zn(ii)-phthalocyanine and phthalocyanine

The recent progress in some spectrum methods on the structures of metal phthalocyanine was introduced. IR and UV/Vis spectral properties of phthalocyanine were presented systematically, especially the effect of the types, numbers and positions of the peripheral substituted groups as well as the different aggregation states in solution on the UV/Vis spectra, the characterization method of the isomers of tetra-substituted metal-phthalocyanine by NMR was also discussed.

Topics: Indoles; Isoindoles; Isomerism; Magnetic Resonance Spectroscopy; Molecular Structure; Organometallic Compounds; Photosensitizing Agents; Spectrophotometry, Infrared; Spectrophotometry, Ultraviolet; Spectrum Analysis; Zinc Compounds

Topics: Cells, Cultured; Hematoporphyrin Photoradiation; Humans; Indoles; Isoindoles; Organometallic Compounds; Photochemotherapy; Photosensitizing Agents; Soft Tissue Infections; Staphylococcal Infections; Streptococcal Infections; Suppuration; Zinc Compounds

A rare gyrobifastigium architecture (GB) was constructed by self-assembly of a tetradentate donor (L) with Pd

Topics: Cell Line, Tumor; HeLa Cells; Humans; Isoindoles; Organometallic Compounds; Photochemotherapy; Photosensitizing Agents; Solvents; Water; Zinc; Zinc Compounds

Metal nanoparticles possess high catalytic activity in various organic transformation reactions. A catalyst must be recovered and re-used effectively and economically to lower the overall reaction cost. The recovery of a catalyst remains a challenge due to their extreme small size. In this research work, catalytic metal nanoparticles were synthesized on Zn-phthalocyanine (ZnPc) and chitosan hydrogel (CH) composite which acts as catalyst support. The ZnPc-CH support facilitate the easy recovery of the loaded metal nanoparticles. Metal nanoparticles (M

Topics: Chitosan; Environmental Pollutants; Hydrogels; Hydrogen; Indoles; Metal Nanoparticles

A nanocomposite of (2-aminoethyl)piperazine ligand substituted with zinc(II) tetra carboxylic acid phthalocyanine (ZnTEPZCAPC) and MWCNTs was constructed and employed to develop an electrochemical sensor with outstanding sensitivity and a low detection limit. The macrocyclic complex ZnTEPZCAPC was first synthesized and then employed for the electrochemical determination of the antipsychotic drug promazine (PMZ). The as-prepared ZnTEPZCAPC and MWCNT nanocomposite was characterized using different techniques, such as Fourier-transform infrared (FT-IR) spectroscopy, X-ray diffraction (XRD), UV-visible spectroscopy (UV-Vis), field emission scanning electron microscopy (FE-SEM), and thermogravimetric analysis (TGA). Further, the prepared ZnTEPZCAPC@MWCNT nanocomposites were modified on a glassy carbon electrode (GCE) surface, and the electrochemical activity was investigated using cyclic voltammetry (CV), differential pulse voltammetry (DPV), and chronoamperometry (CA) tests in pH 7.0 phosphate buffer solution (PBS) in the potential window of 0.0-1 V. The ZnTEPZCAPC@MWCNTs displayed a superior electrochemical performance because of their high electrochemical active surface area (0.453 cm

Topics: Antipsychotic Agents; Piperazines; Promazine; Reproducibility of Results; Spectroscopy, Fourier Transform Infrared; Zinc

Herein, four zinc phthalocyanines (ZnPcs) with chiral lysine modification were synthesized. We found that the chirality of lysine and the chiral structure position strongly influence the properties of ZnPcs. Among the four ZnPcs, d-lysine-modified ZnPc through -NH

Topics: Amino Acids; Animals; Antineoplastic Agents; Apoptosis; Cell Line, Tumor; HeLa Cells; Humans; Isoindoles; Lysine; Mice; Neoplasm Transplantation; Organometallic Compounds; Photosensitizing Agents; Stereoisomerism; Zinc Compounds

In this study, a series of peripherally and non-peripherally tetra-substituted metal-free and zinc(II) phthalocyanines were successfully prepared in good yields by cyclotetramerization of the phthalonitrile derivative bearing a tetraethylene glycol methyl ether group at 3- and 4- positions. All newly synthesized compounds were characterized using spectroscopic methods, such as FT-IR, NMR, mass and UV-Vis spectroscopy. To determine the therapeutic potential of the synthesized phthalocyanines, the effects of the substitution pattern (peripheral and non-peripheral) and central metal atom on the photophysicochemical properties were investigated. When comparing their singlet oxygen generation capabilities (

Topics: Cell Line; Colonic Neoplasms; Humans; Indoles; Isoindoles; Metals; Organometallic Compounds; Polyethylene Glycols; Singlet Oxygen; Spectroscopy, Fourier Transform Infrared; Zinc; Zinc Compounds

Switchable theranostics are of great interest for accurate tumor imaging and targeted therapy. Here, we develop smart engineering to construct nanostructured phthalocyanines self-assembled by amphiphilic zinc phthalocyanines (ZnPcs) and hydrophobic copper phthalocyanines (CuPcs) (ZnPc(PEG)

Topics: Cell Line, Tumor; Fluorescence; Humans; Neoplasms; Organometallic Compounds; Photochemotherapy; Photosensitizing Agents; Phototherapy; Tumor Microenvironment; Zinc Compounds

Photodynamic therapy (PDT) is an antitumor procedure clinically approved for the treatment of different cancer types. Despite strong efforts and promising results in this field, PDT has not yet been approved by any regulatory authority for the treatment of colorectal cancer, one of the most prevalent gastrointestinal tumors. In the search of novel therapeutic strategies, we examined the in vivo effect of PDT with a lipophilic phthalocyanine (Pc9) encapsulated into polymeric poloxamine micelles (T1107) in a murine colon carcinoma model.. In vivo assays were performed with BALB/c mice challenged with CT26 cells. Pc9 tumor uptake was evaluated with an in vivo imaging system. Immunofluorescence, western blot, and flow cytometry assays were carried out to characterize the activation of apoptosis and an antitumor immune response.. Pc9-T1107 effectively delayed tumor growth and prolonged mice survival, without generating systemic or tissue-specific toxicity. The induction of an apoptotic response was characterized by a decrease in the expression levels of Bcl-X. Pc9-T1107 PDT treatment reduced tumor growth, inducing an apoptotic cell death and activating an immune response. Lasers Surg. Med. © 2020 Wiley Periodicals LLC.

