Linking Reagents; Crown Compounds; Dimerization; Ions; Magnetic Resonance Imaging; Models, Chemical; Phenols; Porphyrins; Pyrroles; Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization

Noncovalent binding of fullerenes to bisporphyrins was studied in the gas phase by energy-dependent collision-induced dissociation (CID) with Xe under single-collision conditions. The electrospray ionization mass spectra of calix[4]arene-linked bisporphyrins show that bisporphyrins take up to 3-4 protons, depending on the type of meso-substituents. Of the protonated bisporphyrins, the diprotonated species form stable 1:1 complexes with fullerenes (C(60) and C(70)). CID cracking patterns of the diprotonated bisporphyrins indicate that each monomeric porphyrin moiety is singly protonated. CID yield-energy curves obtained from the 1:1 diprotonated bisporphyrin-fullerene complexes suggest that a fullerene occupies the endo-binding site intercalated between the two singly protonated porphyrin moieties. In the cases of 1:2 diprotonated bisporphyrin-fullerene complexes, CID results show that one fullerene binds inside (endo-binding) and the other outside (exo-binding). The exo-binding mode is energetically almost identical to the binding of fullerenes to singly protonated porphyrin monomers. The endo-binding energy is at least twice the exo-binding energy. To gain insights into the binding mode, we optimized structures of diprotonated bisporphyrins and their 1:1 endo-complexes with fullerenes, and calculated the endo-binding energy for C(60), C(70) (end-on), and C(70) (side-on). The endo-binding of fullerenes to diprotonated bisporphyrins nearly doubles the π-π interactions while reducing the electrostatic repulsion between the two singly protonated porphyrin moieties. The side-on binding of C(70) is favored over the end-on binding because the former exerts less steric strain to the lower rim of calixarene.

Topics: Binding Sites; Calixarenes; Fullerenes; Models, Molecular; Phenols; Porphyrins; Protons; Spectrometry, Mass, Electrospray Ionization

Topics: Anions; Binding Sites; Calixarenes; Ion Transport; Lipid Bilayers; Models, Molecular; Phenols

Two calix[4]arene tetracarboxylates, [calix[4]arene tetraacetate (K(4)CTA) and calix[4]arene tetrabenzoate (K(4)CTB)] as their potassium salts, have been prepared. Employing these as precursors, two Ag(I) coordination polymers incorporating calix[4]arene units have been successfully prepared and their X-ray crystal structures have been determined. In these, the CTA and CTB derivatives are linearly bound to two and four silver atoms, respectively, to generate unusual tubular nanostructures. A comparative NMR study was undertaken to investigate the nature of the metal ion blocking of the tube as observed in the CTA-derived structure. The thermal properties for both coordination polymers were also examined.

Topics: Calixarenes; Carboxylic Acids; Catalysis; Models, Molecular; Molecular Conformation; Phenols; Polymers; Silver; Solvents; Temperature

We developed a metalloporphyrin-based molecular container capped with a calix[4]arene, and its rigid cavity distinguished the slight structural differences in the aromatic guests.

Topics: Calixarenes; Capsules; Metalloporphyrins; Models, Molecular; Molecular Conformation; Phenols; Substrate Specificity; Thermodynamics

Topics: Biosensing Techniques; Calixarenes; Cysteine; Phenols; Proteins; Triazoles; Zinc Compounds

The structure of the calix[4]arene(C4A)-(H(2)O) cluster formed in a supersonic beam has been investigated by mass-selected resonant two-photon ionization (R2PI) spectroscopy, IR-UV double resonance spectroscopy, IR photodissociation (IRPD) spectroscopy and by high-level quantum chemical calculations. The IR-UV double resonance spectrum of C4A-(H(2)O) exhibits a broad and strong hydrogen-bonded OH stretching band at 3160 cm(-1) and a weak asymmetric OH stretching band at 3700 cm(-1). The IRPD measurement of the cluster produced a value of 3140 cm(-1) for the C4A-(H(2)O) --> C4A + H(2)O dissociation energy. High-level electronic structure calculations at the MP2 level of theory with basis sets up to quadruple-zeta quality suggest that the endo-isomer (water inside the C4A cavity) is approximately 1100 cm(-1) more stable than the exo-isomer (water hydrogen bonded to the rim of C4A). The endo-isomer has a best-computed (at the MP2/aug-cc-pVQZ level) value of 3127 cm(-1) for the binding energy, just approximately 15 cm(-1) shy of the experimentally determined threshold and an IR spectrum in excellent agreement with the experimentally observed one. In contrast, the B3LYP density functional fails to even predict a stable structure for the endo-isomer demonstrating the inability of that level of theory to describe the delicate balance between structures exhibiting cumulative OH-pi H-bonding and dipole-dipole interactions (endo-isomer) when compared to the ones emanating from maximizing the cooperative effects associated with the formation of hydrogen bonded homodromic networks (exo-isomer). The comparison of the experimental results with the ones from high-level electronic structure calculations therefore unambiguously assign the endo-isomer as the global minimum of the C4A-(H(2)O) cluster, world's smallest cup of water.

Topics: Calixarenes; Computer Simulation; Hydrogen Bonding; Isomerism; Models, Chemical; Molecular Structure; Phenols; Water

The layer-by-layer (LbL) assembled thin films containing tetraamino-thiacalix[4]arenes (1) and tetraamino-calix[4]arenes (2) were used as nanoreactor to synthesize in situ Ag nanoparticles (Ag NPs). UV-vis spectra and AFM images demonstrate that Ag NPs are included in the (1/Ag NPs)(n) and (2/Ag NPs)(n) multilayer films. The silver ions are absorbed through cation-pi interaction and calix[4]arene-metal ion coordination interaction and are reduced into Ag NPs by calix[4]arenes. TEM images indicated that Ag NPs within aminocalix[4]arene multilayers were highly dispersed and uniform. Moreover, the mean size of Ag NPs is smaller than 10 nm.

Topics: Calixarenes; Metal Nanoparticles; Microscopy, Atomic Force; Microscopy, Electron, Transmission; Models, Chemical; Molecular Structure; Nanostructures; Phenols; Photoelectron Spectroscopy; Polyethyleneimine; Silver; Silver Nitrate; Spectrophotometry, Ultraviolet; Spectroscopy, Fourier Transform Infrared

Cell cycle progression is dependent on the intracellular iron level, and chelators lead to iron depletion and decrease cell proliferation. This antiproliferative effect can be inhibited by exogenous iron. In this work, we present the synthesis of new synthetic calix[4]arene podands bearing alkyl acid and alkyl ester groups at the lower rim, designed as potential iron chelators. We report their effect on cell proliferation, in comparison with the new oral chelator ICL670 (4-[3,5-bis-(2-hydroxyphenyl)-1,2,4-triazol-1-yl]-benzoic acid). The antiproliferative effect of these new compounds was studied in human hepatocarcinoma HepaRG cell cultures using the MTT assay. Their cytotoxicity was evaluated by extracellular LDH activity. Preliminary results indicate that their antiproliferative effect is due to their cytotoxicity. The efficiency of these compounds, comparable to that of ICL670, was independent of iron depletion. This effect remains to be further explored. Moreover, it also shows that novel substituted calix[4]arenes could open the way to new valuable medicinal chemistry scaffolding.

Topics: Benzoates; Calixarenes; Cell Line, Tumor; Cell Proliferation; Deferasirox; Drug Design; Humans; Iron; Iron Chelating Agents; Phenols; Triazoles

A polyvinylchloride (PVC) based liquid membrane ion selective electrode (ISE) for cesium was fabricated with 5-(4'-nitrophenylazo)25,27-bis(2-propyloxy)26,28-dihydroxycalix[4]arene as ionophore. Different membrane constituents were investigated to realise optimum performance of the ISE developed. Of the four plasticizers and two ion additives studied, the best response was observed with membrane having 2-nitro phenyl octyl ether (oNPOE) as plasticizer and potassium tetrakis (perchloro phenyl) borate (KTpClPB) as ion additive. Linear response over concentration range of 10(-5)-10(-1)M CsCl was obtained. The Nernstian slope of the response was 56 mV per decade for Cs with a response time less than 20s. Matched potential method has been applied to find out the selectivity for Cs over several ions like Rb(+), K(+), Na(+), NH(4)(+), Sr(2+), Ba(2+), Ca(2+), Mg(2+), Cu(2+), Pb(2+), Zn(2+), Ni(2+) and Ce(3+). The response of ISE for Cs(+) was fairly constant over the pH range of 3-11. The lifetime of the electrode is 9 months which is the longest life for any membrane-based Cs-ISE so far developed. The concentration of cesium in two simulated high level active waste streams was determined and results agreed well with those obtained independently employing atomic absorption spectrometry.

Topics: Calixarenes; Cesium; Chlorides; Electrochemistry; Hydrogen-Ion Concentration; Ion-Selective Electrodes; Ions; Membranes, Artificial; Phenols; Plasticizers; Polyvinyl Chloride; Potentiometry; Radioactive Waste; Rivers; Spectrophotometry, Atomic; Water Pollutants, Chemical

Three different strategies have been followed to develop the torsional force-field parameters of the inter-ring dihedral angles for calix[4]arene-substituted poly(thiophene)s, a family of highly sensitive ion receptors. These procedures, which are based on the rotational profiles calculated using quantum mechanical methods, differ in the complexity of the model compounds and the processing applied to the quantum mechanical energies before the fitting. The performance of the three sets of developed parameters, which are essentially compatible with the General Amber Force Field, has been evaluated by computing the potential of mean forces for the inter-ring rotation of 2,2'-bithiophene, and its substituted analog bearing a calix[4]arene group in different environments. Finally, the ability of the new sets of torsional parameters to describe a calix[4]arene-substituted poly(thiophene) in tetrahydrofuran solution has been checked using Molecular Dynamics simulations. Specifically, the molecular shape, the polymer conformation, and the effects of the Na(+) ions trapped in the cavity of the receptor have been examined. Although the potential derived from unsubstituted 2,2'-bithiophene is able to reproduce the experimental free energies of the minima, the overall results indicate that the parameters derived from the analog bearing a calix[4]arene group provide the best description of the systems under study. This should be attributed to the strong constraints found in complex substituted poly(thiophene)s, which require parameterization strategies able to capture all the interactions and phenomena involved in their inter-ring rotations.

Topics: Calixarenes; Molecular Dynamics Simulation; Phenols; Polymers; Quantum Theory; Thiophenes

A pyridine-N-oxide functionalized DOTA analogue has been conjugated to a calix[4]arene and the corresponding Gd-complex was characterized with respect to its suitability as MRI contrast agent. The compound forms spherical micelles in water with a cmc of 35 microM and a radius of 8.2 nm. The relaxivity of these aggregates is 31.2 s(-1) mM(-1) at 25 degrees C and 20 MHz, which corresponds to a molecular relaxivity of 125 s(-1) mM(-1). The high relaxivity mainly originates from the short tau(M) (72.7 ns) and the size of the micelles. The interaction with bovine serum albumin (BSA) was studied and an observed relaxivity of up to 40.8 s(-1) mM(-1) (163.2 s(-1) mM(-1) per binding place) at 20 MHz and 37 degrees C was found in the presence of 2.0 mM protein.

Topics: Animals; Calixarenes; Cattle; Chelating Agents; Contrast Media; Gadolinium; Heterocyclic Compounds; Magnetic Resonance Imaging; Micelles; Models, Molecular; Organometallic Compounds; Phenols; Protein Binding; Serum Albumin, Bovine; Water

We present the first type of tetraazide-functionalized calix[4]arene TiO(2) nanoparticles and their coupling to propargyl glycosides under Cu(I)-catalysis (click reaction), resulting in the immobilization of calix[4]arene-based glycoclusters on the TiO(2) surface.

Topics: Alkynes; Azides; Calixarenes; Catalysis; Copper; Glycosides; Nanoparticles; Phenols; Titanium

In this study, 5,17-bis-[(N-methylglucamine)methyl]-25,26,27,28-tetrahydroxy-calix[4]arene (3) was synthesized by the treatment of calix[4]arene with a secondary amine N-methylglucamine and formaldehyde. The calixarene derivative (3) was characterized by a combination of FTIR, (1)H NMR and elemental analyses. Followingly, using the macrocyclic building block, the compound 3 was immobilized by [3-(2,3-epoxypropoxy)propyl]trimethoxysilane-modified Fe(3)O(4) magnetite nanoparticles (EPPTMS-MN). The prepared calix[4]arene immobilized material was characterized by a combination of Fourier transform infrared spectroscopy (FTIR), transmission electron microscopy (TEM) and thermogravimetric analyses (TGA). Moreover, the studies regarding the removal of arsenate and dichromate ions from the aqueous solutions were also carried out by using the compound in solid-liquid extraction experiments. It was found that the calix[4]arene-based magnetic material has high extraction ability towards dichromate and arsenate anions in 66% (at pH 1.5) and in 86% (at pH 3.5), respectively.

Topics: Adsorption; Arsenates; Calixarenes; Chromates; Chromatography, Thin Layer; Ferrosoferric Oxide; Hydrogen-Ion Concentration; Indicators and Reagents; Magnetic Resonance Spectroscopy; Magnetics; Meglumine; Microscopy, Electron, Transmission; Nanoparticles; Phenols; Solvents; Spectrophotometry, Ultraviolet; Spectroscopy, Fourier Transform Infrared; Thermogravimetry

The chemically switchable actions well imitate the function of a "molecular syringe," has been studied in theory using the 1,3-alternate calix [4]arene bearing a nitrogen-containing crown cap at one side and a bis(ethoxyethoxy) group at another side by the pi-basic calixtube as a pipette and the crown ring as a rubber cap. The model is characterized by geometry optimization using density functional theory (DFT) at B3LYP/6-31G level. The obtained optimized structures are used to perform natural bond orbital (NBO) and frequency analysis. The electron-donating heteroatoms: O and N offer lone pair electrons to the contacting RY* (1-center Rydberg) or LP* (1-center valence antibond lone pair) orbitals of K(+), Ag(+). The results indicate that when the nitrogen atom in the crown ring is protonated, K(+) and Ag(+) will be pushed out to the bis(ethoxyethoxy) side through a pi-basic calixtube. When the nitrogen.H(+) in the crown ring is deprotonated, K(+) and Ag(+) are sucked back to the crown-capped side again. In the course of the coordination, both the intermolecular electrostatic interactions and the cation-pi interactions between the metal ion and pi-orbitals of the two pairs facing inverted benzene rings play a significant role. It is believed that this prototype of a "molecular syringe" is a novel molecular architecture for the action of metal cations.

Topics: Binding Sites; Calixarenes; Cations; Computer-Aided Design; Ligands; Metals; Molecular Mimicry; Nitrogen; Oxygen; Phenols; Protons; Quantum Theory; Silver; Thermodynamics

Using a calix[4]arene-benzene complex as a test system, we compare the potential of mean force for when the calix[4]arene is tethered versus free. When the complex is in vacuum, our results show that the difference between tethered and free is primarily due to the entropic contribution to the potential of mean force resulting in a significant binding free energy difference of 6.6 kJ/mol. By contrast, when the complex is in water, our results suggest that there is no appreciable difference between tethered and free. This study elucidates the roles of entropy and enthalpy for this small molecule system and emphasizes the point that tethering the receptor has the potential to dramatically impact the binding properties. These findings should be taken into consideration when using calixarene molecules in nanosensor design.

Topics: Benzene; Calixarenes; Computer Simulation; Models, Molecular; Molecular Conformation; Phenols; Thermodynamics; Water

A new 1,3-diderivative of calix[4]arene appended with hydroxymethyl salicylyl imine has been synthesized and its ion recognition toward biologically relevant M(n+) ions studied. The receptor H(2)L showed selectivity toward Zn(2+) by switch-on fluorescence among the 12 metal ions studied with a detection limit of 192 ppb. The interaction of Zn(2+) with H(2)L has been further supported by absorption studies, and the stoichiometry of the complex formed (1:1) has been established on the basis of absorption and ESI MS. Competitive ion titrations carried out reveal that the Zn(2+) can be detected even in the presence of other metal ions of bioimportance. The mode of interaction of Zn(2+) with conjugate has been established by a fleet of computational calculations carried out in a cascade manner, either on the ligand or on the complex, wherein the final optimizations were carried out by the density functional theory (DFT) and found that the Zn(2+) and Cd(2+) indeed bind differently. In situ prepared [ZnL] complex responds to both inorganic phosphate as well as AMP, ADP, and ATP with a minimum detection limit of 426 ppb wherein the Zn(2+) from the complex is detached and recomplexed by the added phosphate moiety. It has been possible to build an INHIBIT logic gate for the conjugate using Zn(2+) and HPO(4)(2-) as inputs by monitoring the fluorescence emission band at 444 nm as output. The amino acid sensing abilities of [ZnL] have been explored by fluorescence and absorbance spectroscopy where it showed selectivity toward Cys, Asp, and His through the formation of the Zn(2+) complex of these amino acids by chelating through their side chain moieties. Thus, while H(2)L is selective for Zn(2+) among a number of cations, the [ZnL] is selective toward phosphate among a number of anions and also toward Asp, Cys, and His among the naturally occurring amino acids.

Topics: Amino Acids; Calixarenes; Computer Simulation; Ligands; Molecular Structure; Organometallic Compounds; Phenols; Phosphates; Salicylates; Stereoisomerism; Zinc

The racemate of an inherently chiral meta-substituted calix[4]arene derivative 3 has been resolved via enantioselective HPLC. Measured optical rotation dispersion and electronic circular dichroism have been compared with DFT theoretical predictions. The comparison indicates that the absolute configuration of the dextrorotatory enantiomer (+)-3 is cS. The procedure has been successfully tested against a literature precedent confirming the validity of the method.

Topics: Calixarenes; Computer Simulation; Models, Chemical; Molecular Conformation; Phenols; Stereoisomerism

In the present study four new calix[4]arene amide ionophores (4-7) have been prepared by aminolysis of calix[4]arene diester (3) and investigated their extraction ability toward phosphate and dichromate anions at different pH. The (1)H NMR data showed that the synthesized compounds exist in the cone conformation. Liquid-liquid extraction experiments have been performed to evaluate the dichromate and phosphate anions extraction efficiency of both calix[4]arene bearing amide-pyridinium units (4-7) and the calix[4]arene derivative bearing aminomethyl pyridinium units (8, 9). It was observed that, compounds 4-7 exhibited lower affinity toward phosphate ions than the calix[4]arene derivative bearing amine pyridinium units (8, 9). The extraction of phosphate and dichromate anions by these compounds indicates that the partially protonated pyridyl or amino groups play the major role for the formation of hydrogen bonds and electrostatic interactions.

Topics: Calixarenes; Chromates; Hydrogen Bonding; Hydrogen-Ion Concentration; Ionophores; Molecular Conformation; Phenols; Phosphates; Protons; Solutions; Static Electricity; Water Pollutants, Chemical

Two cyclic octanuclear complexes, 2 and 3, of cation composition [{Pd(bpy)}(8)C(4)](8+) (bpy = 2,2'-bipyridine) form side by side when [Pd(bpy)(H(2)O)(2)](2+) and cytosine (H(2)C) are reacted in water. The two complexes are isomers, composed of central metallacalix[4]arene backbones to which four additional Pd(bpy) units are bonded pairwise to exocyclic groups of the C(2-) ligands. As a consequence of differences in the N1-N3 connectivity patterns of the two central Pd(4)C(4) rings and 1,3-alternate rotamer states of cytosinate in both compounds, the spatial arrangements of exocyclic groups are distinctly different, leading to two Pd(3) stacks and two Pd(1) entities in 2, yet to four Pd(2) stacks in 3.

Topics: 2,2'-Dipyridyl; Calixarenes; Cations; Cytosine; Isomerism; Models, Molecular; Palladium; Phenols

Synthetic strategies are described to synthesize the calix[4]arene diamine 4 of partial cone (paco) conformation, which on condensation with 9-anthracene carbaldehyde forms the chemosensor 5 in paco conformation. The chemosensor 5 undergoes fluorescence enhancement in the presence of Ni(2+) ions.

Topics: Calixarenes; Chemistry Techniques, Analytical; Imines; Molecular Conformation; Nickel; Phenols; Spectrometry, Fluorescence; Stereoisomerism

A novel calix[4]arene derivative locked in the 1,3-alternate conformation (2) bearing two pyrene and rhodamine fluorophores was synthesized as a selective sensor for the Hg(2+) ion. The sensoring is based on FRET from pyrene excimer emissions to ring-opened rhodamine absorption upon complexation of the Hg(2+) ion. Addition of Hg(2+) to a mixed solution of 2 gave significantly enhanced fluorescence at ∼576 nm via FRET with excitation at 343 nm. We also found that the pyrene excimer emissions formed by the intramolecular π-π interactions are more effective in obtaining strong FRET bands than those by intermolecular π-π interactions.

Topics: Calixarenes; Chemistry Techniques, Analytical; Dimerization; Fluorescence Resonance Energy Transfer; Mercury; Phenols; Pyrenes; Rhodamines; Spectrometry, Fluorescence; Spectrophotometry, Ultraviolet

We report the first synthesis of a dendritic multicalixarene, featuring twenty-one calixarene units, which when adsorbed onto mica, forms regular assemblies which can then further aggregate to form larger clusters.

Topics: Calixarenes; Dendrimers; Microscopy, Atomic Force; Nanostructures; Phenols

A Mannich base derivative of 5,11,17,23-tetrakis-[(1,4-dioxa-8-azaspiro-[4.5]decanyl)methyl]-25,26,27,28-tetrahydroxy calix[4]arene 3 was synthesized by the treatment of calix[4]arene with a cyclic secondary amine (1,4-dioxa-8-azaspiro-[4.5]decane) and formaldehyde. The compound 3 was treated with dibromoxylene to obtain a calix[4]arene-based copolymer 4. In batch sorption experiments of selected carcinogenic azo dyes and aromatic amines, the compounds 3 and 4 were found to be a better sorbent for azo dyes than for the aromatic amines. It was observed that the percentage of azo dye removal was 95-99% for compound 3 and 83-97% for 4 when the pH of the dye solution was in the range of 2.0-8.0. The sorption of azo dyes and aromatic amines by calix[4]arenes-based compounds indicates that amino groups play the major role for the formation of hydrogen bonds and electrostatic interactions.

Topics: Amines; Azo Compounds; Calixarenes; Carcinogens; Coloring Agents; Hydrogen Bonding; Phenols; Polymers; Static Electricity

Efficient access to the bis(imidazolyl)calixarene 2 and dicationic bis(imidazolium) salts 1a,b x 2X directly bonded to the upper rim of calixarene structure has been reported. Anion binding properties of the new receptors were studied by 1H NMR spectroscopic methods. Bis(N-butylimidazolium) dication 1a exhibited the best recognition properties toward carboxylate anions with a 1:1 receptor-anion binding stoichiometry, whereas the presence of a bulky group such as isopropyl (1b) increased the difficulty of both imidazolium moieties to be able to support the association with the same single anion.

Topics: Anions; Binding Sites; Calixarenes; Catalysis; Copper; Imidazoles; Iodides; Magnetic Resonance Spectroscopy; Molecular Conformation; Phenols

A new poly(vinyl chloride)-based membranes containing p-(4-n-butylphenylazo)calix[4]arene (I) as an electroactive material along with sodiumtetraphenylborate (NaTPB), and dibutyl(butyl)phosphonate in the ratio 10:100:1:200 (I:DBBP:NaTPB:PVC) (w/w) was used to fabricate a new cobalt(II)-selective sensor. It exhibited a working concentration range of 9.2 x 10(-6) to 1.0 x 10(-1)M, with a Nernstian slope of 29.0+/-1.0 mV/decade of activity and the response time of 25s. This sensor shows the detection limit of 4.0 x 10(-6)M. Its potential response remains unaffected of pH in the range, 4.0-7.2, and the cell assembly can be used successfully in partially non-aqueous medium (up to 10%, v/v) without significant change in the slope of working concentration range. The sensor has a lifetime of about 3 months and exhibits excellent selectivity over a number of mono-, bi-, and tri-valent cations including alkali, alkaline earth metal, heavy and transition metal ions. It can be used as an indicator electrode for the end point determination in the potentiometric titration of cobalt ions against ethylenediaminetetraacetic acid (EDTA) as well as for the determination of cobalt ion concentration in real samples.

Topics: Azo Compounds; Calixarenes; Cobalt; Electrons; Hydrogen-Ion Concentration; Molecular Structure; Phenols; Potentiometry; Solutions; Time Factors; Titrimetry

Three new silica gel-immobilized calix[4]arene polymers 9-11 have been prepared via modification of calix[4]arene mono amido derivatives 3-5 with 3-aminopropyl triethoxysilane (APTES) and activated silica gel, respectively. The polymers were characterized by Fourier transform infrared spectroscopy, elemental analysis and thermal gravimetric analysis. The solid-liquid extraction properties of ligands 3-5 along with their immobilized derivatives 9-11 towards dichromate (HCr(2)O(7)(-)/Cr(2)O(7)(2-)) anions were reported. It was found that these calix[4]arene-based polymers have high extraction abilities towards dichromate anions as compared to their monomeric precursors.

