boron and dipyrromethene

Boron-dipyrromethene (BODIPY) and its derivatives play an important role in the area of organic fluorophore chemistry. Recently, the water-soluble boron-dipyrromethene dyes have increasingly received interest. The structural modification of the BODIPY core by incorporating different neutral and ionic hydrophilic groups makes it water-soluble. The important hydrophilic groups, such as quaternary ammonium, sulfonate, oligoethylene glycol, dicarboxylic acid, and sugar moieties significantly increase the solubility of these dyes in water while preserving their photophysical properties. As a result, these fluorescent dyes are utilized in aqueous systems for applications such as chemosensors, cell imaging, anticancer, biolabeling, biomedicine, metal ion detection, and photodynamic treatment. This review covers the most current developments in the design and synthesis of water-soluble BODIPY derivatives and their wide applications since 2014.

Topics: Boron; Fluorescent Dyes; Water

Boron dipyrromethene (BODIPY), as a traditional fluorescent dye, has drawn increasing attention because of its excellent photophysical properties like adjustable spectra and outstanding photostability. BODIPY dyes could be assembled into nanoparticles for cancer imaging and therapy via rational design. In this review, the bio-applications of BODIPY-containing nanoparticles are introduced in detail, such as cellular imaging, near-infrared fluorescence imaging, computed tomography imaging, photoacoustic imaging, phototherapy, and theranostics. The construction strategies of BODIPY-containing nanoparticles are emphasized so the review has three sections-self-assembly of small molecules, chemical conjugation with hydrophilic compounds, and physical encapsulation. This review not only summarizes various and colorific bio-applications of BODIPY-containing nanoparticles, but also provides reasonable design methods of BODIPY-containing nanoparticles for cancer theranostics. This article is categorized under: Diagnostic Tools > in vivo Nanodiagnostics and Imaging.

Topics: Animals; Boron; Diagnostic Imaging; Drug Compounding; Humans; Nanoparticles; Neoplasms; Porphobilinogen

As traditional phototherapy agents, boron dipyrromethene (BODIPY) photosensitizers have attracted increasing attention due to their high molar extinction coefficients, high phototherapy efficacy, and excellent photostability. After being formed into nanostructures, BODIPY-containing nano-photosensitizers show enhanced water solubility and biocompatibility as well as efficient tumor accumulation compared to BODIPY molecules. Hence, BODIPY nano-photosensitizers demonstrate a promising potential for fighting cancer. This review contains three sections, classifying photodynamic therapy (PDT), photothermal therapy (PTT), and the combination of PDT and PTT based on BODIPY nano-photosensitizers. It summarizes various BODIPY nano-photosensitizers, which are prepared via different approaches including molecular precipitation, supramolecular interactions, and polymer encapsulation. In each section, the design strategies and working principles of these BODIPY nano-photosensitizers are highlighted. In addition, the detailed in vitro and in vivo applications of these recently developed nano-photosensitizers are discussed together with future challenges in this field, highlighting the potential of these promising nanoagents for new tumor phototherapies.

Topics: Animals; Antineoplastic Agents; Boron; Humans; Neoplasms; Photosensitizing Agents; Phototherapy; Porphobilinogen

Various molecular and supramolecular systems have been synthesized and characterized recently to mimic the functions of photosynthesis, in which solar energy conversion is achieved. Artificial photosynthesis consists of light-harvesting and charge-separation processes together with catalytic units of water oxidation and reduction. Among the organic molecules, derivatives of BF2-chelated dipyrromethene (BODIPY), "porphyrin's little sister", have been widely used in constructing these artificial photosynthetic models due to their unique properties. In these photosynthetic models, BODIPYs act as not only excellent antenna molecules, but also as electron-donor and -acceptor molecules in both the covalently linked molecular and supramolecular systems formed by axial coordination, hydrogen bonding, or crown ether complexation. The relationships between the structures and photochemical reactivities of these novel molecular and supramolecular systems are discussed in relation to the efficiency of charge separation and charge recombination. Femto- and nanosecond transient absorption and photoelectrochemical techniques have been employed in these studies to give clear evidence for the occurrence of energy- and electron-transfer reactions and to determine their rates and efficiencies.