Topics: Animals; Apoptosis; CD8-Positive T-Lymphocytes; Cell Line, Tumor; Colonic Neoplasms; Immunity; Isoindoles; Mice; Mice, Inbred BALB C; Organometallic Compounds; Photochemotherapy; Photosensitizing Agents; Zinc; Zinc Compounds

Cationic Zn phthalocyanine complexes were synthesized using Knoevenagel reaction starting from a Zn(ii) tetrakis(2-formylphenoxy)phthalocyanine (1) to form Zn(ii) tetrakis(1-butyl-4-(4-(tetraphenoxy)styryl)pyridin-1-ium) phthalocyanine (2) and Zn(ii) tetrakis(4-(4-(tetraphenoxy)styryl)-1-(4-(triphenylphosphonio)butyl)pyridin-1-ium)phthalocyanine (3). The photophysicochemical behaviours of the Pc complexes were assessed. The cationic complexes display high water-solubility and gave moderate singlet oxygen quantum yield in water. The cationic Pcs demonstrate good cellular uptake and photodynamic activity against MCF-7 cells with IC50 values of 8.2 and 4.9 μM for 2 and 3, respectively. The cationic Pcs also demonstrate high photoantimicrobial activity against Escherichia coli with log reductions of 5.3 and 6.0 for 2 and 3, respectively.

Topics: Isoindoles; Organometallic Compounds; Photochemotherapy; Singlet Oxygen; Zinc Compounds

By using an oil-in-water single emulsion method, a series of multifunctional hybrid nanoparticles (NPs) were prepared which consisted of a core of poly(lactic-co-glycolic acid) (PLGA) with a lipoid shell of n-hexadecylamine-substituted hyaluronic acid (HA), encapsulating a zinc(II) phthalocyanine-based photosensitizer (ZnPc). As determined by laser light scattering, these hybrid NPs labeled as ZnPc@PLGA-HA NPs possessed a hydrodynamic diameter of 280 nm and a surface charge of -30 mV, showing high stability in serum. The Q-band absorption of ZnPc exhibited a large red-shift from 674 nm for free ZnPc in dimethylsulfoxide to 832 nm for this nanosystem in water. Upon light irradiation at 808 nm, the encapsulated ZnPc induced a strong photothermal effect instead of photodynamic action, which is usually observed for ZnPc-containing NPs. The tumor-targeting effect of these NPs due to the HA coating was investigated against the human colorectal adenocarcinoma HT29 cells and human lung carcinoma A549 cells, both of which overexpress cluster determinant 44 (CD44) receptors, using the CD44-negative human normal hepatic LO2 cells as a negative control. The photothermal cell-killing effect of these NPs was significantly higher for the two CD44-positive cell lines than that for the negative control. Their in vivo photothermal efficacy was also examined on HT29 tumor-bearing nude mice. Upon irradiation, the NPs caused significant temperature increase at the tumor site and ablation of the tumor. The results showed that these multifunctional NPs could serve as an effective photothermal agent for targeted photothermal therapy. Statement of significance Phthalocyanines are well-known photosensitizers for photodynamic therapy. By encapsulating these molecules into various nanoplatforms, a range of multifunctional photosensitizing systems have been developed for cancer therapy. In this study, we have demonstrated that by careful selection of phthalocyanines and the nanocarriers, as well as the self-assembly and encapsulation methods, the encapsulated phthalocyanine molecules could switch the photoinduced action from photodynamic therapy to photothermal therapy as a result of the enhanced aggregation of the macrocyclic molecules in the nanoparticles. The unique packing of the molecules also resulted in a large red-shift of the Q-band absorption to 832 nm, facilitating the in vitro and in vivo photothermal treatment.

Topics: Animals; Cell Line, Tumor; Glycols; Hyaluronic Acid; Indoles; Isoindoles; Mice; Mice, Nude; Nanoparticles; Organometallic Compounds; Photochemotherapy; Polylactic Acid-Polyglycolic Acid Copolymer; Zinc; Zinc Compounds

1-(2-Methoxyethyl)piperidine sustituted Zn phthalocyanine complex (2) is synthesised and quartenised (3). These complexes are loaded into silica nanoparticles (SiNPs) that are futher surface modified with ampicillin and 1.3-propanesultone. The photophysical and photochemical properties of the complexes and their doped conjugates were investigated in dimethylsulfoxide. The cationic complex (3) is used for photodynamic antimicrobial activity. Log reduction values of above 9 are obtained towards the photoiactivation of Staphyloccocus aureus.