Topics: Adsorption; Calixarenes; Chromates; Phenols; Polymers; Propylamines; Silanes; Silica Gel; Silicon Dioxide

Calixarenes are interesting building blocks in supramolecular receptor design. They can be easily functionalized to give the desired guest binding and sequestration properties. We demonstrate here the use of simple alkylated calixarenes as novel NO(2) sensors. Upon reacting with gaseous NO(2), alkylated calixarenes form stable calixarene-NO(+) (nitrosonium) complexes that have a deep purple color. This specific and selective formation of the colored complex was used to develop a fiber optic based colorimetric NO(2) sensor. Several alkylated calixarenes are used and tested as sensing materials. The calixarene compound was immobilized on a fine mesh silica-gel coated thin layer chromatography plate. The sensing plate was coupled with a fiber optic based photodetector. Gas samples were sampled in a manner where they impinged on the surface of sensing plate. The light transmission through the plate was continuously monitored. For a 5 min sample, the limit of detection was 0.54 ppmv with 1,3-alternate O-hexyl calix[4]arene (1a). There were no significant response differences between different conformations of calixarenes such as 1,3-alternate or cone. This chemistry can form the basis of a colorimetric sensor that relies on extant filter tape technology. With calixarenes however, such a reaction is potentially reversible - color formed upon reaction with NO(2) can be reversed by flushing the sensing plate by purified air. While we found that the removal of the developed color can be accelerated by simultaneous heating and suction, permitting the reuse of the same sensing area multiple times, we also observed that the sensitivity gradually decreased. The nitrosonium calixarene derivative tends to transform to the nitrated form; this process is catalyzed by light. Several methylated calixarenes were synthesized and tested but a fully satisfactory solution has proven elusive.

Topics: Calixarenes; Color; Colorimetry; Gases; Nitrogen Dioxide; Optical Fibers; Phenols

The utility of p-sulphonatocalix[4]arene (s-CX[4]) as a drug delivery vehicle for multinuclear platinum anticancer agents, using trans-[{PtCl(NH(3))(2)}(2)mu-dpzm](2+) (di-Pt; where dpzm=4,4'-dipyrazolylmethane) as a model complex, has been examined using (1)H nuclear magnetic resonance, electrospray ionisation mass spectrometry, molecular modelling and in vitro growth inhibition assays. s-CX[4] binds di-Pt in a side-on fashion in a ratio of 1:1, with the dpzm ligand of the metal complex located within the s-CX[4] cavity with binding further stabilised by ion-ion interactions and hydrogen bonding between the metal complex am(m)ine groups and the s-CX[4] sulphate groups. Partial encapsulation of di-Pt within the cavity does not prevent binding of 5'-guanosine monophosphate to the metal complex. When bound to two individual guanosine molecules, di-Pt also remains partially bound by s-CX[4]. The cytotoxicity of free di-Pt and s-CX[4] and their host guest complex was examined using in vitro growth inhibition assays in the A2780 and A2780cis human ovarian cancer cell lines. Free di-Pt has an IC(50) of 100 and 60 microM, respectively, in the cell lines, which is significantly less active than cisplatin (1.9 and 8.1 microM, respectively). s-CX[4] displays no cytotoxicity at concentrations up to 1.5mM and does not affect the cytotoxicity of di-Pt, probably because its low binding constant to the metal complex (6.8 x 10(4)M(-1)) means the host-guest complex is mostly disassociated at biologically relevant concentrations.

Topics: Anticarcinogenic Agents; Calixarenes; Cell Line, Tumor; Cell Proliferation; Cisplatin; Drug Delivery Systems; Drug Design; Female; Humans; Organoplatinum Compounds; Ovarian Neoplasms; Phenols

A highly nanoporous material has been obtained by self-assembly of calixarene and porphyrin building blocks. This supramolecular zeolite-like structure was successively functionalized by diffusion and coordination of metal ions to form a new bifunctionalized nanoporous material containing a porphyrinic pigment together with a metal center.

Topics: Calixarenes; Chlorides; Crystallography, X-Ray; Diffusion; Models, Molecular; Molecular Conformation; Nanostructures; Nickel; Phenols; Porphyrins; Sodium; Zeolites; Zinc Compounds

Silica gel-immobilized, di-ionizable calix[4]arenes are employed as stationary phases in ion-exchange chromatography for selected heavy metal ions. Sorption efficiencies for Pb(2+) are dependent on the structure of the calix[4]arene ligand and the linker that joins the ligand to the silica gel, as well as the acidity of the sample solution. Although the resins exhibit only poor sorption of Cd(2+), they are found to be scavengers for Hg(2+). Competitive sorption studies are conducted with selected resins.

Topics: Adsorption; Cadmium; Calixarenes; Chromatography, Ion Exchange; Ions; Lead; Mercury; Metals, Heavy; Phenols; Silica Gel; Silicon Dioxide; Water Pollutants, Chemical

The novel amphipilic conjugate of a calix[4]arene with four Gd-1,4,7,10- tetra(carboxymethyl)-1,4,7,10-tetraazacyclododecane (DOTA) chelates has potential as a magnetic resonance imaging contrast agent, both in its monomeric and in its micellar form. The system, illustrated here with its nuclear magnetic relaxation profile, shows good relaxivities, thanks to its high rigidity.An amphiphilic conjugate 1 of a calix[4]arene with four Gd-DOTA chelates (DOTA=1,4,7,10-tetra(carboxymethyl)-1,4,7,10-tetraazacyclododecane) was prepared and the properties relevant to its application as a magnetic resonance imaging (MRI) contrast agent were investigated by NMR, dynamic light scattering (DLS), and cryo-electron microscopy (cryo-TEM). The compound aggregates in water; its critical micelle concentration (cmc) is 0.21 mM (or 0.84 mM for Gd) at 37 degrees C. The relaxivity of the aggregates at 37 degrees C and 20 MHz (18.3 s(-1) per mM Gd or 73.2 s(-1) per mM 1) is about twice that of the monomer. Nuclear magnetic relaxation dispersion (NMRD) profiles show the relaxivity of the monomer to be almost independent of the magnetic field strength up to 60 MHz. At higher concentrations, the NMRD profiles exhibit a maximum at about 20 MHz, which is typical for high molecular volumes. The average water residence lifetime is 1.20 mus at 298 K as determined by (17)O NMR. The rotational correlation time of the monomer (390 ns at 37 degrees C) is very close to the optimal value predicted for high-field contrast agents. Monomer as well as micelles are very rigid systems with negligible local contributions to the overall rotational dynamics. The binding to human serum albumin (HSA) is significant (K(A)=1.2x10(3) M(-1)) and the relaxivity of the HSA adduct at 20 MHz is 24.6 s(-1) per mM Gd or 98.5 s(-1) per mM 1.

Topics: Algorithms; Calixarenes; Gadolinium; Humans; Magnetic Resonance Imaging; Micelles; Models, Chemical; Organometallic Compounds; Organophosphorus Compounds; Phenols; Serum Albumin

A new class of polycalix[4]arene hosts has been constructed based on a carbosilane dendrimer architecture, in which each dendritic branch terminates with a calix[4]arene entity. This study reports the synthesis and characterization of the zeroth generation example with four calix[4]arenes and of the first generation example with 12 calix[4]arenes.

Topics: Calixarenes; Dendrimers; Phenols; Silanes

The physics of nanoscopic systems is strongly governed by thermal fluctuations that produce significant deviations from the behaviour of large ensembles. Stretching experiments of single molecules offer a unique way to study fundamental theories of statistical mechanics, as recently shown for the unzipping of RNA hairpins. Here, we report a molecular design based on oligo calix[4]arene catenanes-calixarene dimers held together by 16 hydrogen bridges-in which loops within the molecules limit how far the calixarene nanocapsules can be separated. This mechanically locked structure tunes the energy landscape of dimers, thus permitting the reversible rupture and rejoining of the individual nanocapsules. Experimental evidence, supported by molecular dynamics simulations, reveals the presence of an intermediate state involving the concerted rupture of the 16 hydrogen bridges. Stochastic modelling using a three-well potential under external load allows reconstruction of the energy landscape.

Topics: Calixarenes; Computer Simulation; Crystallization; Dimerization; Macromolecular Substances; Materials Testing; Models, Chemical; Models, Molecular; Molecular Conformation; Nanostructures; Nanotechnology; Particle Size; Phenols; Stress, Mechanical; Surface Properties

Two novel carboxylphenyl-modified calix[4]arenes, tetrakis-carboxylphenylcalix[4]arene (TCPC) and 1,3-bis-carboxylphenylcalix[4]arene (BCPC), as well as a corresponding analogue for comparison, tetrakis-phenylcalix[4]arene (TPC), have been synthesized by palladium-catalyzed Suzuki cross-coupling of arylboronic acid and tetrabromocalix[4]arene as a key step. The binding properties of these calix[4]arene derivatives with bovine heart cytochrome c (cyt c) in dimethylformamide (DMF) was investigated by fluorescence spectroscopy. The binding affinity in the order of TCPC>BCPC>>TPC reflects a clear dependence on the number of carboxyl ligating groups attached onto a receptor and suggests the electrostatic force may be the predominant factor driving the complexing process. The stable 1:1 complexes of TCPC and BCPC with cyt c were evidenced with the binding constants of 3.15 x 10(6) and 5.85 x 10(5)L mol(-1), respectively. Due to a large overlap between the emission spectrum of TCPC and the absorption spectrum of cyt c, and a short interaction distance (estimated to be 5.6 nm) between them, the fluorescence quenching of TCPC upon complexation with cyt c is attributed to an efficient energy transfer.

Topics: Animals; Calixarenes; Carboxylic Acids; Cattle; Cytochromes c; Dimethylformamide; Energy Transfer; Phenols; Protein Binding; Spectrometry, Fluorescence; Structure-Activity Relationship

A water-soluble calixarene-based heterocyclic podand incorporating a quinolone antibiotic subunit, the nalidixic acid, was synthesised and fully characterised. Its prodrug behaviour was assessed in vitro by HPLC, demonstrating the release of the tethered quinolone in model biological conditions. Microbiological studies performed on various Gram-positive and Gram-negative reference strains showed very interesting antibacterial activities.

Topics: Animals; Anti-Bacterial Agents; Calixarenes; Gram-Negative Bacteria; Gram-Positive Bacteria; Microbial Sensitivity Tests; Nalidixic Acid; Phenols; Prodrugs; Rats; Water

A new p-tert-[(dimethylamino)methyl]-1,3-bisglyciyl-calix[4]arene functionalized aminopropylpolysiloxane resin (APPS-CA) has been prepared and investigated for selective solid-phase extraction (SPE) of trace Cr (III), Cu (II), Ni (II), Co (II) and Zn (II) prior to their determination by inductively coupled plasma optical emission spectrometry (ICP-OES). The characterization of the surface modification was performed on the basis of FT-IR spectroscopy, elemental analysis and thermal gravimetric analysis. The separation/preconcentration conditions of analytes were investigated, including effect of pH, the shaking time, the sample flow rate and volume, the elution condition, the interfering ions and stability test. At pH 4.0, the maximum adsorption capacity of Cr (III), Cu (II), Ni (II), Co (II) and Zn (II) were 47.2, 34.3, 52.8, 29.8 and 36.4 mg g(-1), respectively. The adsorbed metal ions were quantitatively eluted by 2.0 mL of 0.5 mol L(-1) HCl. Common coexisting ions did not interfere with the separation. According to the definition of International Union of Pure and Applied Chemistry, the detection limits (3 sigma) of this method were found to be 0.58, 0.33, 0.47, 0.61 and 0.14 ng mL(-1) for Cr (III), Cu (II), Ni (II), Co (II) and Zn (II), respectively. The relative standard deviation under optimum conditions is less than 4.0%. The application of this new adsorbent to preconcentration trace Cr (III), Cu (II), Ni (II), Co (II) and Zn (II) of two water samples gave high accurate and precise results.

Topics: Calixarenes; Metals; Phenols; Reproducibility of Results; Resins, Synthetic; Siloxanes; Solid Phase Extraction; Water Pollutants, Chemical

Potassium channels are among the core functional elements of life because they underpin essential cellular functions including excitability, homeostasis, and secretion. We present here a series of multivalent calix[4]arene ligands that bind to the surface of voltage-dependent potassium channels (K(v)1.x) in a reversible manner. Molecular modeling correctly predicts the best candidates with a conical C(4) symmetry for optimal binding, and the effects on channel function are assessed electrophysiologically. Reversible inhibition was observed, without noticeable damage of the oocytes, for tetraacylguanidinium or tetraarginine members of the series with small lower rim O-substituents. Apparent binding constants were in the low micromolar range and had Hill coefficients of 1, consistent with a single site of binding. Suppression of current amplitude was accompanied by a positive shift in the voltage dependence of gating and slowing of both voltage sensor motion and channel opening. These effects are in keeping with expectations for docking in the central pore and interaction with the pore domain "turret."

Topics: Animals; Binding Sites; Calixarenes; Crystallography, X-Ray; Dose-Response Relationship, Drug; Electrophysiology; Female; Humans; Kinetics; Kv1.2 Potassium Channel; Ligands; Membrane Potentials; Models, Molecular; Molecular Structure; Oocytes; Phenols; Potassium Channels, Voltage-Gated; Protein Binding; Protein Structure, Secondary; Protein Structure, Tertiary; Xenopus laevis

The sensing response of poly(thiophene)s functionalized with calix[4]arene to Li+, Na+, and K+ has been investigated at the microscopic level using quantum mechanical calculations and molecular dynamics simulations. Results indicate that Na+ interacts electrostatically with the oxygen-rich site of the receptor reducing the conformational flexibility of the polymer backbone. In contrast, Li+ and K+ interact with the tert-butyl groups of the macrocycle enhancing such conformational flexibility. These features are consistent with available experimental data explaining the selectivity of this material for Na+ over Li+ and K+.

Topics: Calixarenes; Computer Simulation; Ions; Lithium; Models, Chemical; Phenols; Polymers; Potassium; Quantum Theory; Sodium; Thiophenes; Time Factors

A ditopic tetrapodal imidazolium-based 1,3-alternate calix[4]arene host binds anions as 1 : 2 complexes via a range of CH...anion hydrogen bonds. Allosteric enhancement of the affinity for the second chloride anion is observed. X-Ray crystal structures of the chloride, bromide and nitrate complexes suggest that this behaviour is linked to inter-binding site communication mediated by the calixarene framework. The imidazolium groups exist as either in-out or out-out conformers with respect to the calixarene, with the chloride complex exhibiting conformational isomorphism such that both forms are present in the same crystal structure.

Topics: Anions; Bromides; Calixarenes; Chlorides; Crystallography, X-Ray; Hydrogen Bonding; Imidazoles; Models, Molecular; Molecular Structure; Nitrates; Phenols

A series of three di-ionizable calix[4]arenes with two pendant dansyl (1-dimethylaminonaphthalene-5-sulfonyl) groups linked to the lower rims was synthesized. Structures of the three ligands were identical except for the length of the spacers which connected the two dansyl groups to the calix[4]arene scaffold. Following conversion of the ligands into their di-ionized di(tetramethylammonium) salts, absorption and emission spectrophotometry were utilized to probe the influence of metal cation (Li+, Na+, K+, Rb+, Cs+, Mg2+, Ca2+, Sr2+, Ba2+, Ag+, Cd2+, Co2+, Fe2+, Hg2+, Mn2+, Pb2+, Zn2+ and Fe3+) complexation in acetonitrile. Upon complexation with these metal cations, emission spectra underwent marked red shifts and quenching of the dansyl group fluorescence for the di-ionized ligand with the shortest spacer. A similar effect was noted for the di-ionized ligand with an intermediate spacer for all of the metal ions, except Ba2+. For the di-ionized ligand with the longest spacer, the metal cations showed different effects on the emission spectrum. Li+, Mg2+, Ca2+ and Ba2+ caused enhancement of emission intensity with a red shift. Other metal cations produce quenching with red shifts in the emission spectra. Transition metal cations interacted strongly with all three di-ionized ligands. In particular, Fe3+ and Hg2+ caused greater than 99% quenching of the dansyl fluorescence in the di-ionized ligands.

Topics: Acetonitriles; Calixarenes; Dansyl Compounds; Fluorescence; Ions; Metals; Phenols; Spectrophotometry

A 2-furaldehyde-selective PVC-membrane electrode is designed based on the host-guest interaction between tetrabenzyl ether Calix[4]arene, as an ionophore, and a lipophilic hydrazone derivative generated in situ from reaction of 2-furaldehyde and Girard's reagent T. At a pH of 9.2, the electrode exhibits a Nernstian response over the 2-furaldehyde concentration range of (5.0 x 10(-5))-(1.0 x 10(-1)) M. The electrode has found to be chemically inert and of adequate stability with a response time of 15 s with a good reproducibility (+/-0.2 mV) and can be used for a long working lifetime. In order to improve the minimum detectable concentration of 2-furaldehyde, further studies have been performed using a coated graphite electrode and coated platinum and gold disks. Some analytical aspects of adsorptive square wave voltammetry have also been presented in order to elucidate the adduct formation between 2-furaldehyde and Girard's reagent T. The interfering effects of some Na(+), K(+), NH(4)(+), formaldehyde, 5-hydroxymethyl 2-furaldehyde (HMF), excess of Girard's reagent T and organic solvents such as isopropyl alcohol and N,N-dimethylformamide on the sensor's response have been studied. The viability of using the electrode for the trace determination of 2-furaldehyde in several Iranian oil refinery wastewater samples is also demonstrated. The results obtained from the developed method for real samples are compared with those from UV-spectrophotometric and high-performance liquid chromatographic experiments.

Topics: Calixarenes; Chromatography, High Pressure Liquid; Electrochemistry; Furaldehyde; Hydrogen-Ion Concentration; Limit of Detection; Membranes, Artificial; Microscopy, Electron, Scanning; Phenols; Spectrophotometry, Ultraviolet

A lower rim naphthylidene conjugate of calix[4]arene [L] has been synthesized and characterized, and the structure has been established on the basis of single crystal XRD. The L has been found to be selective toward Zn(2+), which induces appropriate changes in the arms of L so that the N(2)O(2) coordination results in the formation of a tetrahedral complex; namely, [ZnL]. [ZnL] recognizes Asp, Cys, His, and Glu from among the naturally occurring amino acids owing to the protonation and chelating ability of the amino acid and the pi-pi interaction ability of the side chain of the amino acid with [ZnL]. All of these features have been demonstrated on the basis of fluorescence, absorption, and lifetime measurements. The rechelation of Zn(2+) by the amino acid used in the titration has been demonstrated on the basis of ESI-MS studies in the case of Cys to result in a Zn(2+) complex having either 5- or 6-coordination. [ZnL] has also been shown to be selective toward glutathione and glutathione oxidized. The amino acids present in the proteins also interact with [ZnL], resulting in dechelation of [ZnL] as well as aggregation of the protein, as demonstrated on the basis of absorption and fluorescence spectroscopy and atomic force microscopy. The alpha-helical proteins (namely, albumins) exhibit greater conformational changes, as compared to the beta-sheet proteins (namely, lectins), as studied on the basis of CD spectroscopy. The aggregation of the proteins when treated with [ZnL] follows a trend: peanut agglutinin < bovine serum albumin < jacalin < human serum albumin. The present studies clearly demonstrated the recognition features of [ZnL] toward Asp, Cys, His, and Glu, and the peptides and proteins containing these by spectroscopy and microscopy studies.

Topics: Amino Acids; Animals; Calixarenes; Cattle; Microscopy; Microscopy, Atomic Force; Naphthalenes; Peptides; Phenols; Protein Binding; Protein Structure, Secondary; Proteins; Serum Albumin; Spectrometry, Fluorescence; Spectrometry, Mass, Electrospray Ionization; Zinc

Four novel 1,3-alternate calix[4]arene-bonded silica gel stationary phases possessing different aromatic and aliphatic substituents at the upper rim (CalixNph, CalixBph, CalixHex, and CalixDdc) were prepared and structurally characterized. The comparison and selectivity of these phases were done by using alkylbenzenes, fatty acid p-bromophenacyl esters, aromatic positional isomers, and polynuclear aromatic hydrocarbons as analytes. Quantum chemistry calculations have also been performed (using an ab initio method) to support the experimental findings. The effect of the type and content of organic modifier on the retention and selectivity of the alkylbenzenes was studied. The retention mechanism is also discussed. The results indicate that the stationary phases behave like RP packings. However, inclusion complex formation and hydrophobic and pi-pi interactions seem to be involved in the separation process.

Topics: Calixarenes; Chromatography, Liquid; Gels; Phenols; Quantum Theory; Silicon Dioxide

A number of molecular receptors containing ruthenium(II) bipyridine moiety as fluorophore and calix[4]arene-azacrown hybrid molecule as ionophore have been synthesized and characterized. These receptors (1-4) exhibit strong 3MLCT luminescence bands in the range 613-618 nm. The cation-binding property of these fluoroionophores have been investigated with the ions Na+, K+, Mg2+, Ca2+, Cs+, Zn2+, Cd2+, Hg2+ and Pb2+ and the recognition event monitored by luminescence, 1H NMR spectroscopy, the oxidation potential of metal ion and UV/Vis absorption studies. The luminescence study suggests complexation of all four receptors with Zn2+, Cd2+ and Hg2+ and for 2 and 3 also with Pb2+. The binding constants (Ks, except 4) and stoichiometries of the complexes have been calculated from the luminescence titration data, with values of Ks ranging from 2.53 x 10(5) to 6.27 x 10(3) M(-1). The 1H NMR spectroscopy study exhibits interactions of Na+ and K+ with 1 and 4, K+ and Cs+ with 2, and K+ with 3. Binding constants with these metal ions have been calculated from 1H NMR titrations using computer programs or by a direct method depending on the type of change in the chemical shifts observed upon addition of metal ions. Stoichiometry of the complexes has been determined from Job's plot. Electrochemical properties of 1-4 have been studied in the absence and also in the presence of selected metal ions and the shift of the oxidation potentials of the Ru(II) in the presence of guest ions suggests an interaction of Na+, Hg2+ and Pb2+ with 1 and 2 but not with 3 and 4, indicating a selective electrochemical response towards certain metal ions. The results obtained are presented and discussed in light of ion-binding properties and methods of detection.

Topics: Aza Compounds; Binding Sites; Calixarenes; Electrochemistry; Ions; Molecular Structure; Organometallic Compounds; Phenols; Pyridines; Ruthenium

Solid-state guest dynamics of tetratolyl tetraurea calix[4]arene tetrapentylether dimeric capsules filled with different types of aromatic guests such as benzene-d6, fluorobenzene-d5 and 1,4-difluorobenzene were studied. Upon inclusion, all guest moieties revealed complexation-induced shifts varying from 2.8 ppm to 5.1 ppm. All guest molecules were shown to undergo distinct motions, ranging from mere C6-rotations of benzene-d6 to (ill-defined) 180 degrees phenyl flips of fluorobenzene-d5. In all cases, dynamic heterogeneities were identified based on 2H lineshape deconvolution. In addition, by combination of both a computed nucleus independent chemical shift (NICS) map and explicit 19F and 2H ab initio DFT chemical shift calculations, the preferred orientation of the guest molecules within the host was derived.

Topics: Benzene; Calixarenes; Magnetic Resonance Spectroscopy; Molecular Conformation; Molecular Dynamics Simulation; Phenols; Quantum Theory; Urea

A family of seven topologically isomeric calix[4]arene glycoconjugates was prepared through the synthesis of a series of alkyne-derivatised calix[4]arene precursors that are suitable for the attachment of sugar moieties by microwave-assisted copper(I)-catalysed azide-alkyne cycloaddition (CuAAC). The glycoconjugates thus synthesised comprised one mono-functionalised derivative, two 1,2- or 1,3-divalent regioisomers, one trivalent and three tetravalent topoisomers in the cone, partial cone or 1,3-alternate conformations. The designed glycoconjugates were evaluated as ligands for the galactose-binding lectin PA-IL from the opportunistic bacterium Pseudomonas aeruginosa, a major causative agent of lung infections in cystic fibrosis patients. Binding affinities were determined by isothermal titration calorimetry (ITC), and the interaction with the lectin was shown to be strongly dependant on both the valence and the topology. Whereas the trivalent conjugate displayed enhanced affinity when compared to a monosaccharide model, the tetravalent conjugates are to-date the highest-affinity ligands measured by ITC. The topologies presenting carbohydrates on both faces of calixarene are the most potent ones with dissociation constants of approximately 200 nM. Molecular modelling suggests that such a multivalent molecule can efficiently chelate two of the binding sites of the tetrameric lectin; this explains the 800-fold increase of affinity achieved by the tetravalent molecule. Surface plasmon resonance (SPR) experiments confirmed that this glycoconjugate is the strongest inhibitor for binding of PA-IL to galactosylated surfaces for potential applications as an anti-adhesive agent.