Topics: Biomimetic Materials; Biomimetics; Boron; Electrons; Energy Transfer; Photochemical Processes; Photosynthesis; Porphobilinogen; Solar Energy

We present an overview of the state of the art in long-wavelength boron-dipyrromethene (BODIPY) fluorophores, focusing on strategies to shift the absorption and emission bands into the red/near-infrared (NIR) range of the spectrum. This report also discusses chemical modifications of the chromophoric core to obtain analyte-responsive fluorophores, including examples of pH and metal ion indicators. Finally, we present a new series of phenanthrene-fused BODIPY dyes, emitting with high efficiency in the red/NIR region of the spectrum, as well as discussing potential applications thereof as probes.

Topics: Boron; Boron Compounds; Fluorescent Dyes; Hydrogen-Ion Concentration; Ions; Metals; Models, Chemical; Molecular Structure; Phenanthrenes; Porphobilinogen; Solvents; Spectrophotometry; Spectroscopy, Near-Infrared; Temperature

Topics: Boron; Boron Compounds; Cysteine; Fluorescent Dyes; Glutathione; Hep G2 Cells; Humans; Spectrometry, Fluorescence; Sulfhydryl Compounds

A low-cost and simple boron-dipyrromethene (BODIPY)-labeled aptasensor (B-aptamer) was designed for rapid, sensitive and turn-on catechin detection. B-aptamer as signal indicator and recognition element initially stacked on the surface of multi-walled carbon nanotubes (MWCNTs) via π-π conjugation, resulting in efficient quenching of the fluorescence of the aptasensor. Upon addition of catechin, catechin was adsorbed to B-aptamer, thereby undergoing a conformational change to form B-aptamer/catechin complex, which prompted the release of the signaling probe from the surface of MWCNTs. Hence, the fluorescence intensity (FL) of the B-aptamer was increasing with the increase of catechin concentrations with the limit of detection (LOD) of 5 ng/mL. Furthermore, the method was used to analyze catechin in food samples with the recovery rate of 92.7-107.1 %. This method provided a proper analysis method for clinical analysis and pharmaceutical quality control.

Topics: Aptamers, Nucleotide; Biosensing Techniques; Boron; Catechin; Limit of Detection; Nanotubes, Carbon

Singlet oxygen (

Topics: Alzheimer Disease; Boron; Humans; Neuronal Outgrowth; Photosensitizing Agents; Protein Aggregates; Ruthenium; Singlet Oxygen; tau Proteins

The work is devoted to preparing and characterizing the properties of photosensitive composites, based on chitosan proposed for photodynamic therapy. Chitosan films with a 5% addition of two BODIPY dyes were prepared by solution casting. These dyes are dipyrromethene boron derivatives with N-alkyl phthalimide substituent, differing in the presence of iodine atoms in positions 2 and 6 of the BODIPY core. The spectral properties of the obtained materials have been studied by infrared and UV-vis absorption spectroscopy and fluorescence, both in solutions and in a solid state. Surface properties were investigated using the contact angle measurement. The morphology of the sample has been characterized by Scanning Electron and Atomic Force Microscopy. Particular attention was paid to studying the protein absorption and kinetics of the dye release from the chitosan. Adding BODIPY to the chitosan matrix leads to a slight increase in hydrophilicity, higher structure heterogeneity, and roughness, than pure chitosan. The presence of iodine atoms in the BODIPY structure caused the bathochromic effect, but the emission quantum yield decreased in the composites. It has been found that BODIPY-doped chitosan interacts better with human serum albumin and acidic α-glycoprotein than unmodified chitosan. The release rate of dyes from films immersed in methanol depends on the iodine present in the structure.

Topics: Boron; Chitosan; Fluorescent Dyes; Humans

Antimicrobial photodynamic therapy (aPDT) is an effective strategy to eliminate bacteria without inducing bacterial resistance. As typical aPDT photosensitizers, most of boron-dipyrromethene (BODIPY) are hydrophobic, and nanometerization is imperative to render them dispersible in physiological media. Recently, carrier-free nanoparticles (NPs) are formed via the self-assembly of BODIPYs without the help of any surfactants or auxiliaries, arousing people's interest. So as to fabricate carrier-free NPs, BODIPYs usually need to be derived into dimers, trimers, or amphiphiles through complex reactions. Few unadulterated NPs were obtained from BODIPYs with precise structures. Herein, BNP1-BNP3 were synthesized by the self-assembly of BODIPY, which showed excellent anti-Staphylococcus aureus ability. Among them, BNP2 could effectively fight bacterial infections and promote wound healing in vivo.