Topics: Ampicillin; Anti-Infective Agents; Indoles; Isoindoles; Nanoparticles; Naphthalenesulfonates; Organometallic Compounds; Photochemotherapy; Photosensitizing Agents; Silicon Dioxide; Zinc; Zinc Compounds

Photobiological properties of phthalocyanine photosensitizers, namely, clinically approved Photosens and new compounds Holosens and Phthalosens were analyzed on transitional cell carcinoma of the urinary bladder (T24) and human hepatic adenocarcinoma (SK-HEP-1). Photosens is a sulfated aluminum phthalocyanine with the number of sulfo groups 3.4, which is characterized by a high degree of hydrophilicity, slow cellular uptake, localization in lysosomes and the lowest photodynamic activity. Holosens is an octacholine zinc phthalocyanine, a cationic compound with significant charge. Holosens more efficiently enters the cells; it is localized in Golgi apparatus in addition to lysosomes and exhibits a significant inhibitory effect on cell viability upon irradiation. The highest photodynamic activity was demostrated by Phthalosens. Phthalosens is a metal-free analog of Photosens with a number of sulfo groups 2.5, which determines its amphiphilicity. Phthalosens is characterized by the highest rate of cellular uptake through the outer cell membrane, localization in cell membrane as well as in lysosomes and Golgi apparatus, and the highest activity upon irradiation among the photosensitizers studied. In general, changes in the physicochemical properties of Holosens and Phthalosens ensured an increase in their efficiency in vitro compared to Photosens. The features of accumulation, intracellular distribution and their interrelation with photodynamic activity, revealed in this work, indicate the prospects of Phthalosens and Holosens for clinical practice.

Topics: Cell Line, Tumor; Golgi Apparatus; Humans; Indoles; Isoindoles; Lysosomes; Organelles; Organometallic Compounds; Photochemotherapy; Photosensitizing Agents; Zinc Compounds

Two cationic zinc phthalocyanines have been tested for their interactions with several DNA secondary structures. Despite different aggregation properties, both phthalocyanines bind to DNA in monomeric forms. The strong photodynamic activity of phthalocyanines was demonstrated by in vitro experiments and correlate well with high singlet oxygen yields determined experimentally with 1,3-diphenylisobenzofurane. Both phthalocyanines accumulate in the cell cytoplasm prior to radiation; however, only the octacationic photosensitizer was observed in the cell nuclei after irradiation.

Topics: Cell Communication; Circular Dichroism; Cytoplasm; DNA; Humans; Indoles; Isoindoles; MCF-7 Cells; Microscopy, Confocal; Neoplasms; Organometallic Compounds; Photochemotherapy; Photosensitizing Agents; Singlet Oxygen; Zinc Compounds

This study investigated the activity of photosensitive phthalocyanines on promastigotes and amastigotes of Leishmania (L.) amazonensis. Aluminum phthalocyanine chloride (AlPcCl), Aluminum phthalocyanine hydroxide (AlPcOH) and zinc phthalocyanine (PcZn) were tested in the presence (matte red LED, potency of 2.5-2.3 μW for 30 min) and absence of light against L. amazonensis promastigotes and the parasite viability was evaluated after 24, 48 and 72 h. The amastigote forms were treated with AlPcCl and AlPcOH, following the same lighting protocols described for the promastigote forms, being evaluated after 24 h. Cytotoxicity to human erythrocytes and peritoneal macrophages was also evaluated. The results showed that AlPcCl and AlPcOH in the presence of light have antileishmania activity, with leishmanistatic effects on promastigotes and amastigotes of L. amazonensis, without causing cytotoxicity to peritoneal macrophages and erythrocytes. The concentrations that inhibited 50% of the promastigote forms after 24 h of light exposure were 0.21 ± 0.08 μM for AlPcCl and 0.23 ± 0.06 μM for AlPcOH. In 48 h and 72 h after the treatment, the IC

Topics: Animals; Erythrocytes; Humans; Indoles; Isoindoles; Leishmania; Macrophages; Mice; Mice, Inbred BALB C; Organometallic Compounds; Photochemotherapy; Photosensitizing Agents; Zinc Compounds

The syntheses of a novel 1,4,8,11,15,18,22,25-octahexyloxy-2,3,9,10,16,17,23,24-octa-(4-trifluoromethoxyphenyl) phthalocyanine (

Topics: Chemistry Techniques, Synthetic; Drug Design; Indoles; Isoindoles; Metals; Organometallic Compounds; Photochemical Processes; Photochemotherapy; Photolysis; Singlet Oxygen; Spectrometry, Fluorescence; Spectroscopy, Fourier Transform Infrared; Zinc Compounds

Photodynamic therapy is emerging as a hopeful method for the treatment of oncological diseases. In the search of novel therapeutic strategies for colorectal cancer, in this work we reported the photocytotoxic activity of a lipophilic zinc(II) phthalocyanine on a murine colon adenocarcinoma cell line (CT26 cells). The 2,9(10),16(17),23(24) tetrakis[(2-dimethylamino)ethylsulfanyl]phthalocyaninatozinc(II), named Pc9, was encapsulated into Tetronic® 1107 polymeric poloxamine micelles (T1107) and assayed in 2D and 3D cell cultures. We showed that the formulation Pc9-T1107 was efficient to reduce cell viability after photodynamic treatment both in 2D cultures (IC

Topics: Antioxidants; Apoptosis; Caspase 3; Cell Culture Techniques; Cell Line, Tumor; Cell Survival; Colonic Neoplasms; Drug Carriers; Endoplasmic Reticulum; Humans; Indoles; Isoindoles; Light; Lysosomes; Micelles; Organometallic Compounds; Photosensitizing Agents; Reactive Oxygen Species; Zinc Compounds