Topics: Bacterial Proteins; Calixarenes; Calnexin; Carbohydrate Conformation; Glycoconjugates; Isomerism; Lectins; Ligands; Models, Molecular; Phenols; Protein Binding; Surface Plasmon Resonance

Successive treatment of cyanuric chloride with two aromatic diamines, at least one of them sulfonated, yields water-soluble sulfonated azacalix[4]arenes which may be isolated by crystallisation. Functionalised azacalixarenes may be made by first displacing two chloro substituents from the cyclisation precursor. Attempted formation of an azacalix[6]arene led to a dimeric species for which two structures may be proposed, one of them an azacalixarene catenane.

Topics: Aza Compounds; Calixarenes; Crystallography, X-Ray; Models, Molecular; Molecular Structure; Phenols; Water

A series of new fluorescent calix[4]arenes (2-7; 5 has been isolated as two not yet described conformational isomers) featuring two directly lower rim attached dansyl moieties besides other lower or upper rim site substituents have been synthesized and investigated with reference to their fluorescence properties including potential sensing capability for metal ions. Except for the nitro substituted compound 7, which showed a moderate fluorescence quenching on the addition of Hg2+ in acetonitrile, the calixarenes 2-6 were found to selectively recognize Cu2+ in the 10(-6) mol L(-1) concentration range detectable by the nearly total quenching of their intrinsic fluorescence. Using fluorescence titration experiments, the ideal complexation ratio [metal ion]/[ligand] for three exemplarily investigated calixarenes (3, 5a and 7) was determined to be 2:1. For 5a, a new red shifted signal was observed by the complexation of Cu2+ while the addition of Hg2+ only yields a moderate quenching of the parent signal, indicating a different binding mode for both metal ions. This finding enables the calixarene 5a to be used as a suitable chemosensor for the simultaneous determination of copper and mercury. In this paper we also present the first crystal structures of dansylated calixarenes having the dansyl groups directly attached to the lower rim site. They involve the unsolvated calixarene 5b and the two solvent inclusion compounds 2.CH2(OH)CN and 3.3CH3CN, each showing an extensive pattern of non-covalent interactions. In both solvates, the calixarenes are fixed in a cone conformation while the unsolvated calixarene 5b adopts the partial cone conformation. A solution 1H NMR study in CDCl3 reveals also the cone conformation for all dansylated calixarenes, except the more conformationally flexible upper rim unsubstituted calixarene 5 which showed cone and partial cone conformers 5a and 5b, respectively, in an approximate 2:3 ratio.

Topics: Calixarenes; Crystallography, X-Ray; Fluorescence; Models, Molecular; Molecular Structure; Phenols; Stereoisomerism

A tetra-azido calix[4]arene derivative was allowed to react with ethynyl tetra- O-benzyl- C-galactoside in the presence of CuI and i-Pr 2EtN in three different ionic liquids, that is, [C 8dabco][N(CN) 2], [C 8dabco][Br], and Ammoeng 110. Reactions were performed at 80 degrees C by thermal and MW dielectric heating. In all cases, multiple cycloadditions took place to give a triazole-linked tetra- C-galactosyl-calix[4]arene in up to 90% yield. The [C 8dabco][N(CN) 2] ionic liquid was also used to perform the multiclick reactions with propargyl O-lactoside and S-sialoside.

Topics: Calixarenes; Copper; Galactosides; Glycoconjugates; Microwaves; Organometallic Compounds; Phenols; Triazoles

Calix[4]arene-capped [3-(2-O-beta-cyclodextrin)-2-hydroxypropoxy]propylsilyl-appended silica particles (C4CD-HPS), a new type of substituted beta-cyclodextrin-bonded chiral stationary phase (CSP) for high-performance liquid chromatography (HPLC), have been synthesized by treatment of bromoacetate-substituted [3-(2-O-beta-cyclodextrin)-2-hydroxypropoxy]propylsilyl-appended silica particles (BACD-HPS) with calix[4]arene oxyanions in anhydrous N-methyl-2-pyrrolidone. The synthetic stationary phase is characterized by means of elemental analysis. This new type of CSP has a chiral selector with two recognition sites: calix[4]arene and beta-cyclodextrin (beta-CD). The chromatographic behavior of C4CD-HPS was studied with several disubstituted benzenes and some chiral drug compounds under reversed-phase conditions. The results show that C4CD-HPS has excellent selectivity for the separation of aromatic positional isomers and enantiomers of chiral compounds due to the cooperative functioning of calix[4]arenes and beta-CDs.

Topics: beta-Cyclodextrins; Calixarenes; Chromatography, High Pressure Liquid; Pharmaceutical Preparations; Phenols; Silicon Dioxide

1,3-Alternate cationic calix[4]arene proved highly selective for proton/halogens symport transport and showed antiproliferative activity against murine monocyte/macrophage J774.A1 cancer cells.

Topics: Animals; Calixarenes; Cell Line, Tumor; Cell Proliferation; Chlorides; Ionophores; Macrophages; Mice; Phenols

Tetraurea calix[4]arenes 2 have been synthesized in which two adjacent aryl urea residues are connected to a loop by an aliphatic chain -O-(CH(2))(n)-O-. The remaining urea residues have a bulky 3,5-di-tert-butylphenyl residue and an omega-alkenyloxyphenyl residue. Since this bulky residue cannot pass through the loop, only one homodimer (22) is formed in apolar solvents, for steric reasons, in which the two alkenyl residues penetrate the two macrocyclic loops. Covalent connection of these alkenyl groups by olefin metathesis followed by hydrogenation creates compounds 3, which consist of molecules with hitherto unknown topology. Their molecular structure was confirmed by (1)H NMR spectroscopy and ESIMS, and for one example by single-crystal X-ray analysis.

Topics: Calixarenes; Dimerization; Hydrogen Bonding; Magnetic Resonance Spectroscopy; Models, Molecular; Phenols; Spectrometry, Mass, Electrospray Ionization

New multivalent cationic lipids, one of them showing high efficiency and low toxicity in cell transfection, have been obtained by attaching guanidinium groups at the lower rim of calix[4]arenes.

Topics: Calixarenes; Cell Line, Tumor; DNA; Electrophoresis; Guanidine; Humans; Phenols; Phosphatidylethanolamines; Transfection

An ion-pair receptor, 1, containing both cation- and anion-recognizing sites, has been synthesized and characterized. Single-crystal X-ray diffraction structural studies and (1)H NMR spectroscopic analyses confirmed that 1 forms stable 1:1 complexes with CsF in solution and in the solid state in spite of the large separation enforced between the receptor-bound anion and cation. In 9:1 CDCl3/CD3OD, binding of fluoride anion within the calix[4]pyrrole core of 1 was not observed in the absence of a cobound cesium cation; however, it was seen in this solvent mixture under conditions where a Cs(+) cation was bound to the crown ether-strapped calix[4]arene subunit.

Topics: Calixarenes; Cesium; Crown Ethers; Crystallography, X-Ray; Fluorides; Ions; Magnetic Resonance Spectroscopy; Phenols; Porphyrins

Protein p53 is a transcription factor crucial for cell cycle and genome integrity. It is able to induce both cell arrest when DNA is damaged and the expression of DNA repair machinery. When the damage is irreversible, it triggers apoptosis. Indeed, the protein, which is a homotetramer, is mutated in most human cancers. For instance, the inherited mutation p53-R337H results in destabilization of the tetramer and, consequently, leads to an organism prone to tumor setup. We describe herein a rational designed molecule capable of holding together the four monomers of the mutated p53-R337H protein, recovering the tetramer integrity as in the wild-type structure. Two ligand molecules, based on a conical calix[4]arene with four cationic guanidiniomethyl groups at the wider edge (upper rim) and hydrophobic loops at the narrower edge (lower rim), fit nicely and cooperatively into the hydrophobic clefts between two of the monomers at each side of the protein and keep the tetrameric structure, like molecular templates, by both ion-pair and hydrophobic interactions. We found a good agreement between the structure of the complex and the nature of the interactions involved by a combination of theory (molecular dynamics) and experiments (circular dichroism, differential scanning calorimetry and (1)H saturation transfer difference NMR).

Topics: Calixarenes; Dimerization; Humans; Ligands; Models, Molecular; Mutation, Missense; Phenols; Protein Interaction Domains and Motifs; Protein Structure, Tertiary; Spectrum Analysis; Tumor Suppressor Protein p53

The photophysical properties of the new pyridin-2'-yl-1,2,3-triazole chromophore have been investigated. Spectroscopic experiments and molecular modelling have provided evidence for a photoinduced charge transfer occurring from the triazole group to the pyridine ring. Hepta- and tetrachromophoric systems have been synthesized by covalently linking seven or four chromophores of this kind, respectively, to a beta-cyclodextrin and a calix[4]arene. They exhibit different fluorescence spectra, decays and quantum yields. Special attention has been paid to the binding of cadmium and zinc ions and to the resulting photophysical effects which are various and very different for the grafted beta-cyclodextrin and calix[4]arene systems.

Topics: Absorption; beta-Cyclodextrins; Cadmium; Calixarenes; Color; Fluorescence; Models, Molecular; Phenols; Pyridines; Spectrometry, Fluorescence; Time Factors; Triazoles

Reaction of TiCl(2)(Me(2)Calix) with 2 equiv of LiNHNRR' afforded the corresponding terminal hydrazido(2-) complexes Ti(NNRR')(Me(2)Calix) (R = Ph, R' = Ph (1) or Me; R = R' = Me (3)) which were all structurally characterized. The X-ray structure of Ph(2)NNH(2) is reported for comparison. Compound 1 was also prepared from Na(2)[Me(2)Calix] and Ti(NNPh(2))Cl(2)(py)(3). Reaction of ZrCl(2)(Me(2)Calix) with 2 equiv of LiNHNR(2) afforded only the bis(hydrazido(1-)) complexes Zr(NHNR(2))(2)(Me(2)Calix) (R = Ph or Me). Treatment of Ti(NNMe(2))(Me(2)Calix) (3) with MeI gave the zwitterionic hydrazidium species Ti(NNMe(3))(MeCalix) (6) via a net isomerization reaction which was found to be catalytic in MeI. The corresponding reaction of 3 with CD(3)I gave Ti(NNMe(2)CD(3))(MeCalix) (6-d(3)) with concomitant elimination of MeI. Reaction of 3 with 1 equiv of MeOTf gave [Ti(NNMe(3))(Me(2)Calix)][OTf] (7-OTf) which in turn reacted with (n)Bu(4)NI to form 6 and MeI. Addition of PhCHO to 3 gave the mu-oxo dimer [Ti(mu-O)(Me(2)Calix)](2) and benzaldehyde-dimethylhydrazone. Reaction of either 3 or 6 with (t)BuNCO gave the zwitterionic species Ti{(t)BuNC(NNMe(3))O}(MeCalix) (10) which has been crystallographically characterized. Compound 10 is the formal product of insertion of an isocyanate into the Ti=N(alpha) bond of a titanium hydrazide or hydrazidium species (Me(2)Calix or MeCalix = dianion or trianion of the di- or monomethyl ether of p-tert-butyl calix[4]arene, respectively).

Topics: Calixarenes; Crystallization; Hydrazines; Hydrogen Bonding; Kinetics; Ligands; Magnetic Resonance Spectroscopy; Models, Molecular; Molecular Conformation; Phenols; Probability; Spectrophotometry; X-Ray Diffraction

In the present study, Cu(II) removal from aqueous solutions by sorption was investigated. Aminopropyl silica gel-immobilized calix[4]arene polymer (APSIC[4]P) was used in sorption as sorbent. During the experimental part of this study, the effect of parameters, such as pH, initial Cu(II) concentration, temperature on Cu(II) removal was observed. In addition, sorption isotherm studies and column studies were made. Maximum Cu(II) removal was obtained at pH 6 and 25 degrees C. In the isotherm studies, Langmuir and Freundlich isotherm models were applied and it was determined that the experimental data confirmed to Langmuir isotherm model. Batch sorption capacity (q0) was calculated as 5.08 mg/g. The capacity value for column study was obtained by graphical integration as 1.14 mg/g. The Thomas and the Yoon-Nelson models were applied to experimental data to predict the breakthrough curves and to determine the characteristics parameters of the column useful for process design.

Topics: Adsorption; Calixarenes; Chemistry Techniques, Analytical; Copper; Hydrogen-Ion Concentration; Ions; Kinetics; Models, Chemical; Models, Statistical; Phenols; Polymers; Silicon Dioxide; Temperature; Water; Water Pollutants, Chemical; Water Purification

Novel chiral mono and diamide derivatives of calix[4]arene have been prepared from the aminolysis reaction of 5,11,17,23-tetra-tert-butyl-25,27-diethoxycarbonyl-methoxy-26,28-dihydroxycalix[4]arene 1 and 25,27-diethoxycarbonyl-methoxy-26,28-dihydroxycalix[4]arene 2 with chiral (S)-(-)-1-phenylethylamine (PEA) and (1S,2S)-(+)-2-amino-1-(4-nitrophenyl)-1,3-propanediol, respectively. Spectrophotometric titrations have been performed in CHCl(3) at 20-30 degrees C in order to obtain the binding constants (K) and the thermodynamic quantities (DeltaH and DeltaS) for the stoichiometric 1:1 inclusion complexation of various chiral amines with these new host compounds. Preliminary experiments were undertaken to confirm the complexation properties of receptors 9 and 13 with PEA by (1)H NMR in CDCl(3) at room temperature. The molecular recognition abilities and enantioselectivities for guests (R and S)-alpha-PEA and (R and S)-cyclohexylethylamine (CHEA) are discussed from a thermodynamic point of view.

Topics: Amines; Calixarenes; Diamide; Magnetic Resonance Spectroscopy; Phenols; Spectrophotometry, Ultraviolet; Stereoisomerism

The molecule of azocalix[n]arene is a macrocyclic used effectively in the complexation of the heavy metal pollutants (like silver and mercury). In this work, our main aim is to prepare new chromogenic azocalix[n]arene molecules to elaborate an extractant with high extractant selectivity for metal ions able to detect this type of pollutant. The solvent extraction properties of four acetyls, four methyl ketones and four benzoyls derivatives from azocalix[4]arenes which were prepared by linking 4-ethyl, 4-n-butyl, 4-acetamid anilin and 2-aminothiazol to calix[4]arene through a diazo-coupling reaction, the alkaline earth (Sr2+) and the transition (Ag+, Hg2+, Co2+, Ni2+, Cu2+, Zn2+, Cd2+, Cr3+) metal cations have been determined by extraction studies with metal picrates. Both ketones are better extractants than esters, and show a strong preference for Ag+, while Cu2+ and Cr3+ are the most extracted cation with the esters. Both acetyl and benzoyl esters are good carriers for Ag+ and Hg2+.

Topics: Azo Compounds; Calixarenes; Environmental Pollutants; Esters; Ketones; Ligands; Metals; Phenols; Picrates

Calix[4]arenes substituted by four urea functions are self-complementary molecules that spontaneously combine in apolar solvents in the presence of an ammonium salt to form dimeric capsules held together by a belt of hydrogen bonds. In the presence of tetraethylammonium salts, the Et4N+ cation is included as a guest. The sorting between dimeric capsules formed in a mixture of calix[4]arenes directly depends on the steric crowding of the substituents grafted on the urea groups whether aromatic derivatives or aliphatic chains linking urea functions in mono-, di-, or tetraloop structures. Simple rules allow one to anticipate which capsules will be exclusively formed when calix[4]arenes are mixed in different proportions. The stabilization of the dimeric structures by hydrogen bonds is thwarted by the overlaps of aliphatic loops and/or by bulky groups that cannot pass through these loops. Despite the structural similarity of the calixarenes, the exclusive formation of dimers of well-defined compositions and clear titration breaks are observed by electrospray mass spectrometry. This technique yields reliable information on stoichiometries and composition despite measurements in the gas phase rather than in solution and it does not suffer from excessive peak overlaps in contrast with NMR.

Topics: Calixarenes; Dimerization; Magnetic Resonance Spectroscopy; Models, Molecular; Molecular Structure; Phenols; Stereoisomerism; Urea

This communication describes preparation, characterization, and the evaluation of sorption properties of a calix[4]arene-based chitosan polymer (C[4]BCP). C[4]BCP was used to sorption studies of some heavy metal cations (Co(2+), Ni(2+), Cu(2+), Cd(2+)(,) Hg(2+) and Pb(2+)) and dichromate anions (Cr(2)O(7)(2-)/HCr(2)O(7)(-)) as sorbent material. Also the supporting material (chitosan) was used for comparison in these experiments. The results for heavy metal cations showed that C[4]BCP was excellent sorbent and the effect of chitosan was low. In the sorption studies of dichromate anions, C[4]BCP was highly effective sorbent at pH 1.5.

Topics: Adsorption; Anions; Calixarenes; Chelating Agents; Chitosan; Chromates; Hydrogen-Ion Concentration; Metals, Heavy; Phenols; Polymers

Possible rearrangement mechanisms of hydrogen-bond arrays formed at the lower rim of tetrahydroxycalix[4]arene and tetrahydroxythiacalix[4]arene were studied by means of density functional theory and the resolution identity approximation modification of Møller-Plesset perturbation theory (RI-MP2). Influence of solvent to height of energy barriers was quantified by use of the conductorlike screening model (COSMO) of implicit solvent (chloroform). Generally, two types of mechanisms were investigated. The first is represented by a synchronous single-step jump of all four hydroxyl protons. Pathways of the second mechanism include the rotation of one or more hydroxyl groups around the CAr-O bond. Theoretical results, in agreement with recently published experimental data (Lang et al. J. Chem. Phys. 2005, 122, 044056), prefer a jump mechanism for the methylene-bridged calix[4]arene. Concerning the thiacalix[4]arene, results obtained by COSMO as well as RI-MP2 calculations show that the rotational mechanism is very competitive and it could even be more favorable.

Topics: Calixarenes; Hydrogen Bonding; Hydroxylation; Isomerism; Models, Molecular; Molecular Structure; Phenols; Sulfhydryl Compounds; Thermodynamics

Three novel paramagnetic calix[4]arenes (2, 3 and 4) with two opposite nitroxide radicals on the upper rims were synthesized and characterized. The through-space spin-spin exchange interactions of these calixarene biradicals were investigated, and found to be affected by many factors, such as molecular conformational flexibility, steric hindrance, temperature, solvent effect and complexation of silver ion.

Topics: Calixarenes; Electron Spin Resonance Spectroscopy; Molecular Conformation; Phenols; Silver; Temperature; Toluene

This Communication reports a novel colorimetric sensor to probe histidine in water based on para-sulfonatocalix[4]arene-modified silver nanoparticles; this highly selective sensor allows a rapid quantitative assay of histidine down to a concentration of 5 x 10(-6) M, providing a new tool for the direct measurement of histidine.

Topics: Calixarenes; Colorimetry; Electrodes; Histidine; Metal Nanoparticles; Particle Size; Phenols; Sensitivity and Specificity; Silver; Surface Properties

Tetra-urea calix[4]arenes substituted with four mono- or bisalkenyl residues have been converted into bis- or tetraloop compounds by intramolecular olefin metathesis, with use of a tetratosylurea calix[4]arene as template. The same strategy has now been used to synthesise trisloop compounds and bisloop compounds with adjacent loops, completing the series of the loop-containing tetra-urea derivatives. A tetra-urea calix[4]arene of the AABB type, where A stands for a bisalkenyl- and B for a monoalkenyl-substituted urea unit, was used as precursor for the three loops. It was easily synthesised from a tetraamino calix[4]arene in which two adjacent amino groups were Boc-protected. The ABCB-type precursor for the two adjacent loops was prepared through protection of two opposite amino functions with trityl groups. The capabilities of the novel macrocyclic tetra-ureas for the selective formation of hydrogen-bonded dimers were studied.

Topics: Calixarenes; Dimerization; Magnetic Resonance Spectroscopy; Phenols; Spectrometry, Mass, Electrospray Ionization; Urea

Topics: Animals; Calixarenes; Cell Survival; CHO Cells; Cricetinae; Cricetulus; Fluorescence; HL-60 Cells; Humans; Inhibitory Concentration 50; Molecular Conformation; Phenols; Stereoisomerism

This paper describes a general method to change the surface property of the oleic acid stabilized silver nanoparticles and successful tranferring of the silver nanoparticles from the organic phase into the aqueous phase. By vigorous shaking of a biphasic mixture of the silver organosol protected with oleic acid and p-sulfonated calix[4]arene (pSC4) aqueous solution, it is believed that an inclusion complex is formed between oleic acid molecules and pSC4, and the protective layer of the silver nanoparticles shifts from hydrophobic to hydrophilic in nature, which drives the transfer of silver nanoparticles from the organic phase into the aqueous phase. The efficiency of the phase transfer to the aqueous solution depends on the initial pSC4 concentration. The pSC4-oleic acid inclusion complex stabilized nanoparticles can be stable for long periods of time in aqueous phase under ambient atmospheric conditions. The procedure of phase transfer has been independently verified by UV-vis, transmission electron microscopy, Fourier transform infrared, and 1H nuclear magnetic resonance techniques.

Topics: Calixarenes; Hydrophobic and Hydrophilic Interactions; Metal Nanoparticles; Oleic Acid; Phenols; Silver; Spectrum Analysis; Surface Properties

A novel anticancer vaccine candidate built on a nonpeptidic scaffold has been synthesized. Four S-Tn tumor-associated glycomimetic antigens have been clustered onto a calix[4]arene scaffold bearing an immunoadjuvant moiety (P3CS). The immunogenicity of the synthetic construct has been investigated by immunization of mice in vivo. ELISA assay has evidenced that the tetravalent construct stimulates a higher production of anti-Tn antigen IgG antibodies when compared to an analogous monovalent compound. This result is ascribable to an antigen cluster effect and makes the reported vaccine candidate a good mimic of the natural motifs present on the mucine surface.

Topics: Adjuvants, Immunologic; Animals; Antibodies, Neoplasm; Antigens, Tumor-Associated, Carbohydrate; Calixarenes; Cancer Vaccines; Chromatography, Thin Layer; Dipeptides; Enzyme-Linked Immunosorbent Assay; Female; Immunoglobulin G; Immunotherapy; Indicators and Reagents; Lipoproteins; Magnetic Resonance Spectroscopy; Mice; Mice, Inbred BALB C; Molecular Mimicry; Neoplasms; Phenols; Spectrometry, Mass, Electrospray Ionization

Calixarenes are macrocyclic oligomers having the shape of a conical vase. Their inner cavity can accommodate various guest molecules, i. e. form supramolecules. Thus, calixarenes can be employed to manipulate selectivity in separation sciences. The essential step of separation is the interaction between calixarene and analytes. Therefore, in the present work, the retention mechanisms of benzenediol and naphthol positional isomers on a calix[4]arene column were investigated. The optimized supramolecular structures showed that there exist hydrogen bonding and pi-pi interactions for benzenediol, and for naphthol the pi-pi interactions dominate. Thermodynamic results from quantum chemistry calculations using DFT-B3LYP/STO-3G** basis set were consistent with the retention behaviors of benzenediol and naphthol positional isomers on the calix[4]arene column. This work will provide theoretical support for the design of new calixarene stationary phases.

Topics: Calixarenes; Chromatography, High Pressure Liquid; Hydrogen Bonding; Indicators and Reagents; Models, Molecular; Naphthols; Phenols; Quantum Theory; Thermodynamics

The scope of the reaction of the tetrabromocalixarene derivative 2b with alcohols under solvolytic conditions in trifluoroethanol (TFE) or hexafluoroisopropanol (HFIP) was explored. The reaction proceeded readily with MeOH, EtOH, n-PrOH, ethylene glycol and i-PrOH affording preferentially the rccc isomer of the tetrasubstituted product. The methoxy derivative 6a undergoes isomerization upon attempted recrystallization from CHCl3/MeOH and its rcct and rctt forms were characterized by X-ray crystallography. Incorporation of hydroxy groups on the bridges was accomplished via solvolysis in AcOH, followed by LiAlH4 reduction of the acetoxy groups. Reaction of the tetra-(2-methylfuranyl)calixarene derivative 11 with benzyne followed by deoxygenation with Me3SiCl/NaI afforded in low yield the tetra-(4-methylnaphthyl)calix[4]arene derivative 12. Reaction of de-tert-butylated tetrabromo derivative 2a with m-xylene in HFIP followed by methylation of the crude product afforded the tetraxylyl derivative 14.