Topics: Anti-Bacterial Agents; Boron; Humans; Nanoparticles; Photochemotherapy; Photosensitizing Agents; Staphylococcal Infections; Wound Healing

In vivo optical imaging is an important application value in disease diagnosis. However, near-infrared nanoprobes with excellent luminescent properties are still scarce. Herein, two boron-dipyrromethene (BODIPY) molecules (BDP-A and BDP-B) were designed and synthesized. The BODIPY emission was tuned to the near-infrared (NIR) region by regulating the electron-donating ability of the substituents on its core structure. In addition, the introduction of polyethylene glycol (PEG) chains on BODIPY enabled the formation of self-assembled nanoparticles (NPs) to form optical nanoprobes. The self-assembled BODIPY NPs present several advantages, including NIR emission, large Stokes shifts, and high fluorescence quantum efficiency, which can increase water dispersibility and signal-to-noise ratio to decrease the interference by the biological background fluorescence. The in vitro studies revealed that these NPs can enter tumor cells and illuminate the cytoplasm through fluorescence imaging. Then, BDP-B NPs were selected for use in vivo imaging due to their unique NIR emission. BDP-B was enriched in the tumor and effectively illuminated it via an enhanced penetrability and retention effect (EPR) after being injected into the tail vein of mice. The organic nanoparticles were metabolized through the liver and kidney. Thus, the BODIPY-based nanomicelles with NIR fluorescence emission provide an effective research basis for the development of optical nanoprobes in vivo.

Topics: Animals; Boron; Fluorescence; Mice; Nanoparticles

Phototheranostics integrating optical imaging and phototherapy has attracted extensive attention. Achieving nanophototherapeutics with near infrared (NIR)-light synchronously triggered photodynamic therapy (PDT) and photothermal therapy (PTT) is challenging. Herein, we develop a multifunctional theranostic nanoplatform prepared from the co-assembly of NIR boron dipyrromethene (BODIPY) with a cooperative D-π-A structure of a thiophene-BODIPY core and benzene-diethylamino, and a choline phosphate lipid. The as-fabricated nanoparticles (DBNPs) exhibited desirable NIR absorption, uniform spherical morphology and good colloidal stability. The elaborate molecular design and supramolecular assembly endowed DBNPs with desirable PDT and PTT activities. Upon 808 nm laser irradiation, the DBNPs efficiently generated active singlet oxygen and regional hyperpyrexia, with a photothermal conversion efficiency of 37.6%. The excellent PDT and PTT performance of DBNPs boosted the potent

Topics: Boron; Humans; Lipids; Nanoparticles; Neoplasms; Optical Imaging; Phosphorylcholine

Ferroptosis is a form of programmed cell death and plays an important role in many diseases. Dihydroorotate dehydrogenase (DHODH) and glutathione peroxidase 4 (GPX4) play major roles in cell resistance to ferroptosis. Therefore, inactivation of these proteins provides an excellent opportunity for efficient ferroptosis-based synergistic cancer therapy. In this study, a multifunctional nanoagent (BPN

Topics: Boron; Dihydroorotate Dehydrogenase; Ferroptosis; Humans; Neoplasms

Amino acids are one kind of basic life unit in biological systems. Modification with amino acids may bring interesting properties to the principal molecules. In this work, BDP was modified with L-aspartic acid (Asp) and D-Asp to obtain BDP-LAsp and BDP-DAsp, respectively. The as-synthesized BDPs can self-assemble into uniform nanoparticles (NPs) due to the hydrophilicity of Asp. We found that BDP-LAsp NPs possessed higher photodynamic therapeutic efficacy than BDP-DAsp NPs in fighting against cancer cells and bacteria. This provides a simple design strategy for the modification of photosensitizers in the biomedical field.