Photodynamic therapy (PDT) involves interaction of a photosensitizer, light, and molecular oxygen which produces singlet oxygen and subsequent tumour eradication. The development of second generation photosensitizers, such as phthalocyanines, has improved this technology. Customary monolayer cell culture techniques are, unfortunately, too simple to replicate treatment effects in vivo. Multicellular tumour spheroids may provide a better alternative since they mimic aspects of the human tumour environment. This study aimed to profile 84 genes involved in apoptosis following treatment with PDT on lung cancer cells (A549) grown in a monolayer versus three-dimensional multicellular tumour spheroids (250 and 500 μm). Gene expression profiling was performed 24 h post irradiation (680 nm; 5 J/cm²) with zinc sulfophthalocyanine (ZnPcS

Topics: Cell Line, Tumor; Humans; Indoles; Isoindoles; Organometallic Compounds; Photochemotherapy; Photosensitizing Agents; Spheroids, Cellular; Zinc Compounds

The present work reports the synthesis, photophysical and photochemical characterization and photodynamic evaluation of zinc, aluminum and metal free-base tetracarboxy-phthalocyanines (ZnPc, AlPc and FbPc, respectively). To evaluate the possible application of phthalocyanines as a potential photosensitizer the photophysical and photochemical characterization were performed using aqueous (phosphate-buffered solution, PBS) and organic (dimethyl sulfoxide, DMSO) solvents. The relative lipophilicity of the compounds was estimated by the octanol-water partition coefficient and the photodynamic activity evaluated through the photooxidation of a protein and photohemolysis. The photooxidation rate constants (k) were obtained and the hemolytic potential was evaluated by the maximum percentage of hemolysis achieved (Hmax) and the time (t50) to reach 50% of the Hmax. Although these phthalocyanines are all hydrophilic and possess very low affinity for membranes (log PO/W=-2.0), they led to significant photooxidation of bovine serum albumin (BSA) and photohemolysis. Our results show that ZnPc was the most efficient photosensitizer, followed by AlPc and FbPc; this order is the same as the order of the triplet and singlet oxygen quantum yields (ZnPc>AlPc>FbPc). Furthermore, together, the triplet, fluorescence and singlet oxygen quantum yields of zinc tetracarboxy-phthalocyanines suggest their potential for use in theranostic applications, which simultaneously combines photodiagnosis and phototherapy.

Topics: Animals; Cattle; Dimethyl Sulfoxide; Erythrocyte Membrane; Hemolysis; Humans; Hydrophobic and Hydrophilic Interactions; Indoles; Isoindoles; Light; Models, Molecular; Organometallic Compounds; Oxidation-Reduction; Photolysis; Photosensitizing Agents; Serum Albumin, Bovine; Singlet Oxygen; Spectrometry, Fluorescence; Spectrophotometry, Ultraviolet; Water; Zinc Compounds

The functionalisation of therapeutic nanoparticle constructs with cancer-specific biomolecules can enable selective tumour accumulation and targeted treatment. Water soluble gold nanoparticles (ca. 4 nm) stabilised by a mixed monolayer of a hydrophobic zinc phthalocyanine photosensitiser (C11Pc) and hydrophilic polyethylene glycol (PEG) have been prepared. The C11Pc-PEG gold nanoparticle constructs were further functionalised with jacalin, a lectin specific for the cancer-associated Thomsen-Friedenreich (T) carbohydrate antigen, or with monoclonal antibodies specific for the human epidermal growth factor receptor-2 (HER-2). The two biofunctionalised nanoparticle conjugates produced similar levels of singlet oxygen upon irradiation at 633 nm. Importantly, both nanoparticle conjugates demonstrated extensive, yet comparable, phototoxicity in HT-29 colorectal adenocarcinoma cells (80-90%) and in SK-BR-3 breast adenocarcinoma cells (>99%). Non-conjugated C11Pc-PEG gold nanoparticles were only minimally phototoxic. Lysosomal colocalisation studies performed with the HT-29 colon cancer cells and the SK-BR-3 breast cancer cells revealed that both nanoparticle conjugates were partially localised within acidic organelles, which is typical of receptor-mediated endocytosis. The similarity of the targeted PDT efficacy of the two biofunctionalised C11Pc-PEG gold nanoparticles is discussed with respect to targeting ligand binding affinity and cell surface antigen density as key determinants of targeting efficiency. This study highlights how targeting small cell-surface molecules, such as the T antigen, can mediate a selective photodynamic treatment response which is similar to that achieved when targeting overexpressed protein receptors, such as HER-2. The high prevalence of the T antigen present on the cellular surface of primary tumours emphasises the broad potential applications for lectin-targeted therapies.

Topics: Adenocarcinoma; Antibodies, Monoclonal; Antigens, Tumor-Associated, Carbohydrate; Antineoplastic Agents; Breast Neoplasms; Cell Line, Tumor; Cell Survival; Colorectal Neoplasms; Gold Compounds; Humans; Hydrophobic and Hydrophilic Interactions; Indoles; Isoindoles; Lectins; Lysosomes; Metal Nanoparticles; Molecular Targeted Therapy; Organometallic Compounds; Photochemotherapy; Photosensitizing Agents; Polyethylene Glycols; Receptor, ErbB-2; Singlet Oxygen; Zinc Compounds

A theoretical investigation of self-assembled donor-acceptor dyads (ZnPca, ZnPcb and ZnPcc) formed by axial coordination of zinc phthalocyanines appended with 4-carboxyl pyridine has been conducted with the density functional theory (DFT) method and time-dependent DFT (TD-DFT) calculations. A comparison between the molecular structures, atomic charges, molecular orbitals, UV-vis spectra and infrared (IR) spectra has been studied. Further, as sensitizers for the TiO2-based dye-sensitized solar cells, the photovoltaic performances have been investigated. The ZnPcc-sensitized solar cell exhibits a higher conversion efficiency than the ZnPcb and ZnPca-sensitized ones under AM 1.5G solar irradiation, while the ZnPca-sensitized cell performs the poorest due to the lack of peripheral substituents (n-butyoxyl groups) which can be confirmed by the result of the theoretical research. It shows that the directionality of charge transfer in the self-assembled donor-acceptor dyads is important and benefit for the efficiency of the DSSC.