Topics: Alcohols; Calixarenes; Crystallography, X-Ray; Methane; Models, Molecular; Molecular Structure; Phenols; Propanols; Stereoisomerism; Trifluoroethanol

Ten tetra-urea calix[4]arene derivatives with different ether residues (methyl, pentyl, benzyl, all combinations of methyl and pentyl, 1,3-dibenzyl-2,4-dipentyl), including also the tetrahydroxy compound and the 1,3-dipentyl ether, were synthesised. Their urea groups were substituted with a lipophilic residue to ensure sufficient solubility in cyclohexane. Thus, kinetics for the exchange of the included guest (benzene) against the solvent (cyclohexane) could be followed by 1H NMR spectroscopy. The apparent first order rate constants decrease with increasing size of the ether residues from methyl to benzyl by more than three orders of magnitude. This can be understood by a decreasing flexibility/mobility of the calixarene skeleton. In line with this explanation is the rather slow exchange for the tetrahydroxy compound, where the cone conformation is stabilised by a cyclic array of intramolecular OH...OH hydrogen bonds.

Topics: Benzene; Calixarenes; Cyclohexanes; Dimerization; Ethers; Hydrogen Bonding; Kinetics; Magnetic Resonance Spectroscopy; Molecular Structure; Phenols; Urea

Water-soluble calix[4]resorcinarenes containing 3- and 4-hydroxyproline, d-nipecotic acid, (S)-2-(methoxymethyl)pyrrolidine, (S)-2-pyrrolidine methanol, and (S,S)-(+)-2,4-bis(methoxymethyl)pyrrolidine substituents are synthesized and evaluated as chiral NMR solvating agents. The derivatives with the hydroxyproline groups are especially effective at causing enantiomeric discrimination in the spectra of water-soluble cationic and anionic compounds with pyridyl, phenyl, and bicyclic aromatic rings. Binding studies show that mono- and ortho-substituted phenyl rings associate within the cavity of the calix[4]resorcinarenes, as do naphthyl rings with mono-, 2,3-, and 1,8-substitution patterns. Anthracene derivatives with an amino or sulfonyl group at the 1-position bind within the cavity, as well. Aromatic resonances of the substrates exhibit substantial upfield shifts because of shielding from the aromatic rings of the calix[4]resorcinarene. The effectiveness of the reagents at producing chiral recognition in 1H NMR spectra is demonstrated with sodium mandelate, the sodium salt of tryptophan, and doxylamine succinate. While no one reagent is consistently the most effective, the calix[4]resorcinarenes with trans-4-hydroxyproline and trans-3-hydroxyproline moieties generally produce the largest nonequivalence in the 1H NMR spectra of the substrates.

Topics: Calixarenes; Hydroxyproline; Indicators and Reagents; Magnetic Resonance Spectroscopy; Models, Molecular; Molecular Structure; Phenols; Phenylalanine; Reference Standards; Solubility; Solvents; Stereoisomerism; Water

A new efficient and highly selective fluorescent chemosensor for determination of Pb (2+) has been obtained by covalent attachment of two pendent proton-ionizable dansylcarboxamide groups to the calix[4]arene preorganized in the partial cone conformation. This geometry of the calixarene moiety was chosen on the basis of the prior (1)H NMR study of conformations adopted by the flexible dansyl-containing prototype upon complexation with lead ion. In acidic MeCN-H2O (1:1 v/v) solutions, the partial cone fluoroionophore allowed for detection of Pb (2+) at the levels as low as 2.5 ppb, which is totally compatible with the regulations of the U.S. Environmental Protection Agency and the World Health Organization on the limiting content of this hazardous pollutant in drinking water.

Topics: Calixarenes; Cations, Divalent; Crystallography, X-Ray; Dansyl Compounds; Fluorescent Dyes; Lead; Magnetic Resonance Spectroscopy; Molecular Conformation; Phenols

New chromogenic diazophenylcalix[4]arenes 1 and 2 were synthesized in cone conformation. Compound 1 with the ortho-carboxyl groups in CH(3)CN solution preferentially binds with alkaline earth and transition metal ions, whereas no significant changes in absorption spectra are observed in the presence of alkali metal ions. While 2 with the ortho-ester groups shows selective complexation properties towards transition metal ions over alkali and alkaline earth metal ions. The detection of metal ions gives rise to bathochromic shifts in the absorption spectra (from orange/yellow to red), which is clearly visible even to the naked eye. According to the selective color changes using both receptors upon cation complexation, one can set up a qualitative analytical routine to screen alkali, alkaline earth, and transition metal ions.

Topics: Calixarenes; Color; Diazonium Compounds; Metals; Metals, Alkali; Metals, Alkaline Earth; Phenols; Spectrum Analysis; Structure-Activity Relationship; Transition Elements

A new fluorescent chemosensor based on calix[4]arene bearing four iminoquinoline subunits on the upper rim was conveniently synthesized, which showed a remarkable enhanced fluorescent intensity in the presence of Cu(2+) ion and a high selectivity toward Cu(2+) ion over a wide range of tested metal ions in acetonitrile.

Topics: Calixarenes; Copper; Fluorescent Dyes; Phenols; Quinolines; Spectrometry, Fluorescence

Tetra- and octavalent sialoside clusters were prepared in good yields exploiting for the first time the multiple copper-catalyzed cycloaddition of a propargyl thiosialoside with calix[4]arene polyazides. The cycloadducts featured the hydrolytically stable carbon-sulfur bond at the anomeric position and the 1,4-disubstituted triazole ring as the spacer between the sialic acid moieties and the platform. It was demonstrated that these unnatural motifs did not hamper the desired biological activity of the sialoclusters. In fact, they were able to inhibit, at submillimolar concentrations, the hemagglutination and the viral infectivity mediated both by BK and influenza A viruses.

Topics: Alkynes; Animals; Antiviral Agents; Azides; BK Virus; Calixarenes; Catalysis; Chlorocebus aethiops; Copper; Cyclization; Cytopathogenic Effect, Viral; Glycosides; Hemagglutination Inhibition Tests; Hemagglutination, Viral; Influenza A virus; Microbial Sensitivity Tests; Molecular Structure; N-Acetylneuraminic Acid; Phenols; Sulfhydryl Compounds; Vero Cells

We synthesized a tetrameric amphiphilic molecule ( 1) based on a calix[4]arene building block that self-assembled into different tunable and stable aggregation structures at different pH values in aqueous solution. The amphiphilic calix[4]arene molecule ( 1) formed a spherical structure at pH 3. However, 1 formed a hollow necklacelike structure of 500 nm diameter at pH 7. These results indicate that the self-assembled morphologies of 1 are strongly dependent on pH values. In addition, a 3D dendritic silver nanostructure was obtained by the self-assembly of 1 at pH 7.

Topics: Calixarenes; Circular Dichroism; Crystallization; Electrochemistry; Hydrogen Bonding; Hydrogen-Ion Concentration; Microscopy, Electron, Scanning; Microscopy, Electron, Transmission; Models, Chemical; Molecular Structure; Nanoparticles; Nanostructures; Nanotechnology; Phenols; Silver; X-Ray Diffraction

Topics: Calixarenes; Ethers, Cyclic; Hydrogen Bonding; Imidazoles; Magnetic Resonance Spectroscopy; Models, Molecular; Molecular Structure; Organometallic Compounds; Phenanthrolines; Phenols; Resorcinols; Rhenium; Sensitivity and Specificity; Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization; Stereoisomerism

The acid-base properties of mononitro-calix[4]arene was studied with chemometric methods by measurement of its UV absorbance under different pH. The chemometric method-iterative target transformation factor (ITTFA) was employed to resolve the acid-base fraction curves. Combining with other chemometric methods-principal component analysis (PCA) and evolving factor analysis (EFA), the proton dissociation behavior of the derivative was investigated in detail. The pK(a) values of the derivative were determined and the fraction curves and pure absorbing spectra of each absorbing component were obtained.

Topics: Acids; Buffers; Calixarenes; Ethanol; Factor Analysis, Statistical; Hydrogen Bonding; Hydrogen-Ion Concentration; Molecular Structure; Nitro Compounds; Phenols; Phosphates; Principal Component Analysis; Protons; Solvents; Spectrophotometry, Ultraviolet; Temperature; Water

Various calix[4]arene derivatives, fixed in the cone conformation by decylether groups and functionalized at their wide rim by urea residues, were synthesized. In two compounds (,) sulfur functions were attached to the urea groups via different spacers in order to allow binding to metal surfaces. While they exist as single molecules in polar solvents, tetraurea calix[4]arenes of this type () combine to form dimeric capsules in aprotic, apolar solvents. A solvent molecule is usually included in such a capsule, if no guest with a higher affinity is present. In the presence of an equimolar amount of the tetratosylurea, the exclusive formation of heterodimers, consisting of one molecule of and, is observed. The homo- and heterodimerization of the newly prepared derivatives, were studied by 1H NMR to establish the conditions under which they exhibit the desired dimerization behaviour. Self-assembled monolayers (SAMs) were formed using the single calix[4]arenes, and the heterodimeric capsules. Chloroform, dichloromethane and ferrocenium cations were used as guests in these immobilized heterodimeric capsules. The particular supramolecular architecture of the heterodimers should ensure that, after the immobilization on the metal surface, decomposition of the capsules and release or exchange of the guest is impossible or at least hindered. The self-assembly process and the stability of SAMs formed by capsules filled with ferrocenium cations in electrolyte solutions were tested with surface plasmon spectroscopy. The inclusion of guests, such as dichloromethane or ferrocenium, in the immobilized capsules were confirmed by classical surface plasmon spectroscopy, by gold nanoparticle absorption spectroscopy and by time-of flight secondary ion mass spectrometry (ToF-SIMS). The film stability and quality was tested by cyclic voltammetry.

Topics: Calixarenes; Cations; Chloroform; Dimerization; Electrochemistry; Electrolytes; Ferrous Compounds; Gold; Mass Spectrometry; Methylene Chloride; Models, Chemical; Nanoparticles; Phenols; Solubility; Solutions; Solvents; Sulfur; Surface Plasmon Resonance; Urea

Synthesis and characterization of three novel Schiff bases based on calix[4]arene are described. The synthesis of these compounds had been achieved by the condensation of salicylaldehyde derivatives with the amine group of upper rim of de-butylcalix[4]arene in ethanol. The structures of new compounds were confirmed on the basis of IR, (1)H NMR, (13)C NMR, MS and elementary analysis. Photochromic properties of compounds were studied in CH(3)CN by UV/vis and fluorescence spectra. These Schiff base-calix[4]arene can be used in certain 'supermolecular electronic devices' through combining the photochromic behaviors with others such as non-linear optical or charge transfer properties.

Topics: Calixarenes; Electrons; Light; Phenols; Schiff Bases; Spectrometry, Fluorescence; Spectrophotometry, Ultraviolet; Time Factors

Bisurea calix[4]arenes 1 and 2 possessing L-amino acid moieties at the lower rim were synthesized by reaction of the methyl esters of glycine, L-alanine, or L-isoleucine with the appropriate isocyanate (12 or 13), obtained with a safe and efficient Curtius rearrangement from the corresponding carboxylic acid derivatives. The conformational properties of the ligands 1 and 2 were investigated by means of a combined NMR and molecular modeling study which evidences that they are deeply influenced by strong intramolecular H-bonds between the urea NH groups and the vicinal phenolic oxygen atoms or the opposite urea C=O group. Complexation studies performed by ESI-MS and NMR spectroscopy in acetone solution show that the binding ability of these bisurea hosts decreases by increasing the side chain size of the amino acid. Host 2b has a remarkable binding ability for the N-acetyl-D-phenylalaninate anion with an interesting enantioselectivity (KDass/KLass=4.14), which is explained on the basis of a three-point interaction mode of binding.

Topics: Amino Acids; Anions; Binding Sites; Calixarenes; Chemistry, Organic; Hydrogen; Ligands; Magnetic Resonance Spectroscopy; Models, Molecular; Molecular Structure; Peptides; Phenols; Phenylalanine; Spectrometry, Mass, Electrospray Ionization; Stereoisomerism; Urea

Ion-selective membrane electrodes doped with the urea- or thiourea-functionalised calix[4]arenes, 5,11,17,23-tetra-tert-butyl-25,27-bis[[4-N'-(phenylureido)butyl]oxy]-26,28-dipropoxy calix[4]arene (I) and 5,11,17,23-tetra-tert-butyl-25,27-bis[[4-(N'-phenylthioureido)-butyl]oxy]-26,28-dipropoxy calix[4]arene (II), were evaluated for anion sensing. Potentiometric results show that these calixarene ionophore-based membrane electrodes exhibit a good sensitivity to aqueous solutions of the monohydrogen orthophosphate species HPO(4)(2-) in the concentration range 5.0 x 10(-5) to 1.0 x 10(-1)M, with near-Nernstian response slopes of -33.0 and -28.0 mV dec(-1) for ionophores I and II, respectively. Selectivity coefficient values for monohydrogen orthophosphate over a range of common anions were determined by the fixed interference and matched potential methods and indicated that these membrane electrodes exhibit a good selectivity for HPO(4)(2-) with respect to the other anions, including sulfate and nitrate.

Topics: Anions; Calixarenes; Dose-Response Relationship, Drug; Electrochemistry; Electrodes; Ion-Selective Electrodes; Ions; Magnetic Resonance Spectroscopy; Models, Chemical; Nitrates; Phenols; Phosphates; Potentiometry; Sensitivity and Specificity; Spectroscopy, Fourier Transform Infrared; Sulfates

We present the rational design and anion-binding properties of the first anion-templated pseudorotaxanes and catenanes in which the "wheel" component is provided by a calix[4]arene macrobicyclic unit. The designs and syntheses of two new calix[4]arene macrobicycles, 2 and 3, are presented, and the abilities of these new species both to bind anions and to undergo anion-dependent pseudorotaxane formation are demonstrated. Furthermore, it is shown that performing ring-closing metathesis reactions on some of these pseudorotaxane assemblies gives novel catenane species 14 and 15, in which the yield of interlocked molecule obtained is critically dependent on the presence of a suitable anion template, namely, chloride. Exchange of the chloride anion in catenane 14 a for hexafluorophosphate gives catenane 14 d, which contains a unique anion-binding domain defined by the permanently interlocked hydrogen-bond-donating calix[4]arene macrobicycle and pyridinium macrocycle fragments. The anion-binding properties of this domain are presented, and shown to differ from non-interlocked components.

Topics: Anions; Bridged Bicyclo Compounds; Calixarenes; Magnetic Resonance Spectroscopy; Molecular Structure; Phenols; Spectrometry, Mass, Electrospray Ionization

In this paper, the adsorbents were prepared from cellulose-grafted with calix[4]arene polymers (CGC[4]P-1 and CGC[4]P-2) and their sorption properties studied. The polymers were characterized by Fourier transform infrared spectroscopy, elemental analysis, thermal gravimetric analysis and scanning electron microscopy. They were then used to evaluate the sorption properties of some heavy metal cations (Co(2+), Ni(2+), Cu(2+), Cd(2+), Hg(2+) and Pb(2+)) and dichromate anions (Cr(2)O(7)(2-)/HCr(2)O(7)(-)). Results showed that CGC[4]P-2 was a good sorbent for heavy metal cations while CGC[4]P-1 was ineffective. In the studies of dichromate anion sorption, it was observed that CGC[4]P-2 was a more highly effective sorbent at pH 1.5 than was CGC[4]P-1.

Topics: Adsorption; Calixarenes; Cellulose; Chemistry Techniques, Analytical; Chromates; Ions; Metals, Heavy; Phenols; Polymers

A water-soluble supramolecular sensing assembly, composed of an imidazolium-substituted calix[4]arene and a fluorescent aminodiacetate derivative of 1,8-naphthalimide, was studied. Addition of citrate led to a large fluorescence enhancement, while tartrate, acetate, as well as selected inorganic anions gave smaller effects. The sensing principle and selectivity for citrate rely on the formation of a ternary fluorophore-host-anion complex and complexation-induced pKa shifts of an amino group attached to the fluorophore. The complexation of citrate induces a protonation of the amino group, which switches off intramolecular photoinduced electron transfer as the fluorescence quenching pathway, leading to an enhancement of the optical output signal. The intricate sensor principle was corroborated by pH titrations, binding constants, and structural information as obtained by 1H NMR spectroscopy.

Topics: Calixarenes; Citric Acid; Hydrogen-Ion Concentration; Magnetic Resonance Spectroscopy; Molecular Structure; Naphthalimides; Phenols; Spectrometry, Fluorescence; Titrimetry

A set of cyclic tetranuclear complexes of the metallacalix[4]arene type with formula [{Pt(en)(L)}(4)](4+) (en=ethylenediamine; 2: LH=5-chloro-2-hydroxypyrimidine (5-Cl-Hpymo); 3: LH=5-bromo-2-hydroxypyrimidine (5-Br-Hpymo); 4: LH=5-iodo-2-hydroxypyrimidine (5-I-Hpymo)) have been obtained from the reaction between cis-protected square-planar [Pt(en)(H(2)O)(2)](2+) metal entities and LH in aqueous media. Additionally, the binding properties of 2, 3, 4 and their congener [{Pt(en)(L)}(4)](4+) (1: LH=2-hydroxypyrimidine (Hpymo)) with calf thymus-DNA (ct-DNA) have been studied by using different techniques including circular and linear dichroism (CD and LD, respectively) and UV-visible absorbance spectroscopies, gel electrophoresis, fluorescence competitive-binding studies and atomic force microscopy (AFM). The results are consistent with significant non-covalent interactions taking place between the polynuclear cyclic species and ct-DNA. Moreover, gel electrophoresis, linear dichroism titrations and AFM images of ct-DNA with metallacalixarenes show ct-DNA coiling at low metallacalixarene concentrations and upon subsequent increments in metallacalixarene concentration ct-DNA can be seen to uncoil with concomitant formation of long and inflexible ct-DNA structures.

Topics: Antineoplastic Agents; Binding, Competitive; Calixarenes; Cations, Divalent; Circular Dichroism; DNA; Electrophoresis; Magnetic Resonance Spectroscopy; Microscopy, Atomic Force; Molecular Structure; Organoplatinum Compounds; Phenols; Platinum; Spectrometry, Fluorescence; Spectrophotometry, Ultraviolet; Temperature; Water

To partition effectively Cs(I) and Sr(II), two harmful heat emitting nuclides, from a highly active liquid waste by extraction chromatography, two kinds of macroporous silica-based polymeric materials, Calix[4]arene-R14/SiO(2)-P and TODGA/SiO(2)-P, were synthesized. Two chelating agents, 1,3-[(2,4-diethyl-heptylethoxy)oxy]-2,4-crown-6-calix[4]arene (Calix[4]arene-R14), an excellent supramolecular compound having molecular recognition ability for Cs(I), and N,N,N',N'-tetraoctyl-3-oxapentane-1,5-diamide (TODGA) were impregnated and immobilized into the pores of SiO(2)-P particles support by a vacuum sucking technique. The loading and elution of 11 typical simulated fission and non-fission products from 4.0M or 2.0M HNO(3) were performed at 298K. It was found that in the first column packed with the Calix[4]arene-R14/SiO(2)-P, all of the simulated elements were separated effectively into two groups: (1) Na(I), K(I), Sr(II), Fe(III), Ba(II), Ru(III), Pd(II), Zr(IV), and Mo(VI) (noted as Sr-group); (2) Cs(I)-Rb(I) (Cs-group) by eluting with 4.0M HNO(3) and distilled water, respectively. The harmful element Cs(I) flowed into the second group along with Rb(I) because of their close sorption and elution properties towards Calix[4]arene-R14/SiO(2)-P, while Sr(II) showed no sorption and flowed into Sr-containing group. In the second column packed with TODGA/SiO(2)-P, the Sr-group was separated into (1) Ba(II), Ru(III), Na(I), K(I), Fe(III), and Mo(VI) (non-sorption group); (2) Sr(II); (3) Pd(II); and (4) Zr(IV) by eluting with 2.0M HNO(3), 0.01M HNO(3), 0.05M DTPA-pH 2.5, and 0.5M H(2)C(2)O(4), respectively. Sr(II) adsorbed towards TODGA/SiO(2)-P flowed into the second group and showed the excellent separation efficiency from others. Based on the elution behavior of the tested elements, an advanced PREC (Partitioning and Recovery of two heat generators from an acidic HLW (high activity liquid waste) by Extraction Chromatography) process was proposed.

Topics: Amides; Calixarenes; Cesium; Chromatography, Liquid; Phenols; Silicon Dioxide; Strontium

The synthesis and structural characterization of a samarium-dinitrogen complex supported by a calix[4]arene ligand in which the N-N bond distance has been stretched to 1.611(16) Angstrom are described. The central mu(3)-eta(2):eta(2):eta(2)-hydrazido tetraanion formed is bonded to three Sm(III) centers with an overall butterfly-type arrangement.

Topics: Calixarenes; Lanthanoid Series Elements; Molecular Structure; Nitrogen; Oxidation-Reduction; Phenols; Samarium

A newly designed inherently chiral calix[4]arene was synthesized and resolved to an optically pure form. Enantiomeric recognition ability of the chiral calix[4]arene was examined using 1H NMR experiments with mandelic acid. In addition, the chiral calix[4]arene was applied to asymmetric reactions, as an organocatalyst.

Topics: Calixarenes; Catalysis; Magnetic Resonance Spectroscopy; Mandelic Acids; Molecular Structure; Phenols; Stereoisomerism

The mechanisms of interactions between calix[4]resorcinarene and dopamine in monolayers formed at the air-water interface were studied by analyzing their mechanical, thermodynamic, and electrical properties evaluated from measurements of pressure-area isotherms and Maxwell displacement currents (MDCs). An increased concentration of dopamine in the water subphase resulted in an increase in the area per calix[4]resorcinarene molecule, an increase in the collapse pressure, and a shift in the monolayer phase transitions from the gaseous to the liquid state and from the liquid to the solid state toward higher molecular areas. A contactless method of recording MDCs enabled the monitoring of changes in the charge state of the monolayer-constituting molecules and the determination of a relationship between the phase state of the monolayer and the structural transitions of calix[4]resorcinarene. The changes of the MDC recordings started already in the gaseous state of the monolayer. On the basis of MDC values, we determined the normal component of the dipole moment of calix[4]resorcinarene, as well as that of its complex with dopamine. The dipole moment reached a maximum value of 1040 mD in the region of the phase transition from the liquid to the solid state of the monolayer. The results obtained suggest that the binding of dopamine with calix[4]resorcinarene depends on the orientation of the calixarene molecules in the monolayer. The calix[4]resorcinarene-dopamine interactions were also quantified in terms of the excess of Gibbs free energy, thereby allowing the evaluation of the energy of the calix [4]resorcinarene-dopamine bond, which was in the range from 1.95 to 8.54 kJ/mol depending on the surface pressure. This value implies weak interactions between these molecules.

Topics: Calixarenes; Dopamine; Electrochemistry; Phenols; Phenylalanine; Pressure; Surface Properties; Thermodynamics

The synthesis and the spectroscopic studies of the amidourea based calix[4]arene sensors 1 and 2 are described. The 4-nitrophenyl based sensor 1 was synthesized in two steps from the corresponding calix [4]arene tetraethyl ester and shown to give rise to color changes in the UV-vis spectra in DMSO upon recognition of pyrophosphate and fluoride. Fitting the changes in the absorption spectra using nonlinear regression analysis indicated strong binding of several anions by 1 such as acetate and hydrogen phosphate in 1:1 (Host:Guest) stoichiometry, and at higher concentration in 1:2 stoichiometry. The preorganized calix-cavity was, however, not found to host chlorine while binding of bromide was determined. At high concentrations of these anions, significant colorimetric changes were also observed that were clearly visible to the naked eye for both pyrophosphate and fluoride. The phenyl analogue 2 was made to enable analysis of the anion recognition using 1H NMR titrations and showed that ions such as phosphate were bound in 1:1 stoichiometry, whereas the "urea" protons were shown to be significantly affected upon coordination to the anion.

Topics: Acetates; Anions; Calixarenes; Colorimetry; Diphosphates; Fluorides; Magnetic Resonance Spectroscopy; Nitrophenols; Phenols; Spectrophotometry, Ultraviolet; Urea

A novel calix[4]arene-based chemosensor 1 based on Hg2+-induced fluorescence resonance energy transfer (FRET) was synthesized, and its sensing behavior toward metal ions was investigated by UV/vis and fluorescence spectroscopies. Addition of Hg2+ to a CH3CN solution of 1 gave a significantly enhanced fluorescence at approximately 575 nm via energy transfer (FRET-ON) from the pyrenyl excimer to a ring-opened rhodamine moiety. In contrast, addition of Al3+ induced a distinct increase of pyrenyl excimer emission ( approximately 475 nm), while no obvious FRET-ON phenomenon was observed. Different binding behaviors of 1 toward Hg2+ and Al3+ were also proposed for the interesting observation.