Topics: Amino Acids; Boron; Nanoparticles; Photosensitizing Agents

Heavy-atom-free photosensitizers are envisioned as the next generation of photoactive molecules for photo-theragnosis. In this approach, and after suitable irradiation, a single molecular scaffold is able to visualize and kill tumour cells by fluorescence signalling and photodynamic therapy (PDT), respectively, with minimal side effects. In this regard, BODIPY-based orthogonal dimers have irrupted as suitable candidates for this aim. Herein, we analyse the photophysical properties of a set of formyl-functionalized BODIPY dimers to ascertain their suitability as fluorescent photosensitizers. The conducted computationally aided spectroscopic study determined that the fluorescence/singlet oxygen generation dual performance of these valuable BODIPY dimers not only depends on the BODIPY-BODIPY linkage and the steric hindrance around it, but also can be modulated by proper formyl functionalization at specific chromophoric positions. Thus, we propose regioselective formylation as an effective tool to modulate such a delicate photonic balance in BODIPY-based dimeric photosensitizers. The taming of the excited-state dynamics, in particular intramolecular charge transfer as the key underlying process mediating fluorescence deactivation vs. intersystem crossing increasing, could serve to increase fluorescence for brighter bioimaging, enhance the generation of singlet oxygen for killing activity, or balance both for photo-theragnosis.

Topics: Boron; Boron Compounds; Photochemotherapy; Photosensitizing Agents; Singlet Oxygen

Topics: Boron; Cisplatin; Ligands; Light; Mitochondria; Photochemotherapy; Photosensitizing Agents; Platinum

Dicofol is an organochlorine pesticide, which is widely used in fruits, tea and other crops, and is moderately toxic to humans. Therefore, the monitoring of organochlorine pesticide-dicofol is critical for food safety. In this work, a fluorometric chemosensor based on mercaptoethanol and boron dipyrromethene (BODIPY) was first constructed to detect the dicofol. The chemosensor displayed turn-off fluorescence behavior upon dicofol with a detection limit of 200 ppb. The nucleophilicity of the glutathione and other biological thiols was studied to evaluate the reactivity of thiols with dicofol. In practical applications, an obvious color difference was observed on a paper based microfluidic device modified by phenyltriethoxysilane (PTES). We designed an integrated device for pretreatment and paper-based detection, and successfully used for the detection of dicofol in tea. The applicability was demonstrated by detection of dicofol in real tea samples with good recovery ranging from 86% to 109%. The apparatus was convenient and could be used for on-site evaluation of dicofol.

Topics: Boron; Dicofol; Humans; Pesticides; Porphobilinogen

It is essential to develop novel multifunctional and easily synthesized stable NIR-II fluorescent probes to guide photothermal therapy for tumors. Here, we propose a new strategy to construct boron dipyrromethene (BODIPY) J-aggregates by intermolecular hydrogen bonding (H-bond) and π-π stacking interactions to achieve fluorescence emission in the second near-infrared window (NIR-II, 1000-1700 nm). A novel meso-benzamide galactose hexanoate-BODIPY (Gal-OH-BDP) amphiphilic small molecular dye was synthesized and it formed nanoparticles spontaneously in aqueous solution with a maximum emission wavelength near 1060 nm, which works as a smart nanomedicine for targeting NIR-II imaging-guided photothermal therapy (PTT) of hepatocellular carcinoma. Galactose not only provided hydrogen bonds to regulate the aggregation pattern of the molecules but also effectively targeted hepatocellular carcinoma cells and promoted the formation of well-dispersed nanoparticles of dye molecules due to their hydrophilicity. Moreover, due to high photothermal conversion efficiency (PCE = 55%), Gal-OH-BDP NPs achieve galactose-targeted NIR-II imaging and PTT, which is important for the precise diagnosis and treatment of tumors (Scheme 1). In the present research work, H-bond was introduced for the first time into BODIPY for building J-aggregates to achieve the NIR-II fluorescence.