Topics: Coloring Agents; Indoles; Isoindoles; Models, Molecular; Organometallic Compounds; Solar Energy; Zinc Compounds

In the first part; the syntheses of mono-; di-; and tetra-glycosylated phthalonitriles is described; which are the most used starting materials for the preparation of the corresponding glycosylated metal (mostly zinc) phthalocyanines. In the second section; the preparation of symmetric and unsymmetric mono-; tetra-; and octa- glycosylated zinc phthalocyanines are reviewed; in which the sugar is attached to the phthalocyanine macrocycle; either anomerically or via another one of its OH-groups.

Topics: Glycosylation; Humans; Indoles; Isoindoles; Metals; Molecular Structure; Organometallic Compounds; Zinc Compounds

Phthalocyanines are an important class of organic semiconductors and, thus, their interfaces with metals are both of fundamental and practical relevance. In the present contribution we provide a combined theoretical and experimental study, in which we show that state-of-the-art quantum-mechanical simulations are nowadays capable of treating most properties of such interfaces in a quantitatively reliable manner. This is shown for Cu-phthalocyanine (CuPc) and Zn-phthalocyanine (ZnPc) on Au(111) and Ag(111) surfaces. Using a recently developed approach for efficiently treating van der Waals (vdW) interactions at metal/organic interfaces, we calculate adsorption geometries in excellent agreement with experiments. With these geometries available, we are then able to accurately describe the interfacial electronic structure arising from molecular adsorption. We find that bonding is dominated by vdW forces for all studied interfaces. Concomitantly, charge rearrangements on Au(111) are exclusively due to Pauli pushback. On Ag(111), we additionally observe charge transfer from the metal to one of the spin-channels associated with the lowest unoccupied π-states of the molecules. Comparing the interfacial density of states with our ultraviolet photoelectron spectroscopy (UPS) experiments, we find that the use of a hybrid functionals is necessary to obtain the correct order of the electronic states.

Topics: Adsorption; Copper; Indoles; Isoindoles; Metals; Organometallic Compounds; Photoelectron Spectroscopy; Quantum Theory; Zinc Compounds

High oxidation potential perfluorinated zinc phthalocyanines (ZnF(n)Pcs) are synthesised and their spectroscopic, redox, and light-induced electron-transfer properties investigated systematically by forming donor-acceptor dyads through metal-ligand axial coordination of fullerene (C60) derivatives. Absorption and fluorescence spectral studies reveal efficient binding of the pyridine- (Py) and phenylimidazole-functionalised fullerene (C60Im) derivatives to the zinc centre of the F(n)Pcs. The determined binding constants, K, in o-dichlorobenzene for the 1:1 complexes are in the order of 10(4) to 10(5) M(-1); nearly an order of magnitude higher than that observed for the dyad formed from zinc phthalocyanine (ZnPc) lacking fluorine substituents. The geometry and electronic structure of the dyads are determined by using the B3LYP/6-31G* method. The HOMO and LUMO levels are located on the Pc and C60 entities, respectively; this suggests the formation of ZnF(n)Pc(.+)-C60Im(.-) and ZnF(n)Pc(.+)-C60Py(.-) (n=0, 8 or 16) intra-supramolecular charge-separated states during electron transfer. Electrochemical studies on the ZnPc-C60 dyads enable accurate determination of their oxidation and reduction potentials and the energy of the charge-separated states. The energy of the charge-separated state for dyads composed of ZnF(n)Pc is higher than that of normal ZnPc-C60 dyads and reveals their significance in harvesting higher amounts of light energy. Evidence for charge separation in the dyads is secured from femtosecond transient absorption studies in nonpolar toluene. Kinetic evaluation of the cation and anion radical ion peaks reveals ultrafast charge separation and charge recombination in dyads composed of perfluorinated phthalocyanine and fullerene; this implies their significance in solar-energy harvesting and optoelectronic device building applications.

Topics: Anions; Cations; Chlorobenzenes; Electrochemistry; Electron Transport; Fullerenes; Indoles; Isoindoles; Kinetics; Ligands; Light; Organometallic Compounds; Oxidation-Reduction; Photochemistry; Pyridines; Spectrum Analysis; Toluene; Zinc; Zinc Compounds

Nanoparticles of aluminum and zinc phthalocyanin and metal-free phthalocyanin (AlPc, ZnPc, and H2Pc), whose molecular forms are photosensitizers, can serve as effective "prophotosensitizers" in photodynamic therapy for malignant tumors. Transition (stimulation) of photo-inert nanoparticles into a photoactive photosensitizer is realized locally in the tumor node by its exposure to potent laser pulses. Systemic injection of AlPc, ZnPc, and H2Pc nanoparticles has not led to accumulation of their photoactive form in the skin, which can lead to the development of skin phototoxicity. Effective protocols of photodynamic therapy with ZnPc nanoparticles are determined. The use of these protocols in mice with S-37 sarcoma led to 92-70% tumor growth inhibition, 48% improvement of survival, and cure in 84% cases.