Topics: Calixarenes; Cations, Divalent; Fluorescence Resonance Energy Transfer; Fluorescent Dyes; Mercury; Phenols; Rhodamines; Spectrometry, Mass, Matrix-Assisted Laser Desorption-Ionization; Spectrophotometry, Ultraviolet

The binding behaviors and thermodynamic origins of p-sulfonatocalix[4]arene (C4AS) and p-sulfonatocalix[5]arene (C5AS) with methyl viologen (MV2+) have been investigated by the methods of isothermal titration calorimetry, NMR, and cyclic voltammetry, showing that the binding abilities of C4AS and C5AS and their host selectivity are dramatically pH-controlled, which is closely discussed from the viewpoint of thermodynamics. Moreover, the radical form of MV+* can also be effectively included by C4AS and C5AS.

Topics: Calixarenes; Cations; Free Radicals; Magnetic Resonance Spectroscopy; Models, Molecular; Paraquat; Phenols

Di- and trinuclear copper(II) complexes of [12]aneN3 macrocycles anchored at the upper rim of cone calix[4]arenes in 1,2-, 1,3-, and 1,2,3-positions were investigated as cleaving agents of 6-, 7-, and 17-meric oligoribonucleotides. A kinetic investigation of the cleavage reactions was carried out using gel electrophoresis to separate and analyze reactants and products having a radioactive phosphate label in the terminal 5'-position. The degree of cooperation was assessed on the basis of a comparison with rates of cleavage by mononuclear controls. A remarkable selectivity of cleavage of the CpA phosphodiester bond was observed for all metal complexes, in sharp contrast with the UpU and UpG selectivity previously observed in the cleavage of diribonucleoside monophosphates by the same metal complexes. The highest rate acceleration, brought about in the cleavage of the 5'-pCpA bond in hexanucleotide 9 by 50 muM trinuclear complex 5-Cu3 (water solution, pH 7.4, 50 degrees C), amounts to 5 x 105-fold, as based on the estimated background reactivity of the CpA dimer. Selectivity in the cleavage of oligoribonucleotides by copper(II) complexes closely resembles that experienced by ribonuclease A and by a number of metal-independent RNase A mimicks. The possible role of the dianionic phosphate at the 5'-terminal positions as a primary anchoring site for the metal catalyst is discussed.

Topics: Calixarenes; Catalysis; Molecular Structure; Oligonucleotides; Phenols; Ribonucleases; RNA

Chiral calix[4]arenes bearing long tertiary alkyl groups at the upper rim and S-1-phenylethylamine groups at the lower rim can form heat-set gels and egg-like vesicles enantioselectively with d-2,3-dibenzoyltartaric acid in cyclohexane, which is the first example of heat-set gels resulting from difference in interactions between two component gelators: in addition, the diameter of vesicles decreased with the increase in length of alkyl groups, which could be used to control the size of the vesicles.

Topics: Calixarenes; Cyclohexanes; Gels; Hot Temperature; Molecular Conformation; Particle Size; Phenols; Stereoisomerism; Tartrates

The binding of lanthanide(III) cations with organophosphorous ligands like CMPO and related calix[4]arene-based derivatives have been investigated using two experimental methods. The stability constants of the lanthanum, europium and ytterbium complexes were first determined in methanol by UV absorption spectrophotometry in the presence of nitrate or chloride anions. The results showed that the stoichiometry and the stability of the complexes formed depend on the position of the CMPO moieties either on the wide or the narrow rim of the calixarene scaffold, the nature of the medium, the conformational mobility of the ligands. Complexation of lanthanum was also followed by ESI-mass spectrometry in the same solvent. This method confirmed the stoichiometry of the complexes, giving also structural information, like coordination of anion or solvent molecules to the complexes, and allowed the calculation of distribution curves in good agreement with those derived from the spectrophotometric results. This is an important result showing that ESI-MS can be used to provide with quantitative information when absorption spectrophotometry is not applicable, i.e. for systems where complexation leads to weak spectral changes.

Topics: Calixarenes; Europium; Lanthanum; Phenols; Phosphines; Spectrometry, Mass, Electrospray Ionization; Spectrophotometry, Ultraviolet; Ytterbium

The characteristics of host-guest complexation between p-sulfonated calix[4]arene (SC4A) and lomefloxacin (LMFX) were investigated by fluorescence spectrometry. A 1:1 stoichiometry for the complexation was established and an association constant of 6.48x10(4) l mol-1 at 25 degrees C was calculated by applying a deduced equation. The interaction mechanism of the inclusion complex was discussed and the various factors affecting the inclusion process were examined in detail. It was found that an appropriate amount of cationic surfactant cetyltrimethylammonium bromide (CTAB) can remarkably enhance the fluorescence intensity of the supramolecular complex system. Based on the obtained results, a novel sensitive spectrofluorimetric method for the determination of lomefloxacin based on supramolecular complex was developed with a linear range of 0.01-3.0 microg ml-1 and a detection limit of 0.008 microg ml-1, for the first time. The method was applied for the determination of lomefloxacin in pharmaceutical preparations successfully.

Topics: Calixarenes; Fluoroquinolones; Phenols; Quinolones; Spectrometry, Fluorescence; Sulfonic Acids

Two types of calix[4]arene derived hosts for anions with, respectively, 1,3-alternate and cone conformations have been prepared; the 1,3-alternate system binds dicarboxylate anions in a ditopic manner while the cone compounds are deprotonated by carboxylates.

Topics: Anions; Calixarenes; Crystallography, X-Ray; Dicarboxylic Acids; Models, Molecular; Molecular Structure; Phenols

A new type of diglycidyloxy-calix[4]arene coated fiber made by sol-gel method was initially prepared for capillary electrophoresis (CE) sample pretreatment. By using headspace solid-phase microextraction (SPME) combined with a novel back-extraction facility coupled off-line to capillary zone electrophoresis (CZE), the simultaneous determination of propranolol enantiomers in human urine was achieved. The clean up effect and preconcentration effect were realized for the first time without derivatization during the SPME process in terms of these strong polarity and thermal stable compounds. Ultrasonic back-extraction and field amplified sample injection (FASI) technologies were employed. Extraction and back-extraction parameters were optimized. Preconcentration of the sample by calix[4]arene fiber based SPME and FASI increased the sensitivity, yielding a limit of detection (LOD) of 0.01microg/ml by CZE-diode array detection (DAD). Method repeatability (RSD<6.5%) and fiber reusability (>150 extraction procedures) were observed over a linear range (0.05-10microg/ml) in urine samples. Based on the superior thermal stability, high alkali- and solvent-resistant ability, marvelous repeatability and long lifetime of the novel fiber, this SPME-FASI-CZE procedure could meet the demand of minimum required performance limit (MRPL) set by the World Anti-doping Agency (WADA) for the detection of propranolol in urine samples.

Topics: Adrenergic beta-Antagonists; Calixarenes; Electrophoresis, Capillary; Gels; Phenols; Propranolol; Reproducibility of Results; Sensitivity and Specificity; Stereoisomerism

Spectrofluorometric titrations have been performed to investigate the inclusion behavior of p-sulphonatocalix[4]arene (SC4A) and 9-amino-acridine (AA) in citrate buffer solution (pH 5.92). It was found that the fluorescence intensity of AA quenched regularly upon the addition of SC4A. The proposed interaction mechanism between SC4A and AA indicates that AA partially goes into the cavity of SC4A with the help of strong electrostatic interaction and hydrogen bonding, which formed by the protonated N atom and the amino groups of AA bonding with sulphonyl groups of SC4A, respectively. The inclusion ratio was 1:1 and the inclusion constant was 1.84 x 10(5) L mol(-1) at 25.0 degrees C.

Topics: Aminacrine; Calixarenes; Fluorescence; Macromolecular Substances; Phenols; Spectrometry, Fluorescence; Titrimetry

We have utilized para-hexanoylcalix[4]arene nanocapsules as hosts to carry out phototransformations of cis- and trans-stilbene. Single-crystal X-ray diffraction studies were performed to define precisely the location of encapsulated stilbenes inside the capsule and to analyze possible pathways of phototransformation. cis-Stilbene stacks as a pi-pi dimer located at the center of the capsule, whereas trans-stilbene does not form such a dimer. Irradiation of the crystalline inclusion complexes of each isomer of stilbene in the solid state leads to the appearance of the second isomer, and after prolonged photolysis, photodimerization also occurs. syn-Tetraphenylcyclobutane is formed as the major product of dimerization and its yield depends on the time and intensity of irradiation. In most cases, the single crystals of the complexes remain intact during irradiation; hence, the nanocapsules have the potential to serve as robust nanoreactors in the solid state. The confinement in the nanocapsules is sufficient to keep the reacting molecules together, although this is less restrictive than for trans-stilbene crystals, in which the molecules cannot achieve a favorable orientation for dimerization.

Topics: Calixarenes; Crystallization; Crystallography, X-Ray; Dimerization; Nanocapsules; Phenols; Photochemistry; Stereoisomerism; Stilbenes

The thermodynamic parameters for the inclusion of some naturally occurring amino acids into a series of p-sulfonated calix[4]arenes, were determined via both 1H NMR and calorimetric titrations in buffered aqueous solution at 25 degrees C. The calorimetric data show that inclusion is enthalpically driven in all cases, regardless of flexibility of the host and the nature of the guest. The most efficient receptor is the calix[4]arene tetrasulfonate 1, which exists in solution at pH 7 in a cone conformation, stiffened by H-bonding at the lower rim. Molecular mechanics data help in the understanding of why some hosts do not form inclusion complexes at all. The comparison of our data with literature reports shows that there are dramatic buffer-dependent changes in the binding affinities.

Topics: Amino Acids; Calixarenes; Calorimetry; Magnetic Resonance Spectroscopy; Models, Molecular; Molecular Conformation; Phenols; Solubility; Structure-Activity Relationship; Sulfonic Acids; Thermodynamics

The pinched cone-pinched cone interconversion (PCI) of tetraethoxy substituted calix[4]arene and thiacalix[4]arene was studied by means of molecular dynamics using the GAFF force field and quantum mechanics. Influence of solvent was expressed by changes in cavity geometries as well as in free energy barriers that were calculated using constrained MD simulations. Water and chloroform were found to reduce the energy barriers in comparison with vacuum simulations. Only qualitative agreement between energy barriers calculated by MD and experimental values was achieved. Also, quantum chemical calculations were performed with the RI-MP2 method, and a better description of PCI was achieved than that previously obtained by HF or DFT methods. The combination of qualitative MD data on solvated systems with RI-MP2 gas-phase data gave us very good agreement with experimental results.

Topics: Calixarenes; Molecular Conformation; Phenols; Solubility; Solvents

Diffusion-ordered (1)H NMR spectroscopy techniques have been used to determine the binding strength of p-sulfonatocalix[4]arene (SO(3)[4]) towards a number of charged crown ether species in aqueous conditions. For several (doubly) charged (di)azacrown ethers, all were bound by SO(3)[4] either well or very well with binding constants between 5.1 x 10(2)-9.9 x 10(5) M(-1). These results correlate with, and thus explain the phenomenon of rapid capture of azacrown ethers in molecular capsules based on p-sulfonatocalix[4]arene and lanthanide metals. Similarly, the formation of "Russian doll" superanions in the solution phase is also elucidated. These superanions have been shown to selectively crystallise particular polynuclear aquated metal ions from mixtures in the aqueous phase. Neutral [18]crown-6 is not bound by p-sulfonatocalix[4]arene and displays a binding constant of 0 M(-1). When sodium [18]crown-6 is examined in a similar fashion, binding by SO(3)[4] is observed in solution with K(a) approximately 3.1 x 10(3) M(-1).

Topics: Binding Sites; Calixarenes; Crown Ethers; Crystallography, X-Ray; Magnetic Resonance Spectroscopy; Molecular Weight; Phenols

An extremely complex solid state structure described by two virtual channels and a 2-D square grid of hydrogen bonds is generated by four carboxylic acids groups of calix[4]arene tetrabutyroxycarboxylic acid.

Topics: Calixarenes; Carboxylic Acids; Magnetic Resonance Spectroscopy; Models, Molecular; Phenols

The synthesis of multichromophoric perylene bisimide-calix[4]arene arrays with up to five perylene units (containing orange, violet, and green perylene bisimide chromophores) and of monochromophoric model compounds was achieved by subsequent imidization of mono-Boc functionalized calix[4]arene linkers with three different types of perylene bisimide dye units. The optical properties of all compounds were studied with UV/vis absorption and steady state and time-resolved fluorescence spectroscopy. Upon excitation of the inner orange dye at 490 nm of array 3, strong fluorescence emission of the outer green perylene bisimide (PBI) chromophore at 744 nm is observed. The fluorescence excitation spectra of compounds 3 and 4 (lambdadet = 850 nm) show all absorption bands of the parent chromophores (e.g., all perylene units contribute to the emission from S1 state of the green PBI). Thus, the fluorescence emission and excitation spectra as well as time-resolved data of fluorescence lifetimes in the absence (tauD = 5.1 ns) and in the presence of an acceptor (tauDA = 0.8 ns) suggest efficient energy transfer processes between the perylene bisimide dye units. For the bichromophoric array 4, the energy transfer rate is calculated to a value of 1.05 x 109 s-1. These results demonstrate highly efficient energy transfer in cofacially assembled dye arrays.

Topics: Biomimetic Materials; Calixarenes; Fluorescence Resonance Energy Transfer; Imides; Light-Harvesting Protein Complexes; Perylene; Phenols; Photochemistry; Spectrometry, Fluorescence; Spectrophotometry, Ultraviolet

Octahomotetraoxacalix[4]arenes bearing long alkyl chains on their lower rim were prepared. Ester 4a existed in a 1,2-alternate conformation in its crystal structure, which was examined by single-crystal X-ray diffraction analysis. To prepare liquid crystalline materials possessing calixarene moieties by self-assembling, carboxylic acid derivatives 5 were synthesized. Among them, 5c, the octadecyloxy derivative, showed smectic liquid crystal phase. Homooxacalixarenes 5 also formed liquid crystal phases with longer layer distances when two equivalent moles of 1,2-ethylenediamine were added as a linker. These phases were investigated with X-ray diffraction, differential scanning calorimetry, and polarized optical microscopy.

Topics: Calixarenes; Calorimetry, Differential Scanning; Carboxylic Acids; Crystallization; Liquid Crystals; Microscopy, Polarization; Molecular Structure; Phenols; X-Ray Diffraction

Platelet-derived growth factor (PDGF) and its receptor PDGFR are required for tumor growth and angiogenesis, so disruption of the PDGF-PDGFR interaction should lead to starvation of tumors and reduction of tumor growth. Potent PDGF antagonists have been discovered through the synthesis of a series of calix[4]arene-based compounds that are designed to bind to the three-loop region of PDGF. The effect of lower-rim alkylation, linker and number of interacting head groups on the calix[4]arene scaffold on PDGF affinity and cellular activity has been investigated.

Topics: Amino Acid Sequence; Animals; Antineoplastic Agents; Calixarenes; Female; Humans; Kinetics; Mice; Mice, Nude; Models, Molecular; Molecular Sequence Data; NIH 3T3 Cells; Phenols; Phosphorylation; Platelet-Derived Growth Factor; Protein Binding; Receptors, Platelet-Derived Growth Factor; Structure-Activity Relationship; Xenograft Model Antitumor Assays

Molecular dynamics (MD) simulations have been performed for complexes of a dimeric capsule of a tetraurea calixarene with a series of twelve aromatic guests. A distinct orientational preference and a restriction of the internal mobility was found which depend on the size and electronic properties of the guests. The results are in agreement with the CIS values obtained from (1)H NMR spectroscopic measurements and with complexation selectivities obtained by competition experiments.

Topics: Benzene Derivatives; Binding, Competitive; Calixarenes; Kinetics; Magnetic Resonance Spectroscopy; Models, Molecular; Phenols; Pyrazines; Pyridines; Substrate Specificity; Thermodynamics; Urea

A systematic investigation of fluoride anion binding properties as a function of chelate backbone has been carried out for ferrocene functionalised boronic esters of the types FcB(OR)2 and fc[B(OR)2]2 [Fc = ferrocenyl = (eta5-C5H5)Fe(eta5-C5H4); fc = ferrocendiyl = Fe(eta5-C5H4)2]. Cyclic boronic esters containing a saturated five- or six-membered chelate ring are readily synthesized from ferrocene, and selectively bind fluoride via Lewis acid/base chemistry in chloroform solution. The resulting complexes are characterized by relatively weak fluoride binding (e.g.K = 35.8 +/- 9.8 M(-1) for FcBO2C2H2Ph2-S,S), and by cathodic shifts in the ferrocene oxidation potential that form the basis for electrochemical or colorimetric fluoride detection. The fluoride selectivity of these systems is attributed to relatively weak Lewis acidity, resulting in weak F- binding, and essentially no binding of potentially competitive anions. By contrast, more elaborate Lewis acid frameworks based on calix[4]arene (calixH4), such as (FcB)2calix or fcB2calix, do not survive intact exposure to standard fluoride sources (e.g. [nBu4N]F.xH2O solutions in chloroform or acetonitrile). Instead B-O bond cleavage occurs yielding the parent calixarene; the differences between alkoxo- and aryloxo-functionalised derivatives can be rationalised, at least in part, by consideration of the differences in electron donating capabilities of RO- (R = alkyl, aryl).

Topics: Boronic Acids; Calixarenes; Chelating Agents; Crystallography, X-Ray; Cyclization; Electrochemistry; Esters; Ferrous Compounds; Fluorides; Magnetic Resonance Spectroscopy; Metallocenes; Models, Molecular; Oxidation-Reduction; Phenols

Cell cycle progression is dependent on intracellular iron level and chelators lead to iron depletion and decrease cell proliferation. This antiproliferative effect can be inhibited by exogenous iron. In this work, we present the synthesis of new synthetic calix[4]arene podands bearing two aspartic/glutamic acid, ornithine groups or hydrazide function at the lower rim, designed as potential iron chelators. The synthesis only afforded calix[4]arenes in the cone conformation. We report their effect on cell proliferation, in comparison with the new oral chelator ICL670A (4-[3,5-bis-(2-hydroxyphenyl)-1,2,4-triazol-1-yl]-benzoic acid). The antiproliferative effect of these new compounds was studied in the rat hepatoma cell line Fao by measuring mitochondrial succinate dehydrogenase activity. Their cytotoxicity was evaluated by extracellular LDH activity. Preliminary results indicated that among all tested compounds, monohydrazidocalix[4]arene 2 which is not cytotoxic in Fao cells exhibits interesting antiproliferative activity. This effect, independent on iron depletion, remains to be further explored. Moreover, it also shows that new substituted calix[4]arenes could open the way to new valuable medicinal chemistry scaffolding.

Topics: Animals; Benzoates; Calixarenes; Carcinoma, Hepatocellular; Cell Line, Tumor; Cell Proliferation; Deferasirox; Drug Screening Assays, Antitumor; Hydroxyl Radical; Iron Chelating Agents; Molecular Structure; Phenols; Rats; Solubility; Structure-Activity Relationship; Triazoles; Tumor Cells, Cultured

Calix[4]arenes functionalized at the 1,2-, 1,3-, and 1,2,3-positions of the upper rim with [12]ane-N(3) ligating units were synthesized, and their bi- and trimetallic zinc(II) and copper(II) complexes were investigated as catalysts in the cleavage of phosphodiesters as RNA models. The results of comparative kinetic studies using monometallic controls indicate that the subunits of all of the zinc(II) complexes and of the 1,3-distal bimetallic copper(II) complex 7-Cu(2) act as essentially independent monometallic catalysts. The lack of cooperation between metal ions in the above complexes is in marked contrast with the behavior of the 1,2-vicinal bimetallic copper(II) complex 6-Cu(2), which exhibits high catalytic efficiency and high levels of cooperation between metal ions in the cleavage of HPNP and of diribonucleoside monophosphates NpN'. A third ligated metal ion at the upper rim does not enhance the catalytic efficiency, which excludes the simultaneous cooperation in the catalysis of the three metal ions in 8-Cu(3). Rate accelerations relative to the background brought about by 6-Cu(2) and 8-Cu(3) (1.0 mM catalyst, water solution, pH 7.0, 50 degrees C) are on the order of 10(4)-fold, largely independent of the nucleobase structure, with the exception of the cleavage of diribonucleoside monophosphates in which the nucleobase N is uracil, namely UpU and UpG, for which rate enhancements rise to 10(5)-fold. The rationale for the observed selectivity is discussed in terms of deprotonation of the uracil moiety under the reaction conditions and complexation of the resulting anion with one of the copper(II) centers.

Topics: Calixarenes; Catalysis; Cations, Divalent; Copper; Kinetics; Nitrogen; Organometallic Compounds; Organophosphates; Organophosphorus Compounds; Phenols; Ribonucleotides; RNA; Solubility; Water; Zinc

A route has been paved toward the preparation of triazole glycocluster libraries via the copper(I)-catalyzed modern version of the classical Huisgen 1,3-dipolar cycloaddition of azides to alkynes. Up to four 1,4-disubstituted 1,2,3-triazole rings bearing carbon-linked glycosyl fragments were constructed on various scaffolds via multiple cycloadditions of suitably polyfunctionalized calix[4]arene, adamantane, and benzene derivatives with ethynyl and azidomethyl C-glycosides. Each cycloaddition occurred with high regioselectivity to give exclusively the 1,4-disubstituted triazole ring in very high yield up to an average value of 98%. The high degree of efficiency of this approach and its wide scope constitute a simple and practical means for the attachment of various sugar units to polyfunctionalized substrates.

Topics: Adamantane; Alkynes; Azides; Benzene; Calixarenes; Combinatorial Chemistry Techniques; Cross-Linking Reagents; Glycosides; Monosaccharides; Phenols; Triazoles

We have studied the physical properties of monolayers formed by calix[4]resorcinarene and in mixtures with dipalmitoyl phosphatidylcholine (DPPC) in various molar ratios formed at the air-water interface and at presence of dopamine in water subphase by means of measurements of surface pressure and dipole potential. We showed that both calix[4]resorcinarene as well as its mixture with DPPC form stable monolayers at the water subphase. The presence of dopamine resulted in an increase of the mean molecular area and in a decrease of the compressibility modulus of the monolayers. For mixed monolayers at higher content of calix[4]resorcinarene (> 0.2 molar fraction) a deviation from ideal miscibility took place especially for monolayers in a solid state. This can be connected with formation of aggregates of calix[4] resorcinarene. Lowest miscibility and weakest interaction of dopamine with a monolayer was observed for calix[4]resorcinarene molar fraction of 0.33 in the monolayer.

Topics: 1,2-Dipalmitoylphosphatidylcholine; Adsorption; Air; Calixarenes; Dopamine; Phenols; Phenylalanine; Surface Properties; Water

1,3-Alternate calix[4]arene-based fluorescent chemosensors bearing two-photon absorbing chromophores have been synthesized, and their sensing behaviors toward metal ions were investigated via absorption band shifts as well as one- and two-photon fluorescence changes. Free ligands absorb the light at 461 nm and weakly emit their fluorescence at 600 nm when excited by UV-vis radiation at 461 nm, but no two-photon excited fluorescence is emitted by excitation at 780 nm. Addition of an Al(3+) or Pb(2+) ion to a solution of the ligand causes a blue-shifted absorption and enhanced fluorescence due to a declined resonance energy transfer (RET) upon excitation by one- and two-photon processes. Addition of a Pb(2+) ion to a solution of 1.K(+) results in a higher fluorescence intensity than the original 1.Pb(2+) complex regardless of one- or two-photon excitation, due to the allosteric effect induced by the complexation of K(+) with a crown loop.

Topics: Calixarenes; Phenols

Calix[4]arenes constrained to the 1,3-alternate conformation and functionalized at the upper rim with four and two tert-butylnitroxides have been synthesized and characterized by X-ray crystallography, magnetic resonance (EPR and (1)H NMR) spectroscopy, and magnetic studies. The 1,3-alternate nitroxide tetraradical and diradical provide unique polyradical scaffolds for dissection of the through-bond and through-space intramolecular exchange couplings. In addition, detailed magnetic studies of the previously reported calix[4]arene nitroxide tetraradical, which possesses cone conformation in solution, reveal conformational dependence of exchange coupling. Through-bond coupling between the adjacent nitroxide radicals is mediated by the nitroxide-m-phenylene-CH(2)-m-phenylene-nitroxide coupling pathway, and through-space coupling is found between the diagonal nitroxide radicals at the conformationally constrained N...N distance of 5-6 A. Magnetic studies of the calix[4]arene polyradical scaffolds in frozen solutions show that the through-bond exchange coupling in the 1,3-alternate calix[4]arene tetraradical is antiferromagnetic, while that in cone calix[4]arene tetraradical is ferromagnetic. The through-space exchange couplings are antiferromagnetic in both cone and 1,3-alternate calix[4]arene tetraradical, as well as in the 1,3-alternate calix[4]arene diradical. The exchange coupling constants (|J/k|) are of the order of 1 K.