Topics: Boron; Cell Line, Tumor; Fluorescence; Galactose; Hydrogen Bonding; Nanoparticles; Phototherapy; Photothermal Therapy; Porphobilinogen

The fast relaxation processes in the excited electronic states of functionalized aza-boron-dipyrromethene (aza-BODIPY) derivatives (1-4) were investigated in liquid media at room temperature, including the linear photophysical, photochemical, and nonlinear optical (NLO) properties. Optical gain was revealed for nonfluorescent derivatives 3 and 4 in the near infrared (NIR) spectral range under femtosecond excitation. The values of two-photon absorption (2PA) and excited-state absorption (ESA) cross-sections were obtained for 1-4 in dichloromethane using femtosecond Z-scans, and the role of bromine substituents in the molecular structures of 2 and 4 is discussed. The nature of the excited states involved in electronic transitions of these dyes was investigated using quantum-chemical TD-DFT calculations, and the obtained spectral parameters are in reasonable agreement with the experimental data. Significant 2PA (maxima cross-sections ∼2000 GM), and large ESA cross-sections ∼10

Topics: Boron; Boron Compounds; Fluorescent Dyes; Porphobilinogen; Spectrum Analysis

A boron dipyrromethene (BODIPY) derivative bearing a

Topics: Boron; Boron Compounds; Porphobilinogen; Proline

We report N,O-boron-chelated dipyrromethene derivatives exhibiting circularly polarized luminescence (CPL) in the red/near-infrared region, both in solution and the aggregated state. The CPL is originated from the helical chirality through intramolecular substitution of fluorine by an alkenolic substituent. The self-assembly of the fluorophores significantly enhances the |

Topics: Boron; Boron Compounds; Luminescence; Porphobilinogen

There is an urgent need to develop efficient and safe antimicrobials to augment traditional antibiotics for fighting drug-resistant bacteria. Antimicrobial photodynamic therapy (aPDT), is a promising antimicrobial stize antibiotic resistance and may reduce systemic side effects. Boron-dipyrromethene (BODIPY) is a type of photosensitizer (PSs) for aPDT with tunable structures and rational photophysical features. Herein, six kinds of BODIPY derivatives (BDP1-BDP6) modified with different atoms or groups such as iodine atoms, thiophene, cyano, phenyl, aldehyde and nitro groups were synthesized and their photophysical behaviors were characterized. The results indicated that BDP3, which had 2, 6-diiodo and 8-phenyl substitution, was the best PS candidate with the highest reactive oxygen species (ROS) generation efficacy. BDP3 and BDP5 could rapidly kill Staphylococcus aureus (S. aureus) with the minimum inhibitory concentration (MIC) of 10 nM upon illumination. They also possessed excellent biofilm inhibition ability against S. aureus and could efficaciously restrain the formation of bacterial biofilm. The results of Live/Dead staining assay and scanning electron microscopy (SEM) demonstrated that BDP3 destroyed the cell membrane structure of bacteria by generating ROS, which ultimately led to bacterial lysis and death. Finally, the biosafety evaluation toward the mouse fibroblasts (L929 cells) suggested BDP3 had good cytocompatibility. This work exhibits the great potential of rational designs of PS for aPDT applications.

Topics: Animals; Anti-Bacterial Agents; Anti-Infective Agents; Bacteria; Boron; Boron Compounds; Mice; Photochemotherapy; Photosensitizing Agents; Porphobilinogen; Reactive Oxygen Species; Staphylococcus aureus

The linear and nonlinear optical properties of two BODIPY derivatives, 1,7-Diphenyl-3,5-bis(9,9-dimethyl-9H-fluoren-2-yl)-boron-diuoride-azadipyrromethene (ZL-61) and 1,7-Diphenyl-3,5-bis(4-(1,2,2-triphenylvinyl)phenyl)-boron-diuoride-azadipyrromethene (ZL-22), were comprehensively investigated based on experimental and theoretical studies. It was found that both compounds show a strong two-photon absorption response in the near-infrared regime, and the two-photon-absorption cross-section values of ZL-61 and ZL-22 were determined to be 8321 GM and 1864 GM at 800 nm, respectively. The improvement of the two-photon absorption cross section in ZL-61 was attributed to the enhancement of the donor group, which was confirmed by transient absorption measurements and DFT calculation. Our results indicate that these BODIPY derivatives are a promising candidate for optical limiting and two-photon imaging applications.