Topics: Animals; Azo Compounds; Female; Fluorescence; Imidazoles; Indoles; Isoindoles; Laser Therapy; Mice; Nanostructures; Organometallic Compounds; Photochemotherapy; Photosensitizing Agents; Sarcoma; Zinc Compounds

The formation of self-assemblies between CdSe quantum dots (QDs) and Zn phthalocyanines (Pc) and azaphthalocyanines (AzaPc) bearing alkylsulfanyl substituents and the photophysical properties of these assemblies were studied using both steady-state and time-resolved luminescence/absorption spectroscopy. The formation of the self-assemblies was accompanied by a blue shift of the Q band of the dyes and by a quenching of the CdSe QDs luminescence. The largest spectral shift of the Q-band was approximately 7 nm and was observed for pentan-3-ylsulfanyl-functionalised phthalocyanine (). Assuming a 1 : 1 stoichiometry, the calculated binding constant was 4 × 10(4) M(-1). Pc substituted with the bulky tert-butylsulfanyl groups (1) exhibited a smaller shift of the Q band. The quenching of the CdSe QDs luminescence by 1 was more effective than that observed for 3. The results indicated that the luminescence quenching may be due to a photoinduced charge transfer between 1 or 3 and the CdSe QDs. In contrast, the AzaPc (2) with the same substituents as 1 had little effect on the QDs luminescence. For all cases, we found an inefficient resonance energy transfer between the attached dyes and the CdSe QD. The formation of the self-assemblies had negligible effects on the photogeneration of the singlet oxygen, O2((1)Δg), that was fully controlled only by the absorption of the light by the macrocycles.

Topics: Cadmium Compounds; Indoles; Isoindoles; Organometallic Compounds; Particle Size; Quantum Dots; Quantum Theory; Selenium Compounds; Solvents; Spectrometry, Fluorescence; Zinc Compounds

The novel phthalonitrile containing azine segment and its corresponding tetra aldazine substituted metal free- and metallo-phthalocyanines (Zn(II) and Ni(II)) were synthesized and characterized by IR, (1)H NMR, Mass, UV-Vis spectroscopy and elemental analysis and addition to these techniques for substituted phthalonitrile (13)C NMR have been used. In addition, dc and ac electrical properties of the films of these novel phthalocyanines were investigated as a function of temperature (295-523 K) and frequency (40-10(5)Hz). Activation energy values of the films of the phthalocyanines were calculated from straight portions of the Arrhenius plot (lnσ(dc)-1/T curves) as 0.70 eV, 0.93 eV and 0.91 eV for the films of metal free, nickel- and zinc-phthalocyanines, respectively. From impedance spectroscopy measurements, it is observed that bulk resistance decreases with increasing temperature indicating semiconductor property.

Topics: Dielectric Spectroscopy; Electric Conductivity; Indoles; Isoindoles; Nickel; Nitriles; Organometallic Compounds; Semiconductors; Spectrum Analysis; Thioridazine; Zinc Compounds

A series of unsymmetrical phthalocyanine sensitizer candidates with different donor and acceptor substituents, namely ZnPcBPh, ZnPcBOPh, ZnPcBtBu, ZnPcBN(Ph)₂, ZnPcBNHPh, ZnPcBNH₂, ZnPcBNHCH₃ and ZnPcBN(CH₃)₂, were designed and calculated using density functional theory (DFT) and time-dependent DFT calculations. The molecular orbital energy levels, the molecular orbital spatial distributions and the electronic absorption spectra of the ZnPcB series molecules were compared with those of TT7 and TT8 to reveal the substituent effects of different donor and acceptor groups on the phthalocyanine compounds and select good sesitizer candidates. The results show that some of these compounds have considerably smaller orbital energy gaps, red-shifted absorption bands and better charge-separated states, causing them to absorb photons in the lower energy region. Several new absorption bands emerge in the 400-600 nm region, which makes it possible for them to become panchromatic sensitizers. This characteristic is superior to the phthalocyanine sensitizers reported previously, including the current record holder, PcS6. The sensitizer candidates screened in the current work are very promising for providing good performance and might even challenge the photon-to-electricity conversion efficiency record of 4.6% for phthalocyanine sensitizers.

Topics: Coloring Agents; Electrons; Indoles; Isoindoles; Models, Molecular; Organometallic Compounds; Photons; Quantum Theory; Solar Energy; Static Electricity; Sunlight; Time Factors; Zinc Compounds

The local electronic structures of crystalline and amorphous films of zinc phthalocyanine (ZnPc) and metal-free phthalocyanine (H(2)Pc) have been studied by soft x-ray emission spectroscopy (XES). We found a clear crystalline structure dependence of the elastic-peak shape in the resonant XES spectra. The elastic peaks of both ZnPc and H(2)Pc are found to show an asymmetric shape due to resonant inelastic x-ray scattering (RIXS) at the nitrogen sites for the α-crystalline films, but not for the amorphous films. The observed RIXS feature is ascribed to the charge transfer excitation due to the Raman-active intermolecular interaction, which dominates the excited-electron dynamics in α-crystalline phthalocyanine films.

Topics: Crystallization; Indoles; Isoindoles; Membranes, Artificial; Molecular Structure; Organometallic Compounds; Spectrometry, X-Ray Emission; Zinc Compounds

The absorption, emission and excitation spectra of ZnPc and H(2)Pc trapped in Ne, N(2), Ar, Kr and Xe matrices have been recorded in the region of the Q states. A comparison of the matrix fluorescence spectra with Raman spectra recorded in KBr pellets reveals very strong similarities. This is entirely consistent with the selection rules and points to the occurrence of only fundamental vibrational transitions in the emission spectra. Based on this behaviour, the vibronic modes in emission have been assigned using results obtained recently on the ground state with large basis-set DFT calculations [Murray et al. PCCP, 12, 10406 (2010)]. Furthermore, the very strong mirror symmetry between excitation and emission has allowed these assignments to be extended to the excitation (absorption) bands. While this approach works well for ZnPc, coupling between the band origin of the S(2)(Q(Y)) state and vibrationally excited levels of S(1)(Q(X)), limits the range of its application in H(2)Pc. The Q(X)/Q(Y) state coupling is analysed from data obtained from site-selective excitation spectra, revealing pronounced matrix and site effects. From this analysis, the splitting of the Q(X) and Q(Y) states has been determined more accurately than in any previous attempts.