Topics: Calixarenes; Crystallography, X-Ray; Electron Spin Resonance Spectroscopy; Ferric Compounds; Hydrogen; Molecular Conformation; Nitrogen; Nitrogen Oxides; Oxygen; Phenols; Temperature

A solid powder of hydrogen bonded dimers of a tetraurea calix[4]arene is able to exchange the encapsulated guest in contact with the vapor of a second guest. The molecules of a guest-free powder obtained from a polar solvent cannot rearrange in the solid phase to form new guest-filled capsules under these conditions.

Topics: Calixarenes; Dimerization; Hydrogen Bonding; Magnetic Resonance Spectroscopy; Molecular Conformation; Phenols; Urea

The experimental IR and Far IR spectra of the calix[4]arene, p-tert-butylcalix[4]arene, thialcalix[4]arene and p-tert-butylthiacalix[4]arene were examined at different temperatures and interpreted. The band frequencies and intensities in the IR spectra of the calix[4]arene and thialcalix[4]arene were calculated. The absorption curves of the four possible calix[4]arene conformations: cone, partial cone, 1,2- and 1,3-alternate were computed. The bands characteristic for each conformation are defined and assigned. The obtained spectra-structure correlation can be used for the characteristic of calixarenes conformation.

Topics: Calixarenes; Molecular Structure; Phenols; Spectroscopy, Near-Infrared; Sulfides

A new concept of protein sensing at the air-water interface is introduced, based on amphiphilic receptor molecules embedded in a lipid monolayer. The process begins with incorporation of a small amount (0.13 equiv) of one or two different calix[4]arenes, adorned with charged functional groups at their upper rims, into a stearic acid monolayer. These doped monolayers are subsequently shown to attract peptides and proteins from the aqueous subphase. Depending on the host structure, the monolayers can be made selective for basic or acidic proteins. A working model is proposed, which explains the large observed p/A shifts with reincorporation of excess receptor molecules into the lipid monolayer after complex formation with the oppositely charged protein. This requires a self-assembly of multiple calixarene units over the protein surface, which bind the protein in a cooperative fashion. Oppositely charged calixarene derivatives do not form molecular capsules inside the monolayer, but rather remain separate inside the lipid layer, adopting a perpendicular orientation. They combine their hydrogen bond donor and acceptor capacities, and thus markedly enhance the sensitivity of the sensor system toward proteins, pushing the detection limits to 10 pM concentrations. The response pattern obtained from various receptor units inside the monolayer toward the same protein creates a fingerprint for this protein, which can hence be selectively detected at nanomolar concentrations (pattern recognition).

Topics: Amino Acids; Benzyl Compounds; Biosensing Techniques; Calixarenes; Models, Molecular; Organophosphonates; Phenols; Protein Binding; Proteins; Quaternary Ammonium Compounds; Stearic Acids; Substrate Specificity

A 120 member library of peptidocalix[4]arenes was synthesized and screened for catalysis of the hydrolysis of p-nitrophenyl acetate. His-Ser-His-calix[4]arene was found to catalyze this reaction with v(0)=3.24 x 10(-8)M/s, an increase of 1520% above background and 30% above the tripeptide (His-Ser-His) alone.

Topics: Bridged-Ring Compounds; Calixarenes; Catalysis; Hydrolysis; Models, Chemical; Nitrophenols; Oligopeptides; Phenols; Time Factors

The synthesis of a new class of amphiphilic calix[4]arene-based ionophores, relying on direct reductive amination as a key step, and the evaluation of their H+ and Na+ transporting properties is described.

Topics: Calixarenes; Cholic Acids; Hydrogen-Ion Concentration; Ionophores; Molecular Conformation; Phenols; Sodium; Stereoisomerism

A high-affinity ligand of cholera toxin, the divalent glycocalix[4]arene 1, was obtained by exploiting a combination of structure-based design of glycomimetic monovalent ligands and affinity enhancements by multivalent presentation through a calix[4]arene scaffold. It exhibits a slightly higher affinity for the toxin than its natural ligand, the GM1 oligosaccharide.

Topics: Calixarenes; Carbohydrate Sequence; Cholera Toxin; Glycocalyx; Kinetics; Ligands; Molecular Sequence Data; Oligosaccharides; Phenols

A calix[4]arene functionalized at one phenolic group with a pendant ethoxy acetate group, forms an inclusion complex that is stable even in the presence of other potential guest molecules.

Topics: Calixarenes; Hydrogen Bonding; Models, Molecular; Molecular Conformation; Phenols; Structure-Activity Relationship; Toluene

Upper rim substituted tetraiodo calix[4]arenes are coupled to a variety of acrylamides using the palladium catalysed Heck reaction. Tetra-acrylamido upper rim substituted calix[4]arenes are obtained in good yields with exceptionally high stereoselectivity, to produce the all-trans isomers. Tetra-acrylamido calix[4]arenes derived from secondary acrylamides are shown to dimerise via eight hydrogen bonds to form dimeric capsules, which are able to include small organic molecules.

Topics: Acrylamides; Calixarenes; Dimerization; Hydrogen Bonding; Magnetic Resonance Spectroscopy; Models, Molecular; Phenols

This article describes the synthesis and binding properties of highly selective noncovalent molecular receptors 1(3).(DEB)6 and 3(3).(DEB)6 for different hydroxyl functionalized anthraquinones 2. These receptors are formed by the self-assembly of three calix[4]arene dimelamine derivative molecules (1 or 3) and six diethylbarbiturate (DEB) molecules to give 1(3).(DEB)6 or 3(3).(DEB)6. Encapsulation of 2 occurs in a highly organized manner; that is, a noncovalent hydrogen-bonded trimer of 2 is formed within the hydrogen-bonded receptors 1(3).(DEB)6 and 3(3).(DEB)6. Both receptors 1(3).(DEB)6 and 3(3).(DEB)6 change conformation from staggered to eclipsed upon complexation to afford a better fit for the 2(3) trimer. The receptor selectivity toward different anthraquinone derivatives 2 has been studied using 1H NMR spectroscopy, X-ray crystallography, UV spectroscopy, and isothermal microcalorimetry (ITC). The pi-pi stacking between the electron-deficient center ring of the anthraquinone derivatives 2a-c and 2e-g and the relatively electron-poor melamine units of the receptor is the driving force for the encapsulation of the guest molecules. The selectivity of the hydrogen-bonded host for the anthraquinone derivatives is the result of steric interactions between the guest molecules and the calix[4]arene aromatic rings of the host.

Topics: Anthraquinones; Barbiturates; Calixarenes; Crystallography, X-Ray; Models, Molecular; Molecular Structure; Phenols; Triazines

Tetraurea calix[4]arenes with four loops form exclusively heterodimers with open-chain urea calix[4]arenes when they are dissolved in aprotic solvents. These assemblies can be considered as pseudorotaxanes. If open-chain tetraureas ending with maleic imide functions are used, their Diels-Alder reaction with 1,4,5,8-tetrapentoxyanthracene leads to tetra[2]rotaxanes which cannot be split into the single calixarene parts by hydrogen bond breaking solvents.

Topics: Calixarenes; Crystallography, X-Ray; Magnetic Resonance Spectroscopy; Models, Molecular; Molecular Structure; Phenols; Rotaxanes

The syntheses of calix[4]arene dimelamines that are functionalized with alkyl, aminoalkyl, ureido, pyridyl, carbohydrate, amino acid and peptide functionalities, and their self-assembly with barbituric acid or cyanuric acid derivatives into well-defined hydrogen-bonded nanostructures are described. The thermodynamic stability of these hydrogen-bonded assemblies was studied by CD spectroscopy in mixtures of CHCl3 and MeOH. The stability of the assemblies depends on several steric factors and the polarity of the functional groups connected to the assembly components.

Topics: Amines; Amino Acids; Barbiturates; Calixarenes; Carbohydrates; Circular Dichroism; Hydrogen Bonding; Molecular Conformation; Nanostructures; Peptides; Phenols; Stereoisomerism; Thermodynamics; Triazines

Selective and independent dimerization of tri- and tetraurea derivatives was used to build up dendritic assemblies which are uniform in size and structure. Dendrimers with the total molecular masses of about 25 000 g/mol were obtained. The existence of uniform assemblies was proved by 1H and 1H DOSY NMR experiments and also by dynamic light scattering.

Topics: Calixarenes; Hydrogen Bonding; Magnetic Resonance Spectroscopy; Models, Molecular; Molecular Conformation; Phenols; Urea

[Reaction: see text]. Fluorogenic calix[4]arenes (1 and 2) bearing a pendent ethyleneamine on their triazacrown rings, respectively, were synthesized in the cone conformation. Compared with 4, free 1 and 2 display a relatively weak emission, reflecting that a PET process from the pendent amine group (-CH2CH2NH2) to the fluorogenic pyrenes is mainly operated. Addition of various metal ions or anions to the solution of 1 or 2 reduces the PET because the pendent alkylamine takes part in the complexation, causing their fluorescence spectra to be changed. When Pb2+, a quenching metal ion, is added to 1 or 2, their pyrene monomer emission is enhanced with their excimer emission quenched, which is due to conformational changes of the facing carbonyl groups as well as to the participation of the ethyleneamine into the three-dimensional Pb2+ ion encapsulation. In contrast, upon addition of alkali metal ions to the 1 and 2, both monomer and excimer emissions are observed to increase, which is attributable to the CHEF effect and the retained conformations. For anion sensing, both 1 and 2 show a high selectivity for F- ions over other anions tested. When the F- ion is bound to 1 or 2 by hydrogen bonding between the amide NH of the triazacrown ring and F-, both their monomer and excimer emissions are weakened due to PET from the bound F- to the pyrene units.

Topics: Calixarenes; Computers, Molecular; Fluorescence; Models, Molecular; Phenols; Photometry; Positron-Emission Tomography; Pyrenes; Radiopharmaceuticals

[reaction: see text] The complexation of p-sulfonatocalix[4]arene (CX4) with 2,3-diazabicyclo[2.2.1]hept-2-ene (1), 2,3-diazabicyclo[2.2.2]oct-2-ene (2), 2,3-diazabicyclo[3.2.2]non-2-ene (3), 1-methyl-4-isopropyl-2,3-diazabicyclo[2.2.2]oct-2-ene (4), and 1-phenyl-2,3-diazabicyclo[2.2.2]oct-2-ene (5) was studied in D2O at pD 7.4 by 1H NMR spectroscopy. The formation of deep inclusion complexes was indicated by large upfield 1H NMR shifts of the guest protons (up to 2.6 ppm), which were also used to assign, in combination with 2D ROESY spectra, a preferential inclusion of the isopropyl group of 4 and a dominant inclusion of the azo bicyclic residue for 5. The bicyclic azoalkanes 1-3 showed exceptionally high binding constants on the order of 1000 M(-1), 1-2 orders of magnitude larger than for previously investigated noncharged organic guest molecules. The strong binding was attributed to the spherical shape complementarity between the guest and the conical cavity offered by CX4. Interestingly, although the derivatives 4 and 5 are more hydrophobic, they showed a 2-3 times weaker binding, which was again attributed to the deviation from spherical shape in these bridgehead-substituted derivatives. The preferential inclusion of the hydrophilic but spherical bicyclic residue of 5 rather than the hydrophobic aromatic phenyl group provides a unique observation in aqueous host-guest chemistry and corroborates the pronounced spherical shape affinity of CX4.

Topics: Azo Compounds; Bridged Bicyclo Compounds, Heterocyclic; Calixarenes; Magnetic Resonance Spectroscopy; Molecular Conformation; Phenols; Reference Standards

The calix[4] open-chain crown ether, 5,11,17,23-tetra-tert-butyl-25,27-di(2-allyloxyethoxyl)-26,28-dihydroxycalix[4]arene was synthesized and used for preparation of solid-phase microextraction (SPME) fibers of enhanced extraction efficiency. The new SPME coating made from calix[4] open-chain crown ether and hydroxyl-terminated silicone oil was developed with the aid of vinyltriethoxylsilane as bridge using sol-gel method and cross-linking technology. The efficiency of the novel fiber in the extraction of polar aromatic and aliphatic compounds, such as phenols, alcohols, and volatile fatty acids, was also investigated. Due to the introduction of the polar open-chain crown ether in calix[4]arene molecules, the calix[4] open-chain crown ether fiber showed much better selectivity and sensitivity to these polar compounds in comparison with calix[4]arene fiber. It also had superior extraction efficiency when compared to commercial poly(dimethylsiloxane)-divinylbenzene and polyacrylate fibers. Parts per billion to parts per trillion level detection limits were achieved for most of the analytes through SPME in conjunction with GC and flame ionization detector. The linear ranges were two to four orders of magnitude, and the RSD values were below 7% for all analytes. The novel fiber was applied to determine volatile alcohols and fatty acids in wine samples. The volatile-free wine prepared in this work was used to assure similar chemical environment for analytes in both calibration solutions and in real wine samples, thus compensating for possible matrix interferences. The established internal standard method using 4-methyl-2-pentanol as internal standard showed satisfactory accuracy and precision.

Topics: Alcohols; Anions; Calixarenes; Crown Ethers; Fatty Acids, Volatile; Microchemistry; Molecular Structure; Phenols; Polymers; Sensitivity and Specificity; Wine

A simple, sensitive, and accurate method for the determination of propranolol in human urine has been developed based on solid-phase microextraction (SPME) followed by GC-flame ionization detection (FID). The sol-gel 5,11,17,23-tetra-tert-butyl-25,27-dihydroxy-26,28-diglycidyloxycalix[4]arene/hydroxy-terminated silicone oil (diglycidyloxy-C[4]/OH-TSO) fiber was prepared to accommodate to the harsh extraction conditions. It possesses excellent alkali-proof ability and retains its extraction characteristics intact even after treatment with highly alkaline (4 mol/L) NaOH solution. Direct chemical bonding of the coating to the fiber surface provides it with excellent solvent resistance and the introduction of calixarene enhances its thermal stability. The newly developed sol-gel calixarene coating was effectively used for the extraction of propranolol in human urine. No interference with the determination of propranolol was observed from the urine components. Standard curves were linear in the range 50-5000 microg/L for headspace-SPME (HS-SPME) and 25-25000 microg/L for direct-SPME (Dir-SPME) with correlation coefficients better than 0.9999. The detection limit was 0.275 microg/L for HS-SPME and 0.193 microg/L for Dir-SPME. The method was validated using standard addition methodology and recovery values were between 91.4 and 117% for both the sampling modes with the RSDs less than 6% at different concentration levels in the linear ranges. The results obtained by both the sampling modes were feasible, and no significant differences between them regarding accuracy, precision, and detection limits were seen.

Topics: Calixarenes; Chemistry; Chromatography, Gas; Dose-Response Relationship, Drug; Humans; Male; Models, Chemical; Phenols; Propranolol; Regression Analysis; Reproducibility of Results; Sensitivity and Specificity; Sodium Hydroxide; Temperature

The solvent control on the ability of a partially substituted lower rim calix(4)arene derivative 5,11,17,23,tetra-tert-butyl[25,27-bis(hydroxy)-26,28-bis(ethylthioethoxy)]-calix(4)arene, 1 to host soft metal cations (Hg(II) and Ag(I)) is demonstrated through 1H NMR, electrochemical (conductance measurements), and thermodynamic characterization of the complexation process in a wide variety of solvents. Solvent-ligand interactions were assessed from 1H NMR measurements involving 1 and various solvents in CDCl3. Thus, the formation of a 1:1 1-CH3CN adduct is reported. As far as metal cations are concerned, depending on the medium their complexation with 1 was only observed for Hg(II) and Ag(I). Thus, in acetonitrile, 1 is more selective for Hg(II) relative to Ag(I) by a factor of 2.2 x 10(3). In methanol the selectivity is reversed to an extent that the affinity of 1 for Ag(I) is 1.4 x 10(3) higher than that for Hg(II). However, 1 is unable to recognize selectively these cations in N,N-dimethylformamide while in propylene carbonate the ability of 1 to interact with these cations is lost. An outstanding feature of thermodynamics emerges when an assessment is made of the ligand effect on the complexation of these cations and analogues calix(4)arene derivatives. Thus, in acetonitrile the thermodynamics of cation complexation by the hydrophilic cavity of a calix(4)arene containing mixed pendant groups is built up from thermodynamic data for the same process involving derivatives with common functionalities at the narrow rim. This is a unique example of the additive contribution of pendant arms in the field of thermodynamics of calixarene chemistry.

Topics: Acetonitriles; Calixarenes; Ligands; Magnetic Resonance Spectroscopy; Mercury; Methanol; Molecular Structure; Organometallic Compounds; Phenols; Silver; Solvents; Thermodynamics

The interaction of a calix(4)arene derivative, namely 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetra[2-(4-pyridyl)methoxy]calix(4)arene, 1a, and its monomeric component, p-tert-butylphenoxy-4-pyridine, 1b, with metal cations has been investigated in acetonitrile and methanol. (1)H NMR measurements carried out in CD(3)CN show the primary role played by the pyridyl nitrogens in their complexation with metal cations. Conductance measurements demonstrated that for all cations (except mercury) the composition of the metal ion complexes of 1a is 1:1 (ligand:metal cation). However, 1a hosts two mercury cations per unit of ligand. For the monomer 1b, complexes of 2:1 (ligand:metal cation) stoichiometries are formed with the exception of Pb(2+) (1:1 composition). The thermodynamics of complexation of these systems are reported in acetonitrile. Data in methanol are limited to stability constant values for mercury(II) and these ligands. This paper demonstrates for the first time that thermodynamic data for the complexation of the monomeric component of the ligand and metal cations contribute significantly to the interpretation of systems involving cation-calixarene interactions in solution.

Topics: Calixarenes; Cations; Metals, Heavy; Models, Molecular; Molecular Conformation; Phenols; Pyridines; Thermodynamics

This paper reports thermodynamic data for the transfer of calixarene derivatives and their metal-ion complexes in dipolar aprotic solvents. These data are used to assess the effect of solvation of these compounds on the selective complexation shown by these macrocycles for soft metal cations in different media. Thus, solubilities and derived Gibbs energies of solution of 5,11,17,23-tetra-tert-butyl[25,27-bis(hydroxyl)-26,28-bis(ethylthioethoxy)]calix(4)arene, 1, and 5,11,17,23-tetra-tert-butyl-[25,27-bis(ethylenethanoate)-26,28-bis(ethylthioethoxy)]-calix(4)arene, 2, in various solvents at 298.15 K are reported. Solvation of these ligands in one medium relative to another is analyzed from their standard transfer Gibbs energies using acetonitrile as the reference solvent. These data are combined with transfer enthalpies (derived from standard solution enthalpies obtained calorimetrically) to calculate the corresponding entropies of transfer of these calix(4)arene derivatives from acetonitrile to methanol and N,N-dimethylformamide. As far as the metal-ion salts (silver and mercury) in their free and complex forms are concerned, standard solution enthalpies were determined in acetonitrile, methanol, and N,N-dimethylformamide. These data are used to derive their transfer enthalpies from one medium to another. It is concluded that the extent of complexation of these macrocycles with soft metal cations is controlled by not only the solvation changes that the free cation undergoes in moving from one medium to another but also those for the ligand and its complex cation in these solvents.

Topics: Calixarenes; Calorimetry; Cations; Ligands; Mercury; Metals; Phenols; Solubility; Solutions; Solvents; Thermodynamics

5,11,17,23-Tetra-tert-butyl-25,27-diethoxy-26,28-dihydroxycalix[4]arene/hydroxy-terminated silicone oil coated fiber was first prepared and applied for solid-phase microextraction (SPME) with sol-gel technology. The possible sol-gel mechanism was discussed and confirmed by IR spectra. It showed wonderful selectivity and sensitivity to polar (aromatic amines), nonpolar (benzene derivatives, polycyclic aromatic hydrocarbons) and high boiling point compounds (phthalates) and the extraction equilibria were reached quite fast. The coating has high thermal stability (380 degrees C) and solvent stability (organic and inorganic), thus its lifetime is longer than conventional fibers. In addition, it has surprising fiber-to-fiber and batch-to-batch reproducibility. The detection limits were quite low and the linear ranges were pretty broad for all analytes.

Topics: Calixarenes; Gels; Phenols; Reproducibility of Results; Sensitivity and Specificity

Calixarenes bearing optically pure alpha,beta-amino alcohol groups at their lower rim exhibit exceptional and efficient chiral recognition ability in discrimination of racemic mandelic acid, 2,3-dibenzoyltartaric acid and 2-hydroxy-3-methylbutyric acid. [structure: see text]

Topics: Amino Alcohols; Calixarenes; Carboxylic Acids; Hemiterpenes; Mandelic Acids; Molecular Structure; Pentanoic Acids; Phenols; Stereoisomerism; Tartrates

We investigate the self-assembly of modified calix[4]arene on gold surfaces. Calix[4]arene was modified through a reaction sequence which led to assembling of the crown-5 moiety and to the insertion of two thioether groups into the starting molecule. The so-obtained calix[4]arene-crown-5 bis(7-thiatridecyloxy) (hereafter called calix[4]arene) was in the stable 1,3-alternate conformation. The calix[4]arene/gold interface was investigated by means of spectroscopic ellipsometry (SE), scanning tunneling microscopy (STM) and cyclic voltammetry (CV). SE data indicate a layer thickness compatible with the formation of a monomolecular layer. This result is confirmed by STM imaging which shows the formation of a high density of small pits, one gold layer deep, a typical feature of self-assembled organosulphur monolayers on gold. CV measurements performed in presence of the [Ru(NH(3))(6)(2+/3+)] redox couple indicate a passivation of the metal electrode, resulting in a reduction of the redox current, after the layer deposition. CV has also been used to investigate the selectivity properties of calix[4]arene-covered gold electrodes by measuring the redox current decrease in the presence of different salt solutions. It is found that calix[4]arene-covered electrodes are able to complex K(+) and Ba(2+), while no complexation is observed in the case of Li(+), Na(+), Cs(+), Mg(2+) and Ca(2+).

Topics: Adsorption; Calixarenes; Coated Materials, Biocompatible; Crystallization; Electric Impedance; Electrochemistry; Materials Testing; Organic Chemicals; Phenols; Sulfur Compounds

Two-armed neutral anion receptors (4,5), were prepared and examined for their anion-binding ability using UV-vis, fluorescence and 1H NMR spectra in DMSO. The results of non-linear curve fitting indicate that 4 or 5 form 1 : 1 stoichiometric complexes with dicarboxylate anions by multiple hydrogen bonding interactions and the sensitivity for recognition of dicarboxylate depends on the chain length of these dicarboxylate anions. Receptors 4 and 5 have no binding ability with acetate, dihydrogen phosphate and the halogen (Cl-, Br-, I-) anions. This demonstrates that receptors 4 or 5 could be used as chemical sensors for some special dicarboxylate anions.

Topics: Amides; Anions; Calixarenes; Carboxylic Acids; Molecular Structure; Phenols; Thiourea

[structure: see text] We have synthesized a number of calix[4]arene derivatives presenting thiourea functional groups at their upper rims by the condensation of a 1,3-di(p-amino)calix[4]arene with alkyl isothiocyanates. Mono- and dithiourea-substituted calix[4]arenes were prepared selectively in good yields, and homocoupling of the former led to calix[4]arene dimers with a thiourea linker. X-ray crystallography revealed interesting intra- and intermolecular hydrogen bonding patterns. (1)H NMR data and computational studies also provided some insight into the hydrogen bonding patterns.

Topics: Calixarenes; Hydrogen Bonding; Models, Chemical; Molecular Conformation; Phenols; Solutions; Thiourea

Complexation of free and N-acetylated alpha-amino acid anions (Gly, Ala, Phe) and some structurally related guests by a dicationic cyclophane-type N,N'-dibenzylated chiral derivative of a bisisoquinoline macrocyclic alkaloid S,S-(+)-tetrandrine (DBT) has been studied by (1)H-NMR titrations in D(2)O. In contrast to other macrocyclic hosts like cyclodextrins and calixarenes, DBT shows highest affinity and large enantioselectivity (K(S)/K(R) >/=10) toward smaller N-acetylalanine and binds larger phenylalanine derivatives more weakly and non-selectively. With 1,2,3,4-tetrahydroisoquinoline-3-carboxylate, a rigid analog of phenylalanine, binding again becomes enantioselective with K(S)/K(R)= 3.8. The binding specificity of DBT is rationalized on the basis of molecular mechanics calculations.

Topics: Acetylation; Alkaloids; Amino Acids; Anions; Benzyl Compounds; Benzylisoquinolines; Calixarenes; Cyclodextrins; Deuterium Oxide; Kinetics; Magnetic Resonance Spectroscopy; Models, Molecular; Molecular Structure; Phenols; Stereoisomerism

The formation of a hydrogen-bonded receptor in niosomal membranes is reported in this communication. The niosomes prepared from non-ionic surfactants C12EO3 and C14EO3 provide a stable system that allows the self-assembly of hydrogen-bonded receptors to occur in contact with aqueous environments. We demonstrate here by CD, TEM and Confocal Microscopy that the incorporation of the building blocks, calix[4]dimelamine 1 and PerBAR, within the niosomal membranes led to the formation of well-defined hydrogen-bonded assembly 13.(PerBAR)6 within these membranes.