Topics: Boron; Boron Compounds; Fluorescent Dyes; Porphobilinogen

We report a boron dipyrromethene that is chiral at boron and carbon (B*C*-BODIPY) and accessible through a two-pot, one-step synthesis-an interrupted Knoevenagel condensation. The electronic circular dichroism spectra of chiral high performance liquid chromatography-resolved enantiomers show clear Cotton effects (∣

Topics: Boron; Carbon; Circular Dichroism; Porphobilinogen

For long-term live-cell fluorescence imaging and biosensing, it is crucial to work with a dye that has high fluorescence quantum yield and photostability without being detrimental to the cells. In this paper, we demonstrate that neutral boron-dipyrromethene (BODIPY)-based molecular rotors have great properties for high-light-dosage demanding live-cell fluorescence imaging applications that require repetitive illuminations. In molecular rotors, an intramolecular rotation (IMR) allows an alternative route for the decay of the singlet excited state (S

Topics: Boron; Boron Compounds; Molecular Probes; Oxygen; Porphobilinogen

The regulation of photochemical properties of phototheranostics, especially the absorption, fluorescence, singlet oxygen (

Topics: Boron; Boron Compounds; HeLa Cells; Humans; Nanoparticles; Neoplasms; Photoacoustic Techniques; Photothermal Therapy; Porphobilinogen

The presence of apoptosis inhibition proteins renders the cancer cells resistant to apoptosis, severely compromising the antitumor efficacy of sonodynamic therapy (SDT). Here, an intelligent anticancer nanoplatform based on an Aza-boron-dipyrromethene dye (denoted as Aza-BDY) is elaborately established for ferroptosis augmented SDT through cysteine (Cys) starvation. After endocytosis by tumor cells, Aza-BDY serves as both a ferroptosis inducing agent and a sonosensitizer for tumor treatment. The specific Cys response facilitates the disruption of redox homeostasis and initiation of cellular ferroptosis. Meanwhile, the released sonosensitizer causes efficient SDT and augments ferroptosis under ultrasound irradiation. Detailed in vitro and in vivo investigations demonstrate that the synergistic effect of Cys depletion and singlet oxygen (

Topics: Boron; Cell Line, Tumor; Cysteine; Ferroptosis; Humans; Nanoparticles; Neoplasms; Porphobilinogen; Reactive Oxygen Species; Singlet Oxygen

Hypoxia-activated prodrugs (HAPs) have drawn increasing attention for improving the antitumor effects while minimizing side effects. However, the heterogeneous distribution of the hypoxic region in tumors severely impedes the curative effect of HAPs. Additionally, most HAPs are not amenable to optical imaging, and it is difficult to precisely trace them in tissues. Herein, we carefully designed and synthesized a multifunctional therapeutic

Topics: Azo Compounds; Boron; Boron Compounds; Camptothecin; Cell Line, Tumor; Humans; Hyperthermia, Induced; Hypoxia; Nanoparticles; Neoplasms; Phototherapy; Photothermal Therapy; Porphobilinogen; Prodrugs

Increasing Investigations show that photosensitizers (PSs) which target mitochondria are useful for enhancing photodynamic therapy (PDT) efficacy. Herein, we carefully designed and synthesized four triphenylphosphonium (TPP)-modified boron dipyrromethene (BDP)-based PSs through Cu(I)-assisted "3+2" cycloaddition reaction. All of them exhibit intense red light absorption with maxima between 659 and 663 nm, considerable fluorescence emission with quantum yields of 0.16-0.23, high singlet oxygen generation efficiency ranging from 0.22 to 0.34, excellent mitochondria-targeting ability, and good biocompatibility. Upon illumination, they induce significant cancer cell death through a mitochondria-related apoptosis pathway. The IC

Topics: Boron; Coloring Agents; Mitochondria; Photochemotherapy; Photosensitizing Agents; Porphobilinogen; Singlet Oxygen

A boron dipyrromethene (BODIPY)-based metal-organic framework (MOF) nanoemitter was for the first time designed with enhanced electrochemiluminescence (ECL) intensity due to the suppression of non-radiative dissipation originating from the ordered arrangement of BODIPY molecules in the framework. Thus, an ECL biosensor was developed for telomerase detection with excellent performance in real samples.