Topics: Indoles; Isoindoles; Luminescent Measurements; Molecular Structure; Organometallic Compounds; Quantum Theory; Stereoisomerism; Zinc Compounds

A panchromatic 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene-zinc phthalocyanine conjugate (Bodipy-ZnPc) 1 was synthesized starting from phthalocyanine aldehyde 4, via dipyrromethane 3 and dipyrromethene 2. Conjugate 1 represents the first example in which a Bodipy unit is tethered to the peripheral position of a phthalocyanine core. Electrochemical and optical measurements provided evidence for strong electronic interactions between the Bodipy and ZnPc constituents in the ground state of 1. When conjugate 1 is subjected to photoexcitation in the spectral region corresponding to the Bodipy absorption, the strong fluorescence characteristic of the latter subunit is effectively quenched (i.e., > or = 97%). Excitation spectral analysis confirmed that the photoexcited Bodipy and the tethered ZnPc subunits interact and that intraconjugate singlet energy transfer occurs with an efficiency of ca. 25%. Treatment of conjugate 1 with N-pyridylfulleropyrrolidine (8), an electron-acceptor system containing a nitrogen ligand, gives rise to the novel electron donor-acceptor hybrid 1<-->8 through ligation to the ZnPc center. Irradiation of the resulting supramolecular ensemble within the visible range leads to a charge-separated Bodipy-ZnPc(*+)-C(60)(*-) radical-ion-pair state, through a sequence of excited-state and charge transfers, characterized by a remarkably long lifetime of 39.9 ns in toluene.

Topics: Boron Compounds; Dimerization; Electrochemistry; Fluorescence; Fullerenes; Indoles; Isoindoles; Models, Chemical; Organometallic Compounds; Photochemistry; Porphobilinogen; Spectrometry, Fluorescence; Spectrophotometry, Ultraviolet; Zinc Compounds

The study of uptake mechanisms of therapeutic drugs has a growing interest in biomedical research. In this work the cell uptake and phototoxicity of the photosensitizer Zn(II)-phthalocyanine (ZnPc) in dipalmitoyl-phosphatidyl-choline liposomes have been studied in the presence or absence of inhibitors of macropinocytosis (cytochalasin D), and clathrin-mediated endocytosis (dynasore). No differences in the uptake or photodynamic damage were observed in A-549 cells subjected to incubation with either ZnPc alone or in combination with cytochalasin D. On the contrary, co-incubation of A-549 cells with ZnPc and dynasore resulted in a significant decrease of photodamage as well as negligible uptake of the photosensitizer. These results indicate that ZnPc is internalized into cells preferentially by a mechanism of clathrin-mediated endocytosis.

Topics: 1,2-Dipalmitoylphosphatidylcholine; Biological Transport; Cells; Cellular Structures; Clathrin; Cytochalasin D; Endocytosis; Indoles; Isoindoles; Liposomes; Organometallic Compounds; Photosensitizing Agents; Zinc Compounds

Unsymmetrical phthalocyanine derivatives have been widely studied as photosensitizers for photodynamic therapy (PDT), targeting various tumor types. However, the preparation of unsymmetrical phthalocyanines is always a challenge due to the presence of many possible structural isomers. Herein we report a new unsymmetrical zinc phthalocyanine, pentalysine beta-carbonylphthalocyanine zinc (ZnPc-(Lys)(5)), that was prepared in large quantity and high purity. This is a water-soluble cationic photosensitizer and maintains a high quantum yield of singlet oxygen generation similar to that of unsubstituted zinc phthalocyanine (ZnPc). Compared with anionic ZnPc counterparts, ZnPc-(Lys)(5) shows a higher level cellular uptake and 20-fold higher phototoxicity toward tumor cells. Pharmacokinetics and PDT studies of ZnPc-(Lys)(5) in S180 tumor-bearing mice showed a high ratio of tumor versus skin retention and significant tumor inhibition. This new molecular framework will allow synthetic diversity in the number of lysine residues incorporated and will facilitate future QSAR studies.

Topics: Animals; Antineoplastic Agents; Cell Line; Humans; Indoles; Isoindoles; K562 Cells; Mice; Neoplasms; Oligopeptides; Organometallic Compounds; Photochemotherapy; Photosensitizing Agents; Singlet Oxygen; Zinc Compounds

Photodynamic therapy (PDT) has emerged as an alternative and promising noninvasive treatment for cancer. It is a two-step procedure that uses a combination of molecular oxygen, visible light, and photosensitizer (PS) agents; phthalocyanine (Pc) was supported over titanium oxide but has not yet been used for cell inactivation. Zinc phthalocyanine (ZnPc) molecules were incorporated into the porous network of titanium dioxide (TiO(2)) using the sol-gel method. It was prepared from stock solutions of ZnPc and TiO(2). ZnPc-TiO(2) was tested with four cancer cell lines. The characterization of supported ZnPc showed that phthalocyanine is linked by the N-pyrrole to the support and is stable up to 250°C, leading to testing for PDT. The preferential localization in target organelles such as mitochondria or lysosomes could determine the cell death mechanism after PDT. The results suggest that nanoparticulated TiO(2) sensitized with ZnPc is an excellent candidate as sensitizer in PDT against cancer and infectious diseases.