Topics: Barbiturates; Biomimetic Materials; Calixarenes; Circular Dichroism; Hydrogen Bonding; Liposomes; Membranes, Artificial; Perylene; Phenols; Receptors, Cell Surface; Surface-Active Agents; Triazines

Wide rim tetraurea derivatives (2a,b) have been prepared from a calix[4]arene rigidified in the cone conformation by two diethyleneglycol ether bridges between adjacent oxygens. In comparison to the analogous tetraurea derivatives (3a,b) of a tetrapentoxy calix[4]arene, 2a,b show an increased thermodynamic stability in mixtures of CDCl(3) and DMSO-d(6). Their kinetic stability as expressed by the rate of guest exchange (benzene or cyclohexane against the solvent benzene-d(6)) is also strongly increased by factors of 30-38. Noticeable differences for the inclusion of selected guests are found.

Topics: Calixarenes; Kinetics; Magnetic Resonance Spectroscopy; Molecular Conformation; Molecular Structure; Phenols; Thermodynamics; Urea

Two novel regioisomeric calix[4]arene derivatives (2 and 3), decorated with two aza[18]crown-6 units at vicinal (1,2) or diagonal (1,3) positions of the upper rim, were synthesized. The catalytic activities of their dinuclear Ba2+ complexes were investigated in the ethanolysis of esters 8-11, endowed with a carboxylate anchoring group. Major results are as follows: 1) the two metal ions in the dinuclear catalysts work together in a cooperative fashion; 2) the vicinal calix[4]arene catalyst 2 is far superior to its diagonal regioisomer 3 in the reactions of all of the investigated esters; and 3) the distance between the carboxylate and ester carbonyl, which increases regularly from 8 to 11, influences reactivity of catalytic ester cleavage in a way that is decidedly suggestive of the importance of a good match between ester size and metal-to-metal distance. However, the superiority of the vicinal catalyst 2 relative to 3 cannot be explained on the basis of the putative match of ester size to intermetal distance, thus providing an indication that additional, still poorly understood effects may contribute significantly to catalytic efficiency.

Topics: Barium; Calixarenes; Catalysis; Crystallography, X-Ray; Esters; Ligands; Models, Molecular; Molecular Structure; Organometallic Compounds; Phenols

The stability of some porphyrin-calix[4]arene sodium-ion complexes were determined by a collision-activated decomposition (CAD) method utilizing electrospray ionization mass spectrometry (ESI-MS). Comparing the values of E(1/2), the collision energy at which the relative intensity of the complex ion is 0.5, we found that the porphyrin-calix[4]arene complex with the higher value of E(1/2) corresponded to that with the larger association constant (Kass), as measured by 1H-NMR in CDCl3. Both our ESI-MS and NMR studies proved that the number of hydrogen bonds and the rigidity of the calix[4]arene stabilized the complex. The ESI-MS technique could be successful in screening the binding affinity in host-guest systems with a small amount of sample.

Topics: Algorithms; Calixarenes; Gases; Kinetics; Macromolecular Substances; Magnetic Resonance Spectroscopy; Microchemistry; Phenols; Porphyrins; Protons; Spectrometry, Mass, Electrospray Ionization

Icosahedral and cuboctahedral arrangements of calixarenes, a nanometer-scale, spheroidal assembly of 12 calixarene molecules, can be manipulated in a highly controlled fashion. Previously, such assemblies were observed to favor placement of the calixarenes at the vertexes of an icosahedron. A supramolecular constraint is employed in order to enforce molecular alignment and produce a cuboctahedral arrangement. The internal volume of the cuboctahedron is approximately 30% greater than that of the icosahedron. Furthermore, in stark contrast to that of the icosahedral Platonic solid, the shell of the cuboctahedral Archimedean solid is porous.

Topics: Biomimetic Materials; Calixarenes; Hydrophobic and Hydrophilic Interactions; Lanthanoid Series Elements; Macromolecular Substances; Models, Molecular; Organometallic Compounds; Phenols; Sulfonic Acids; Viruses

We have designed and synthesized a modified calixarene derivative (1) that allows, for the first time, the isolation of a stable cation radical salt that binds a single molecule of nitric oxide deep within its cavity with remarkable efficiency (KNO >108 M-1), as demonstrated by isolation of a crystalline complex [1, NO]+ and its characterization by X-ray crystallography as well as by optical spectroscopy. Furthermore, the ready accessibility of the calixarene cation radical will allow the exploration of its use for developing efficient sensing devices for nitric oxide based on the accompanied color changes.

Topics: Biosensing Techniques; Calixarenes; Cations; Colorimetry; Free Radicals; Kinetics; Nitric Oxide; Phenols

A fluorescent poly(phenylene ethynylene) containing calix[4]arene-based receptor units has a sensitivity to quenching by the N-methylquinolinium ion that is over three times larger than that seen in a control polymer lacking calix[4]arenes.

Topics: Calixarenes; Fluorescence; Phenols; Polymers; Quinolinium Compounds

A new fluorescent chemosensor with two different types of cation binding sites on the lower rims of a 1,3-alternate calix[4]arene (1) is synthesized. Two pyrene moieties linked to a cation recognition unit composed of two amide groups form a strong excimer in solution. For 1, the excimer fluorescence is quenched by Pb2+, but revived by addition of K+ to the Pb2+ ligand complex. Thus, metal ion exchange produces an on-off switchable, fluorescent chemosensor. Computational results show that the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbitals (LUMO) of the two pyrene moieties interact under UV irradiation of 1 and its K+ complex, while such HOMO-LUMO interactions are absent in the Pb2+ complex.

Topics: Calixarenes; Cations; Fluorescent Dyes; Lead; Metals; Models, Molecular; Phenols; Potassium; Pyrenes; Spectrometry, Fluorescence

The ditopic receptors Calix-COU1 and Calix-COU2 consist of a calix[4]biscrown containing one or two dioxycoumarin fluorophores, respectively, inserted into the crown. They can form 1:1 and 2:1 (metal:ligand) complexes with caesium ions. The photophysical properties of the 1:1 complexes can be explained by (i) cation tunneling through the tube-shaped cavity (composed of the four phenyl rings) of the calix[4]biscrown, (ii) photodisruption of the interaction between the bound cation and the oxygen atoms belonging to both the coumarin moiety and the crown, (iii) photoinduced motions of the cation.

Topics: Algorithms; Calixarenes; Cesium; Chelating Agents; Coumarins; Crown Ethers; Models, Chemical; Phenols; Spectrometry, Fluorescence; Spectrophotometry

A novel solid-phase microextraction (SPME) fiber coated with 25,27-dihydroxy-26, 28-(1', 10'-dioxa-4', 7'-diaza-3', 8'-dioxooctylene ) -p-tert-butylcalix [ 4 ] arene/hydroxy-terminated silicone oil (amide bridged -C[4]/OH-TSO) was prepared with sol-gel technology and applied to the analysis of aliphatic amines and aromatic amines without derivatization. It demonstrated high thermal stability of up to 380 degrees C and stability in organic and inorganic solvents, a prolonged lifetime of over 200 times for headspace SPME, great fiber-to-fiber reproducibility with a relative standard deviation (RSD) of no more than 6.3% for aromatic amines, etc. Due to the introduction of polar amide bridge in calixarene molecules, polarity of the coating increases and thus the fiber shows better extraction efficiency in most of the investigated aliphatic amines and aromatic amines compared to the extraction efficiency of commercial fibers, indicating specific selectivity and sensitivity to amines. The detection limits (LODs) were determined to be 0.19 - 39.51 microg/L, the linear ranges were 3 orders of magnitude with a precision better than 5.1% for aliphatic amines, and they were 1.21 - 40.73 ng/L, 4 - 6 orders of magnitude with a precision better than 6.0% for aromatic amines. The application of this SPME technique coupled with gas chromatography has been shown to be feasible for the rapid determination of fish freshness.

Topics: Amines; Animals; Calixarenes; Chromatography, Gas; Fishes; Gels; Osmolar Concentration; Phenols; Polymethyl Methacrylate; Reproducibility of Results; Sensitivity and Specificity

A calix[4]arene derivative containing ethoxycarbonylmethoxy groups in the coordination sphere and an iminopyridinium indicator group was studied by FT-IR spectroscopy in acetonitrile solution. The characteristic changes of v(C=O) stretching vibration offered an opportunity for the improvement on selectivity of the ion recognition process of this ligand. The shift of the carbonyl stretching vibration band depended on complex formation as well as on the equilibrium constants of complex formation. In the case of sodium complex, a well-defined isobestic point was detected in the v(C=O) region while altering the sodium concentration. The affinity of thallium(III) to form complex with calixarene 1 was found comparable with those of lithium, sodium or calcium. The complex was found to be an M2L type supramolecule, whereas one molecule of triethylamine was necessary for the formation of each complex.

Topics: Acetonitriles; Calcium; Calixarenes; Ethylamines; Ions; Lithium; Models, Chemical; Phenols; Sodium; Spectrophotometry; Spectroscopy, Fourier Transform Infrared; Thallium; Time Factors

[structure: see text] Appending tetraphenylporphyrin units to the calix[4]arene skeleton via the ureido function leads to novel anion receptors designed for anion and/or cation detection by UV-vis spectroscopy. Calixarenes in the cone or 1,3-alternate conformations bearing two ureido moieties on the upper rim represent well-preorganized cavities where the anion can be held by synchronous hydrogen bonding interaction with the NH groups.

Topics: Anions; Binding Sites; Calixarenes; Molecular Conformation; Phenols; Porphyrins; Spectrum Analysis; Structure-Activity Relationship

Contact mode atomic force microscopy has been carried out on gels of four current polymers, carbopol 980, carbopol 2020, hyaluronic acid and xanthan containing dispersions of solid lipid nanoparticles (SLNs) of amphiphilic calixarenes. Imaging shows that the SLNs are dispersed within the gels as discrete particles of 150nm in diameter and show little or no aggregation. The simultaneous use of lateral force, topographic and force modulation mode imaging allows a clear interpretation of the observed images, showing the presence of nanoparticles in the sub-surface region and that the SLNs affect the local mechanical properties of the gels. Photon correlation spectroscopy similarly demonstrates a lack of interaction in suspensions.

Topics: Bridged-Ring Compounds; Calixarenes; Excipients; Gels; Hyaluronic Acid; Microscopy, Atomic Force; Nanotechnology; Particle Size; Phenols; Polysaccharides, Bacterial

The preparation and stability parameters of para-acyl-calix[4]arene based solid lipid nanoparticles (SLNs) have been investigated. Atomic force microscopy (AFM) and photon correlation spectroscopy (PCS) show a mean particle size of 130 nm. In terms of preparation parameters, using the solvent displacement method, the nature and the volume of the organic solvent, the concentration of the amphiphile and the presence of a co-surfactant in the organic phase have been shown to affect significantly the size of the produced SLNs. In contrast, the stirring speed, the viscosity and the acidity of the aqueous phase and the amphiphile hydrophobic chain length have been shown to have no effect. In terms of stability parameters, the ionic strength has been shown to affect the short-time SLN stability depending on both the anion and the cation studied, with sodium sulphate causing precipitation. Ultrasonic, ultraviolet or microwave treatments of the SLN suspensions have no effect on the size of the SLNs. The study of the effects of short time thermal treatment revealed that the SLNs are not affected by one freezing-defreezing cycle and are stable at 100 degrees C in suspension. It is difficult to reconstitute the SLN suspensions after freeze-drying. Finally, the temporal stability of these suspensions in water has been shown to be superior to 1 year. The long-term temporal stability of suspensions stored in saline solution has been investigated. It has been demonstrated that the most destabilising effects arise from the presence in the storage suspension of sulphate ions.1H NMR, X-ray powder diffraction (XPD) and AFM have also been carried out on the calix-arene based SLNs and demonstrate the presence of a semi-organised matrix structure for the SLNs.

Topics: Calixarenes; Crystallization; Drug Carriers; Drug Stability; Fatty Acids; Freeze Drying; Hydrogen-Ion Concentration; Hydrophobic and Hydrophilic Interactions; Magnetic Resonance Spectroscopy; Microscopy, Atomic Force; Microspheres; Microwaves; Nanotechnology; Osmolar Concentration; Particle Size; Phenols; Solvents; Surface-Active Agents; Temperature; Ultrasonics; Ultraviolet Rays; Viscosity; X-Ray Diffraction

A hydrogen ion-selective poly(vinyl chloride) membrane electrode was constructed using 5,11,17,23-tetra-tert-butyl-25,26,27,28-tetracyanomethoxycalix[4]arene as a neutral carrier. The electrode showed an apparent Nernstian response in the 2-11.5 pH range with a slope of 54.0 +/- 0.2 mV/pH at 20 +/- degrees C. This electrode showed a rapid response of the emf to changes in the pH, high ion selectivity with respect to lithium, sodium and potassium, and characteristics similar to those reported for the conventional pH glass membrane electrode. It can be used as a potentiometric indicator electrode in hydrofluoric acid solutions. The effects of iodide, thiocyanate, perchlorate and bromide on the characteristics of the electrode were also considered.

Topics: Calixarenes; Hydrogen; Hydrogen-Ion Concentration; Ion-Selective Electrodes; Phenols; Polyvinyl Chloride; Reference Values; Sensitivity and Specificity; Time Factors

The complexation luminescence behavior of a water soluble calix[4]arene derivative, 5,11,17,23-tetra-sulfonate-25,26,27,28-tetra-carboxymethoxycalix[4]arene (L) with lanthanoid ion (Tb(3+)) has been investigated in gelation solution at 25 degrees C by using UV-vis and fluorescence spectra. The results obtained indicated that the water soluble calix[4]arene derivative can form an efficient energy transfer complex with terbium ion(III). The fluorescence of L x Tb(3+)complex is partially quenched by gelatin in gelation solution. The quenching intensity is related to the concentration and the hydrolysis degree of gelatin. Absorption and fluorescence spectra analysis show that the -COO(-) groups on gelatin have a definite binding ability to Tb(3+), and then, gelatin could compete binding with calix[4]arene derivative upon complexation with Tb(3+), leading to the relative fluorescence quenching of the formation complex of terbium(III) ion with calix[4]arene derivative.

Topics: Calixarenes; Gelatin; Luminescence; Phenols; Spectrometry, Fluorescence; Spectrophotometry, Ultraviolet; Terbium

The interaction of Solid Lipid Nanoparticles (SLN) based on amphiphilic calix[4]arene with one of the major circulatory protein, serum albumin, has been investigated by Photon Correlation Spectroscopy (PCS) and Atomic Force Microscopy (AFM). The carrier systems have shown the ability to interact with bovine serum albumin (BSA), which forms a capping layer up to 17nm in depth. AFM imaging revealed that the SLNs are protected by this layer against flattening on surfaces.

Topics: Adsorption; Calixarenes; Drug Delivery Systems; Lipids; Microscopy, Atomic Force; Phenols; Serum Albumin, Bovine

Calix[4]arene derivatives containing amide ferrocene units at the wide rim and ethyl ester groups at the narrow rim, L1-L3, were synthesized and their anion binding and sensing properties were investigated. It was found from (1)H NMR titrations that L1-L3 were able to bind selectively with carboxylate anions. Moreover, cyclic voltammetry and square wave voltammetry showed that L1-L3 were able to act as electrochemical sensors for carboxylate anions. [structure: see text]

Topics: Amides; Anions; Biosensing Techniques; Calixarenes; Carboxylic Acids; Electrochemistry; Ferrous Compounds; Magnetic Resonance Spectroscopy; Metallocenes; Models, Molecular; Phenols; Sensitivity and Specificity; Titrimetry

We have synthesized three types of calix[4]arene- nucleoside hybrid efficiently by amide bond formation between the amine functional groups of 1,3-diaminocalix[4]arene and the carboxyl groups of thymidine nucleoside derivatives. X-ray crystallography of a homocoupled calix[4]arene-nucleoside hybrid revealed an interesting hydrogen bonding pattern between thymine bases and the amide linkages. We designed the calix[4]arene-oligonucleotide hybrids (5'-AAAAGATATCAAXTTGATATCTTTT-3', 5'-T12-X-T12-3', and 5'-A12-X-T12-3') to be V-shaped oligodeoxyribonucleotides and synthesized them by using a calix[4]arene-nucleoside hybrid (X) as a key building block. Thermal denaturation experiments, monitored by UV spectroscopy at 260 and 284 nm, and circular dichroism spectra of the calix[4]arene-oligonucleotide hybrids suggest that the modified oligonucleotides indeed adopt V-shaped conformations, making them suitable for use as building blocks in the construction of programmed oligonucleotide nanostructures

Topics: Amides; Bridged-Ring Compounds; Calixarenes; Chromatography, High Pressure Liquid; Circular Dichroism; Crystallography, X-Ray; Electrophoresis, Polyacrylamide Gel; Hydrogen Bonding; Models, Molecular; Nucleic Acid Conformation; Nucleic Acid Denaturation; Nucleosides; Oligodeoxyribonucleotides; Phenols; Thymidine

A new class of ionophore consisting of two calix[4]arene units linked through the lower rim by two ethylene chains, in combination with propyl ether and phenolic functional groups, has been developed. These calix[4]semitube molecules exhibit remarkable selectivity and fast complexation kinetics for potassium over all Group 1 metal cations. Molecular modelling studies, using structural models derived from crystallographic data, suggest the potassium cation is complexed by a horizontal, side-on route and not through the calix[4]arene annulus. The length of the bridging alkylene chain between the respective calix[4]arenes of the semitube structure dictates the strength and selectivity of alkali metal cation binding.

Topics: Calixarenes; Crystallography, X-Ray; Ionophores; Kinetics; Magnetic Resonance Spectroscopy; Metals, Alkali; Models, Molecular; Molecular Structure; Phenols; Potassium; Thermodynamics

We here report a novel example of artificial glycoviral vectors constructed via number- and size-controlled gene (pCMVluc, 7040 bp) coating with micellar glycocluster nanoparticles (GNPs) of calix[4]resorcarene-based macrocyclic glycocluster amphiphiles having eight or five saccharide moieties with terminal alpha-glucose (alpha-Glc), beta-glucose (beta-Glc), or beta-galactose (beta-Gal) residues. The resulting glycoviruses are compactly packed (approximately 50 nm) and well charge-shielded (zeta approximately equal 0 mV), undergo saccharide-dependent (alpha-Glc > beta-Gal >> beta-Glc) self-aggregation, and transfect cell (Hela and HepG2) cultures as triggered by the pinocytic form of endocytosis. The semilogarithmic linear size-activity correlation suggests that size-restricted pinocytosis (<100 nm) is effective only for monomeric viruses. The activities of oligomeric and otherwise poorly active beta-Gal-functionalized viruses toward hepatic HepG2 cells are approximately 10(2)-times higher than expected on the size basis, owing to the receptor-mediated specific pathway involving the asialoglycoprotein receptors on the hepatic cell surfaces. The scope and prospect of artificial glycoviruses are discussed.

Topics: Calixarenes; Cytomegalovirus; Genetic Vectors; HeLa Cells; Humans; Luciferases; Particle Size; Phenols; Plasmids; Polysaccharides; Promoter Regions, Genetic; Transfection

Calix[4]arenes, calix[4]resorcarenes, and anionic cyclodextrin derivatives were examined as chiral NMR solvating agents. The calix[4]arenes were prepared by attachment of amino acids through the hydroxyl groups of the phenol rings. Chloroform-, methanol-, and water-soluble derivatives were prepared and tested with a range of substrates. Chloroform-soluble chiral calix[4]resorcarenes were prepared by attachment of chiral primary and secondary amines and examined in NMR applications with a variety of substrates. Sulfated and carboxymethylated beta-cyclodextrin are effective at causing enantiomeric discrimination in the (1)H NMR spectra of organic cations. Lanthanide ions associate at the carboxymethyl groups and cause sizeable shifts and enhancements in enantiomeric discrimination in the spectra of organic cations. The enhancements caused by the lanthanide ion are large enough that much lower concentrations of the cyclodextrin can be used as compared to conventional analyses.

Topics: Calixarenes; Catechols; Cations; Cyclodextrins; Hydrolysis; Lanthanoid Series Elements; Magnetic Resonance Spectroscopy; Models, Chemical; Phenols; Polymers; Stereoisomerism; Temperature

The thiourea group has been exploited to link two or four carbohydrate units at the upper rim of tetrapropoxycalix[4]arene derivatives in the cone conformation. Two synthetic methodologies were used, the first one consisting of the condensation of di- and tetraminocalix[4]arenes with the isothiocyanate of monosaccharides in dry CH2Cl2 at room temperature and the second one exploiting the condensation of an aminolactoside with a calixarene isothiocyanate. The first method allows the glycoconjugates to be obtained in 75-80% overall yields. The disfunctionalized derivatives exist in a closed flattened cone conformation in CDCl3 and CD3OD due to the formation of intramolecular hydrogen bonds involving the thiourea groups which are broken in DMSO-d6 to give an open flattened cone conformation. The thiourea groups act not only as linkers but also as binding units for anionic substrates as evidenced by solution 1H NMR and ESI-MS experiments. Turbidimetric analysis indicates that the tetraglucoside and tetragalactoside clusters give specific interactions with Concanavalin A (Con A) and peanut lectin (PNA), respectively. Both features show that the neoglycoconjugates could also be used as site specific molecular delivery systems.

Topics: Calixarenes; Concanavalin A; Glycoconjugates; Hydrogen Bonding; Molecular Conformation; Nephelometry and Turbidimetry; Organophosphorus Compounds; Peanut Agglutinin; Phenols; Spectrometry, Mass, Electrospray Ionization; Substrate Specificity; Thiourea

The affinities of ferrocene (2) and the cobaltocenium cation (3+), which have roughly the same size and differ in their charge, towards the inner cavity of the dimeric capsule formed by tetraurea calix[4]arene (1) were studied in C2D4Cl2 solutions. While 3+, which occupies more than 75% of the internal volume of the dimer, is readily encapsulated this is not the case for 2. This is probably due to cation-pi interactions, which operate only between 3+ and the aromatic rings of the calix[4]arene dimer. We found that the affinity of the cobaltocenium cation is higher than that of the tropylium cation (4+) and is only 2-3 times less than that of the tetraethylammoniun cation (5+). From the variable temperature 1H NMR spectra of this capsule, the free energy of activation at 298 K (deltaGdouble dagger(298K)) for the reorientation of the hydrogen bonded belt between the two parts of the dimer could be determined by total line shape analysis for the aromatic protons of the calixarene. The value of 14.3 +/- 0.2 kcal mol(-1) for the dimeric capsules of 3+ PF6- is very similar to the free activation energy found for dimeric capsules of 1 with 4+ PF6- and 5+ PF6- in C2D4Cl2. It becomes significantly lower, if PF6- is replaced by BF4-. We also found that ten times more DMSO is needed to disrupt the capsule 1 x 3+ x 1 than the corresponding 1 x 1 dimer containing benzene as guest. This demonstrates again the importance of the cation-pi interactions for the stability of such hydrogen-bonded dimeric capsules.

Topics: Calixarenes; Cations; Cobalt; Diffusion; Dimerization; Ferrous Compounds; Hydrogen Bonding; Magnetic Resonance Spectroscopy; Metallocenes; Organometallic Compounds; Phenols; Tetraethylammonium; Urea

The molecular recognition of tetra(p-t-butyl)tetrathiocalix[4]arene (I)and its three derivatives to heavy metal ions has been investigated by UV spectroscopy and solvent extraction. These derivatives include 5,11,17,23,-tetra-t-butyl-25,26,27,28-tetrakis(acetylmethoxy)tetrathiocalix[4]arene (II), 5,11,17,23-tetra-t-butyl-25,26,27,28-tetrakis(2'-hydroxypropyloxy) tetrathiocalix[4]arene (III), 5,11,17,23,-tetra-t-butyl-25,27-bis(3'-hydroxy propyloxy)tetrathiocalix[4]arene (IV). The UV spectra and solvent extraction of I show that it has an effective molecular recognition to heavy metal ions, especially to Cd(2+), while IV has a special molecular recognition to Ag(+) ion. These results confirmed the feasibilities for I to be applied in separation for toxic heavy metal ions Pb(2+), Cd(2+) and IV to be used as the sensor compound of Ag(+) ion-selective electrode.

Topics: Calixarenes; Metals, Heavy; Phenols; Solvents; Spectrophotometry, Ultraviolet

[structure: see text] Water-soluble models of heme-protein active sites are obtained via the self-assembly of cationic porphyrins 1 and tetrasulfonato calix[4]arene 2 (K(1.2)() = 10(5) M(-)(1)). Selective binding of ligands either outside or inside the cavity of assemblies 1.2 via coordination to the zinc center has been observed. Small ligands such as 4-methylpyridine and 1-methylimidazole are encapsulated, while the bulkier caffeine is bound outside. Assemblies Co-1.2, in which the Zn porphyrin moiety has been replaced by a Co(II) porphyrin, can act as O(2) carriers.