Topics: Calorimetry, Differential Scanning; Cell Line, Tumor; Cells, Cultured; Humans; Indoles; Isoindoles; Light; Organometallic Compounds; Oxygen; Photochemotherapy; Photosensitizing Agents; Spectrum Analysis, Raman; Titanium; Zinc Compounds

The effect of ionic substituents in zinc and aluminum phthalocyanine molecules and of membrane surface charge on the interaction of dyes with artificial membranes and enterobacterial cells, as well as on photosensitization efficiency was studied. It has been shown that increasing the number of positively charged substituents enhances the extent of phthalocyanine binding to Escherichia coli cells. This, along with the high quantum yield of singlet oxygen generation, determines efficient photodynamic inactivation of Gram-negative bacteria by zinc and aluminum octacationic phthalocyanines. The effect of Ca2+ and Mg2+ cations and pH on photodynamic inactivation of enterobacteria in the presence of octacationic zinc phthalocyanine has been studied. It has been shown that effects resulting in lowering negative charge on outer membrane protect bacteria against photoinactivation, which confirms the crucial role in this process of the electrostatic interaction of the photosensitizer with the cell wall. Electrostatic nature of binding is consistent with mainly electrostatic character of dye interactions with artificial membranes of different composition. Lower sensitivity of Proteus mirabilis to photodynamic inactivation, compared to that of E. coli and Salmonella enteritidis, due to low affinity of the cationic dye to the cells of this species, was found.

Topics: Cations; Enterobacteriaceae; Escherichia coli; Fluorescent Dyes; Hydrogen-Ion Concentration; Indoles; Isoindoles; Organometallic Compounds; Photosensitizing Agents; Singlet Oxygen; Static Electricity; Zinc Compounds

In this study we evaluated the photophysical, photochemical properties of the zinc phthalocyanine/ magnetic fluid (ZnPC/MF) complex in liposomal medium. As a result of the present investigation we propose the liposome-encapsulated ZnPC/MF complex as a very promising nanostructured device for cancer treatment. The spectroscopy characterization and the in vitro dark toxicity of both ZnPC and ZnPC/MF complex in Hank's and in liposomal medium are reported. Our findings revealed that the spectroscopic properties of the ZnPC associated or not with MF presented little differences and are very close to what one expects from an ideal photosensitizer compound. Indeed, the ZnPC/MF complex in liposomal medium presented lower dark toxicity compared to the ZnPC/MF complex in Hank's, strongly supporting the use of the former for cancer treatment.

Topics: Animals; Drug Carriers; Drug Delivery Systems; Humans; Indoles; Isoindoles; Liposomes; Magnetics; Mice; Nanotechnology; Neoplasms; Organometallic Compounds; Oxygen; Photochemotherapy; Spectrometry, Fluorescence; Zinc Compounds

The synergistic effect of ultrasound (US) and chemicals on cells is known as sonodynamic therapy. In this work, two phthalocyanines (zinc and chloroaluminum) have been tested as potential sonosensitizers for sonodynamic therapy. We studied the effect of US and phthalocyanines on carp erythrocytes, as a nucleated cell model. The level of hemolysis, osmotic fragility, lipid peroxidation and oxidation of hemoglobin were the markers of these reactions. Red blood cells were preincubated with phthalocyanines and exposed to 1 MHz continuous wave at the intensity of 2.44 W/cm2 for 5 min. It was noticed that US and phthalocyanines exposure led to an increase in the level of hemolysis, lipid peroxidation product and osmotic fragility in comparison to US alone and phthalocyanines alone. However, these factors did not cause changes in the degree of hemoglobin oxidation. The results lead to the conclusion that phthalocyanines caused synergistic effect with US, and it can be used as a sonosensitizer for sonodynamic therapy, but the mechanism of this action is still unclear.

Topics: Animals; Carps; Cells, Cultured; Combined Modality Therapy; Erythroblasts; Hemolysis; Indoles; Isoindoles; Lipid Peroxidation; Methemoglobin; Models, Animal; Organometallic Compounds; Osmotic Fragility; Photosensitizing Agents; Ultrasonic Therapy; Zinc Compounds

The monomer electronic absorption spectra of the ZnPcS2P2 (disulfonated diphthalimidomethyl phthalocyanine zinc) in 11 kinds of solvents and 5 kinds of unsubstituted metal phthalocyanines in DMF were investigated. The monomer electronic absorption spectra of some substituted phthalocyanine zinc including ZnPcS4 (tetrasulfonated phthalocyanine zinc), ZnPcS4 (tetraphthalimidomethyl phthalocyanine zinc), ZnPc(NO2)4 (tetranitro phthalocyanine zinc) and ZnPcS2P2 in the same solvent were also studied. The result showed that (1) with the strengthening of coordination ability of the solvent, the maximum absorption wavelength of ZnPcS2P2 increased slightly. (2) with the increasing of electronegativity of central ion, the maximum absorption wavelength of MPcs had a little blue shift. (3) the electron-donating substituting group caused slightly blue shift. The monomer fluorescence spectra of ZnPcS4, ZnPcP4, and ZnPcS2P2 in different solvents were determined. The result showed that (1) the electron-withdrawing substituting group caused slightly red shift of the fluorescence spectra. (2) with the strenghtening of coordination ability of the solvent, the maximum emission wavelength increased slightly. (3) the fluorescence intensity of ZnPcS2P2 in the solution which contains Cremophor EL was remarkable stronger than that in other solvents. This is an important suggest to the development of photodynamic diagnose agent. The effect of solvents, central ions and substituents on spectra were partly explained by means of the quantrum chemistry.

Topics: Electrochemistry; Humans; Indoles; Isoindoles; Organometallic Compounds; Photochemotherapy; Photosensitizing Agents; Solubility; Solvents; Spectrometry, Fluorescence; Spectrophotometry, Atomic; Structure-Activity Relationship; Zinc Compounds