Topics: Binding Sites; Caffeine; Calixarenes; Calorimetry; Cobalt; Hemeproteins; Imidazoles; Ligands; Magnetic Resonance Spectroscopy; Models, Molecular; Peptides; Phenols; Porphyrins; Pyridines; Structure-Activity Relationship; Water; Zinc

We have synthesized three types of calix[4]arene-nucleoside hybrids efficiently by amide bond formation between the amine functional groups of 1,3-diamino-calix[4]arene and the carboxyl groups of thymidine nucleoside derivatives. X-Ray crystallography of a homocoupled calix[4]arene-nucleoside hybrid revealed an interesting hydrogen bonding pattern between thymine bases and the amide linkages. We designed the calix[4]arene-oligonucleotide hybrids to be V-shaped oligodeoxyribonucleotides and synthesized them by using a calix[4]arene-nucleoside hybrid as a key building block. Thermal denaturation experiments, monitored by UV spectroscopy at 260 and 284 nm, and circular dichroism spectra of the calix[4]arene-oligonucleotide hybrids suggest that the modified oligonucleotides indeed adopt V-shaped conformations, making them suitable for use as building blocks in the construction of programmed oligonucleotide nanostructures.

Topics: Calixarenes; Circular Dichroism; Nucleosides; Oligonucleotides; Phenols; Spectrophotometry, Ultraviolet

Two chromogenic calix[4]arene derivatives having identical coordination sphere (consisting of ester groups) but different chromogenic units (pyridinium type and dinitro-phenyl type) were the subject of structural studies with sodium(I) and thallium(I) ions in solid state, both as bulk and surface complexes. Their diffuse reflectance infrared Fourier transform (DRIFTS) spectra were recorded and the characteristic changes of the vibrational spectra due to complex formation were analysed based on curve fitting.

Topics: Calcium; Calixarenes; Lithium; Phenols; Sodium; Spectroscopy, Fourier Transform Infrared

In this paper, we report on the formation and properties of a water-stabilized dimer comprising calix[4]arene-guanosine conjugate cG 2. The 1,3-alternate calixarene cG 2 was poorly soluble in dry CDCl(3) and gave an ill-resolved NMR spectrum, consistent with its nonspecific aggregation. The compound was much more soluble in water-saturated CDCl(3). Two sets of well-resolved (1)H NMR signals for the guanosine residues in cG 2, present in a 1:1 ratio, indicated that the compound's D(2) symmetry had been broken and provided the first hint that cG 2 dimerizes in water-saturated CDCl(3). The resulting dimer, (cG 2)(2).(H(2)O)(n)(), has a unique property: it extracts alkali halide salts from water into organic solution. This dimer is a rare example of a self-assembled ion pair receptor. The identity of the (cG 2)(2).NaCl.(H(2)O)(n)() dimer was confirmed by comparing its self-diffusion coefficient in CDCl(3), determined by pulsed-field gradient NMR, with that of control compound cA 3, an adenosine analogue. The dimer's stoichiometry was also confirmed by quantitative measurement of the cation and anion using ion chromatrography. Two-dimensional NMR and ion-induced NMR shifts indicated that the cation binding site is formed by an intermolecular G-quartet and the anion binding site is provided by the 5'-amide NH groups. Once bound, the salt increases the dimer's thermal stability. Both (1)H NMR and ion chromatography measurements indicated that the cG 2 dimer has a modest selectivity for extracting K(+) over Na(+) and Br(-) over Cl(-). The anion's identity also influences the association process: NaCl gives a soluble, discrete dimer whereas addition of NaBPh(4) to (cG 2)(2).(H(2)O)(n)() leads to extensive aggregation and precipitation. This study suggests a new direction for ion pair receptors, namely, the use of molecular self-assembly. The study also highlights water's ability to stabilize a functional noncovalent assembly.

Topics: Calixarenes; Circular Dichroism; Dimerization; Guanosine; Magnetic Resonance Spectroscopy; Molecular Conformation; Phenols; Water

A calix[4]arene-derived ditopic receptor 1 has been synthesized. In the absence of Na+, the receptor binds acetate in preference to diphenyl phosphate (as the tetrabutylammonium salts), but in the presence of Na+, the selectivity is reversed and the receptor, instead, binds diphenyl phosphate, and not acetate, which preferentially forms a salt ion-pair in free solution. [structure: see text]

Topics: Acetates; Calixarenes; Cations; Phenols; Phosphates; Sodium

The molecular recognition properties of calixarenes to 2,3-diaminonaphthalene (DAN) were investigated. We found that the fluorescence emission of DAN has a blue shift after p-sulfonic sodium calix[4]arece (SSCA) was added to DAN. The proposed mechanism of the molecular recognition between SSCA and DAN indicates that DAN goes into the cavity of SSCA with the help of the hydrogen bonding between the amino group of DAN and sulphonyl group of SSCA. The inclusion ratios and inclusion constants of the host-guest complexes are determined by using the deduced equations.

Topics: 2-Naphthylamine; Calixarenes; Hydrogen Bonding; Macromolecular Substances; Phenols; Spectrometry, Fluorescence

[reaction: see text] Calix[4]arenes bearing one, two, or four 1,8-naphthyl imide groups at the wide rim and bis-calix[4]arenes connected via perylene-bisimide dye spacers have been synthesized. The low-temperature NMR spectrum of the tetranaphthylimide suggests, in agreement with a crystal structure, a C2-symmetrical pinched cone conformation stabilized via face-to-face pi-pi interactions between opposite naphthylimide groups. UV-vis and fluorescence studies have been carried out for the perylene bis-calix[4]arene dyes.

Topics: Calixarenes; Coloring Agents; Fluorescent Dyes; Imides; Molecular Structure; Naphthalenes; Perylene; Phenols

After heat erases the order in 1,3-O,O'-bis(dodecyl)calix[4]arene, it self-organizes the phenyl units into a rigid calix bowl first at T2 = 111 degrees C, followed by the formation of all-trans alkyl chains at T1 = 62 degrees C, which eventually yields a stable cone-shaped structure at room temperature.

Topics: Calixarenes; Calorimetry, Differential Scanning; Hot Temperature; Macromolecular Substances; Molecular Conformation; Phenols; Spectroscopy, Fourier Transform Infrared; Temperature

The complexation spectroscopic behavior of three p-tert-butylcalix[4]arene Schiff bases i.e. 5,11,17,23-tetra-tert-butyl-25,27-bis[2-[N-(3-nitrobenzylidene)amino]ethoxy]-26,28-dihydroxycalix[4]arene (1), 5,11,17,23-tetra-tert-butyl-25,27-bis[2-[N-(2-hydroxybenzylidene)amino]ethoxy]-26,28-dihydroxycalix[4]arene (2), and 5,11,17,23-tetra-tert-butyl-25,27-bis[2-[N-(2-hydroxy-3-methoxybenzylidene)amino]ethoxy]-26,28-dihydroxycalix[4]arene (3) with lanthanoid nitrates (Tb3+ and Eu3+) has been investigated in anhydrous acetonitrile at 25 degrees C by using UV-vis and FT-IR as well as fluorescence spectra. The results obtained indicated that the spectroscopic behavior of compounds 1-2 upon complexation with lanthanoid ions did not show any significant larger difference in comparison with free compounds 1 and 2, which may be contributed to the poor binding ability. Contrary to compounds 1 and 2, the lower rim functional groups in compound 3 can form two large pi electron conjugate system with lanthanide ion and encapsulate lanthanide ions tightly, displaying the novel spectroscopic behavior upon complexation with lanthanide ions. As compared with compound 3, the formation complexes of compound 3 with Tb3+ and Eu3+ showed new broad intense absorption at 398 nm, respectively, and IR spectra showed that O-H stretching vibration at 3413.40 cm(-1) displayed a large drop. It is interestingly noted that the narrow emission line spectra were observed only for 3 complex with Tb3+, but did not for 3-Eu3+ complex. In the 3-Eu3+ complex, the broad-band emission at lambda(max) = 534 nm was obtained at the excitation of 398 nm. The spectroscopic behavior of three calix[4]arene derivatives upon complexation with lanthanoids was discussed from the relationship between the host structure and the properties of guest lanthanide ions.

Topics: Acetonitriles; Calixarenes; Lanthanoid Series Elements; Light; Nitrates; Phenols; Spectrometry, Fluorescence; Spectrophotometry, Ultraviolet; Spectroscopy, Fourier Transform Infrared

The catalysis effect of water-soluble calix[4]arene C[4] (calix[4]arene-5,11,17,23-tetrasulfonate) on hydrolysis of ATP in aqueous solution was studied by HPLC. Using laser photolysis and pulse radiolysis, the supramolecular interaction between water-soluble calix[4]arene and ATP was investigated.

Topics: Adenosine Triphosphate; Calixarenes; Hydrolysis; Lasers; Phenols; Photolysis; Pulse Radiolysis

A new class of cryptand-like ionophore based on a bis calix[4]arene structure has been developed. These molecules proved highly selective for complexation of potassium over all group I metal cations and barium. A range of symmetric and asymmetric calix[4]tubes featuring either alkyl or phenyl substituents at the upper rim have been synthesized in exceptional yield. Alteration of the calix[4]arene upper rim environment enables fine-tuning of the rate of potassium uptake, which can be evaluated through the conformational change on binding by NMR studies. Selectivity of potassium complexation has been demonstrated using NMR and electrospray mass spectral techniques. Molecular modeling studies, derived from crystallographic data, confirm that the potassium metal cation is complexed via the axial route, passing through the calix[4]arene annulus, and provide evidence for complexation rate and selectivity.

Topics: Calixarenes; Crystallography, X-Ray; Ionophores; Magnetic Resonance Spectroscopy; Models, Molecular; Molecular Conformation; Molecular Structure; Phenols; Potassium

The ion transport activity of calix[4]arene tetrabutylamide 1,3-alt 2 was studied in liposomes, planar lipid bilayers, and HEK-293 cells. These experiments, when considered together with (1)H NMR and X-ray crystallography data, indicate that calix[4]arene tetrabutylamide 2 (1) forms ion channels in bilayer membranes, (2) mediates ion transport across cell membranes at positive holding potential, (3) alters the pH inside liposomes experiencing a Cl(-) gradient, and (4) shows a significant Cl(-)/SO(4)(2)(-) transport selectivity. An analogue, calix[4]arene tetramethylamide 1, self-assembles in the presence of HCl to generate solid-state structures with chloride-filled and water-filled channels. Structureminus signactivity studies indicate that the hydrophobicity, amide substitution, and macrocyclic framework of the calixarene are essential for HCl binding and transport. Calix[4]arene tetrabutylamide 2 is a rare example of an anion-dependent, synthetic ion channel.

Topics: Amides; Calixarenes; Cell Line; Cell Membrane; Chlorides; Humans; Hydrochloric Acid; Hydrogen Bonding; Ion Channels; Lipid Bilayers; Liposomes; Membrane Potentials; Models, Molecular; Nuclear Magnetic Resonance, Biomolecular; Patch-Clamp Techniques; Phenols; Sulfates

Bis- and tetra-O- and C-glycosyl calixarenes (calixsugars) have been prepared by tethering carbohydrate moieties to a tetrapropoxycalix[4]arene scaffold through alkyl chains. Two methodologies have been employed. One consisted of the stereoselective multiple glycosylation of upper rim calix[4]arene polyols leading to calix-O-glycosides; the other involved a multiple Wittig olefination of upper rim calix[4]arene-derived polyaldehydes by the use of sugar phosphoranes and reduction of the alkene double bonds affording calix-C-glycosides. The NMR spectra and NOE experiments of bis-glycosylated products indicate that compounds bearing sugar-protected residues exist preferentially in solution in a flattened cone arrangement (far conformation) whereas deprotected derivatives adopt a close conformation. Calculations by molecular mechanics of the latter compounds point to a close conformation as well in gas phase.

Topics: Calixarenes; Catalysis; Chemistry, Organic; Glycosides; Glycosylation; Ionophores; Ligands; Magnetic Resonance Spectroscopy; Models, Molecular; Molecular Conformation; Molecular Structure; Phenols

The use of a novel cationic calixarene, p-(quaternary ammonium) calix[4]arene, as selectivity modifier in capillary electrophoresis coupled with electrochemical detection was reported. The calixarene displayed good selectivity for the positional isomers of benzenediol and aminophenol and their successful separation was obtained under optimum conditions. The interaction mechanism between p-(quaternary ammonium) calix[4]arene and the solutes is discussed using the molecular modeling method. The detection limits by electrochemical detection for the most solutes studied here were below picogram level, which was approximately 2 orders of magnitude lower than those reported in the literature using UV detection. The results showed that electrochemical detection is especially suitable for an electrophoresis system where calixarenes are used as modifier.

Topics: Calixarenes; Electrochemistry; Electrophoresis, Capillary; Models, Molecular; Phenols; Sensitivity and Specificity

The absorption spectrum and fluorescence spectrum of calix[n]arenes are studied systematically. The self-association of calix[n]arenes is proposed and the self-association constant is also obtained. The recognition properties of calix[n]arenes are studied and the inclusion constant is calculated.

Topics: Calixarenes; Molecular Structure; Phenols; Spectrometry, Fluorescence; Spectrophotometry, Ultraviolet

The high background K+ concentration in plant cells is a problem for intracellular measurements of Na+ using ion-selective microelectrodes. The discrimination between Na+ and K+ of the microelectrode ionophore molecule limits the usefulness of this technique. A new Na+-selective microelectrode with an ionophore incorporating a tetramethoxyethyl ester derivative of p-t-butyl calix[4]arene has been developed. Microelectrodes made with this new sensor have superior selectivity for Na+ over K+ resulting in a lower limit of detection when compared with microelectrodes made using a commercially available ionophore (ETH227). Both types of microelectrodes were insensitive to changes in ionic strength and physiological ranges of pH, but only the calixarene-based electrodes showed no protein interference. To test the suitability of the calixarene-based microelectrodes for measurements in plants, they were used to measure Na+ in epidermal cells in the zone 10-20 mm from the root apex of barley (Hordeum vulgare L.). Seedlings were grown in a nutrient solution containing 200 mM NaCl for 1-6 d. The range of intracellular Na+ activity (a(Na)) measured varied from < or =0.1 mM (limit of detection) to over 100 mM, and these values increased significantly with time. The membrane potential (E(m)) of these cells was variable, but the values became significantly more negative with time, although there was no significant correlation between E(m) and a(Na). These intracellular measurements could not be separated into distinct populations that might be representative of subcellular compartments.

Topics: Acetamides; Biosensing Techniques; Calixarenes; Cell Membrane; Cell Membrane Permeability; Chelating Agents; Cytoplasm; Hordeum; Intracellular Membranes; Ion-Selective Electrodes; Ionophores; Macromolecular Substances; Membrane Potentials; Microelectrodes; Phenols; Plant Roots; Potassium; Sodium; Sodium Chloride

Topics: Bridged-Ring Compounds; Calixarenes; Chelating Agents; Cyclodextrins; Enzymes; Heterocyclic Compounds, Bridged-Ring; Molecular Mimicry; Phenols

The amplification of supramolecular chirality has been studied in dynamic chiral hydrogen-bonded assemblies 1(3).(CA)(6) using "Sergeants and Soldiers" experiments. Previously, we have shown that chiral centers present in either the dimelamine component 1 or the cyanurate component CA quantitatively induce one handedness (M or P) in the assembly. This offers the possibility to study the amplification of chirality under two different kinetic regimes. When chiral dimelamines 1 are used, the exchange of chiral components and (M/P)-interconversion, i.e., interconversion between the (M)- and (P)-isomers of assembly 1(3).(CA)(6), take place via identical pathways (condition A). When chiral cyanurates CA are used, the exchange of chiral components occurs much faster than (M/P)-interconversion (condition B). Experimentally, a much stronger chiral amplification is observed under condition B. For example, the observed chiral amplification for a mixture of chiral and achiral components (40:60) is 46% under condition B and 32% under condition A. Kinetic models were developed to fit the experimental data and to simulate chiral amplification in dynamic systems in general. These simulations show that it is theoretically possible that the diastereomeric excess in a dynamic system is more than 99% with less than 1% chiral component present!

Topics: Barbiturates; Calixarenes; Hydrogen Bonding; Kinetics; Models, Chemical; Phenols; Stereoisomerism; Thermodynamics; Triazines

Topics: Calixarenes; Electron Transport; Macromolecular Substances; Molecular Conformation; Molecular Mimicry; Phenols; Porphyrins; Proteins; Spectrometry, Fluorescence

Rigid calix[4]arene cone conformers, which are efficient receptors for quaternary ammonium salts, are usually obtained through the functionalization of their lower rim with suitable groups. Using flexible cone conformer of calix[4]arene, bearing four 4-hydroxybenzyl groups as cooperative and rigidifying structural elements at the upper rim of the calix, which act as anion binding groups, a new heteroditopic cavitand, 7, was synthesized. Whereas the tetramethoxy derivative 8 does not show any complexing ability, its tetrahydroxy analogue 7 recognizes tetramethylammonium salts with high efficiency. The binding abilities of this new receptor toward a series of tetramethylammonium salts (tosylate, chloride, acetate, trifluoroacetate, and picrate) have been investigated in CDCl(3) solution and compared to the monotopic and rigidified, through the lower rim, cone biscrown-3-calix[4]arene 9. The results obtained confirmed that in CDCl(3) ion pairing strongly affects binding. In particular, the rigid monotopic receptor 9 experiences good efficiency toward tetramethylammonium salts having anions with low ion-pairing ability such as trifluoroacetate or picrate. On the contrary, for the new heteroditopic cavitand 7, a reverse order of efficiency was found. In the latter case a different complexation mode was hypothesized in which the tetramethylammonium cation is deeply entrapped into the host cavity and its counteranion participates to the recognition process by coordination via hydrogen bonding by the four OH groups. To further support the role of the anion in the recognition process, a "dual host" approach, employing 7 or 9 in the presence of a specific receptor for chloride anion (10), was utilized. Molecular modeling studies confirmed that in the complexes formed by 7 and TMA salts the counteranion is involved in hydrogen bonding with the host OH groups and that the guests are bound as ligand-separated ion pairs.

Topics: Allosteric Regulation; Anions; Calixarenes; Hydrogen Bonding; Indicators and Reagents; Kinetics; Magnetic Resonance Spectroscopy; Models, Molecular; Molecular Conformation; Phenols; Quaternary Ammonium Compounds; Receptors, Drug

The varied extracortical targets of layer V make it an important site for cortical processing and output, which may be regulated by differences in the pyramidal neurons found there. Two populations of projection neurons, regular spiking (RS) and intrinsic bursting (IB), have been identified in layer V of some sensory cortices, and differences in their inhibitory inputs have been indirectly demonstrated. In this report, IB and RS cells were identified in rat auditory cortical slices, and differences in thalamocortical inhibition reaching RS and IB cells were demonstrated directly using intracellular GABA(A) blockers. Thalamocortical synaptic input to RS cells was always a combination of excitation and both GABA(A) and GABA(B) inhibition. Stimulation seldom triggered a suprathreshold response. IB cell synaptic responses were mostly excitatory, and stimulation usually triggered action potentials. This apparent difference was confirmed directly using intracellular chloride channel blockers. Before intracellular diffusion, synaptic responses were stable and similar to control conditions. Subsequently, GABA(A) was blocked, revealing a cell's total excitatory input. On GABA(A) blockade, RS cells responded to synaptic stimulation with large, suprathreshold excitatory events, indicating that excitation, while always present in these cells, is masked by GABA(A). In IB cells that had visible GABA(A) input, it often masked an excitatory postsynaptic potential (EPSP) that could lead to additional suprathreshold events. These findings indicate that IB cells receive less GABA(A)-mediated inhibitory input and are able to spike or burst in response to thalamocortical synaptic stimulation far more readily than RS cells. Such differences may have implications for the influence each cell type exerts on its postsynaptic targets.

Topics: Action Potentials; Animals; Auditory Cortex; Biotin; Calixarenes; Chelating Agents; Chloride Channels; Excitatory Postsynaptic Potentials; GABA-A Receptor Antagonists; GABA-B Receptor Antagonists; In Vitro Techniques; Phenols; Rats; Rats, Long-Evans; Reaction Time; Synapses; Thalamus

Calcium-activated Cl(-) secretion is an important modulator of regulated ion transport in murine airway epithelium and is mediated by an unidentified Ca(2+)-stimulated Cl(-) channel. We have transfected immortalized murine tracheal epithelial cells with the cDNA encoding the permeabilizing P2X(7) purinoreceptor (P2X(7)-R) to selectively permeabilize the basolateral membrane and thereby isolate the apical membrane Ca(2+)-activated Cl(-) current. In P2X(7)-R-permeabilized cells, we have demonstrated that UTP stimulates a Cl(-) current across the apical membrane of CF and normal murine tracheal epithelial cells. The magnitude of the UTP-stimulated current was significantly greater in CF than in normal cells. Ion substitution studies demonstrated that the current exhibited a permselectivity sequence of Cl(-) > I(-) > Br(-) > gluconate(-). We have also determined a rank order of potency for putative Cl(-) channel blockers: niflumic acid > or = 5-nitro-2-(3-phenylpropylamino)benzoic acid > 4, 4'-diisothiocyanostilbene-2,2'-disulfonate > glybenclamide >> diphenlyamine-2-carboxylate, tamoxifen, and p-tetra-sulfonato-tetra-methoxy-calix[4]arene. Complete characterization of this current and the corresponding single channel properties could lead to the development of a new therapy to correct the defective airway surface liquid in cystic fibrosis patients.

Topics: 4,4'-Diisothiocyanostilbene-2,2'-Disulfonic Acid; Animals; Bromine; Calcium; Calcium Channel Blockers; Calixarenes; Cell Line; Cell Membrane; Chelating Agents; Chlorides; Cystic Fibrosis; DNA, Complementary; Electrophysiology; Epithelium; Gluconates; Glyburide; Hypoglycemic Agents; Iodine; Ions; Mice; Niflumic Acid; Nitrobenzoates; ortho-Aminobenzoates; Phenols; Receptors, Purinergic P2; Receptors, Purinergic P2X7; Tamoxifen; Time Factors; Trachea; Uridine Triphosphate

The calix[4]arene platform was used for the syntheses of novel rhenium(V) complexes, that may have potential applications as radiopharmaceuticals. The reaction of ReO(PPh3)2Cl3 with tetradentate N2O2-calix[4]arene ligand 8 in ethanol gave the novel mixed-ligand rhenium complex 9 with the structure ReO(N2O2-calix)OEt. The configuration was elucidated by using a number of 1H NMR techniques. In 9, the ethoxy ligand could be easily and quantitatively exchanged for another monodentate ligand to give complex 12. Tetradentate N2S2-calix[4]arene ligand 15 formed the rhenium complex 16 either via reaction with ReO(PPh3)2Cl3 in an organic solvent or by reaction with rhenium gluconate in an aqueous solution. Complex 16 showed good stability in phosphate-buffered saline solution (37 degrees C, 5 d). The crystal structures of a mono- and a bimetallic complex were determined. The bimetallic N2O2-calixarene complex dimer 11 crystallized in the monoclinic space group C2/c, with a = 38.963(5) A, b = 23.140(6) A, c = 27.382(6) A, beta = 128.456(10) degrees, V = 19,333(7) A3, Z = 8, and final R = 0.0519. The monometallic N2S2 model complex 17 crystallized in the monoclinic space group Cc, with a = 15.715(2) A, b = 12.045(2) A, c = 20.022(3) A, beta = 94.863(12) degrees, V = 3776.3(10) A3, Z = 4, and final R = 0.0342.

Topics: Calixarenes; Magnetic Resonance Spectroscopy; Models, Molecular; Molecular Structure; Phenols; Radiopharmaceuticals; Rhenium; Spectrometry, Mass, Fast Atom Bombardment

An absorbance based calcium ion sensor is presented which applies a new immobilized chromogenic calix[4]arene. The membrane consists of a hydrogel/1,3-pentanedial mixture and the 1,3-bis(indoaniline)-derived 2,4-bis-[(ethylcarbonyl)methoxyl-calix[4]arene as calcium receptor. The indicator entrapped within the gel was not rapidly washed out. Upon calcium complexation a bathochromic shift up to 70 nm was observed along with an increase of the absorption coefficient. The dynamic range of calcium measurements is from 3 to 10 mM with a point of inflection of the calibration curve at a calcium concentration of about 7 mM. The concentration of calcium ions can be calculated from either absorbance at a distinct wavelength or--preferably when indicator leaching occurs--from the wavelength shift of the absorbance occurring when calcium levels are increased.

Topics: Calcium; Calibration; Calixarenes; Chelating Agents; Coloring Agents; Hydrogels; Ionophores; Membranes, Artificial; Phenols; Polyurethanes; Spectrophotometry, Infrared; Spectrophotometry, Ultraviolet