Topics: Biosensing Techniques; Boron; Boron Compounds; Electrochemical Techniques; Limit of Detection; Luminescent Measurements; Metal-Organic Frameworks; Porphobilinogen; Telomerase

Cancer phototheranostics that combines diagnosis with phototherapy has emerged as a new mode of precise treatment. Nevertheless, taking highly effective phototheranostics into consideration, it is still a tremendous challenge to design multifunctional photothermal agents (PTAs) that combine the features of intensive near-infrared (NIR) absorption/emission, high photothermal conversion efficiency (PCE) and preferable tumor accumulation. Herein, seeking a convenient method to facilitate absorption red-shift, promote the accumulation of drugs in tumors and heighten the PCE appears to be particularly important for cancer theranostics. In this work, heavy-atom-free boron dipyrromethene (BODIPY) was assembled with F127 to fabricate ultra-small J-aggregated nanoparticles (named as BNPs). Compared to free BODIPY, BNPs exhibited 63 nm redshifted absorption, deep-tissue fluorescence imaging, enhanced cellular uptake, preferable tumor accumulation, elevated PCE, excellent photothermal stability and water dispersibility.

Topics: Boron; Cell Line, Tumor; Humans; Nanoparticles; Neoplasms; Theranostic Nanomedicine

A boron-dipyrromethene (BODIPY) derivative reactive towards amino groups of proteins (

Topics: Amines; Boron; Fluorescent Dyes; Molecular Docking Simulation; Serum Albumin, Bovine; Solvents

People spend up to 90% of their time indoors, and yet our understanding of indoor air quality and the chemical processes driving it are poorly understood, despite levels of key pollutants typically being higher indoors compared to outdoors. Nitrous acid (HONO) is a species that drives these indoor chemical processes, with potentially detrimental health effects. In this work, a BODIPY-based probe was synthesized with the aim of developing the first selective passive sampler for atmospheric HONO. Our probe and its products are easily detected by UV-Vis spectroscopy with molar extinct coefficients of 37 863 and 33 787 M

Topics: Air Pollution, Indoor; Boron; Humans; Nitrites; Nitrous Acid; Porphobilinogen

We disclose an interesting concept for developing heavy atom-free chemiluminogenic photosensitizers. To accomplish this, conjugates

Topics: Boron; Boron Compounds; Luminol; Photochemotherapy; Photosensitizing Agents; Porphobilinogen; Singlet Oxygen

We report herein the synthesis of a novel dicationic boron dipyrromethene derivative (compound 3) which is symmetrically substituted with two trimethylammonium styryl groups.. The antibacterial photodynamic activity of compound 3 was determined against sixteen methicillin-resistant Staphylococcus aureus (MRSA) strains, including four ATCC type strains (ATCC 43300, ATCC BAA-42, ATCC BAA-43, and ATCC BAA-44), two mutant strains [AAC(6')-APH(2") and RN4220/pUL5054], and ten nonduplicate clinical strains of hospital- and community-associated MRSA. Upon light irradiation, the minimum bactericidal concentrations of compound 3 were in the range of 1.56-50 μM against all the sixteen MRSA strains. Interestingly, compound 3 was not only more active than an analogue in which the ammonium groups are not directly connected to the n-conjugated system (compound 4), but also showed significantly higher (p < 0.05) antibacterial potency than the clinically approved photosensitizer methylene blue. The skin irritation of compound 3 during topical application was tested on human 3-D skin constructs and proven to be non-irritant in vivo at concentrations below 1.250 mM. In the murine MRSA infected wound study, the colony forming unit reduction of compound 3 + PDT group showed significantly (p < 0.05) higher value (>2.5 log. In conclusion, the present study provides a scientific basis for future development of compound 3 as a potent photosensitizer for photodynamic therapy for MRSA wound infection.

Topics: Animals; Anti-Bacterial Agents; Anti-Infective Agents; Boron; Humans; Methicillin-Resistant Staphylococcus aureus; Mice; Microbial Sensitivity Tests; Photochemotherapy; Photosensitizing Agents; Porphobilinogen

Through a simple 1,3-cycloaddition reaction, three BODIPY-peptide conjugates that target the extracellular domain of the epidermal growth factor receptor (EGFR) were prepared and their ability for binding to EGFR was investigated. The peptide ligands K(N

Topics: Boron; Boron Compounds; Cell Line, Tumor; ErbB Receptors; Fluorescent Dyes; Humans; Ligands; Peptides, Cyclic; Porphobilinogen; Protein Binding; Surface Plasmon Resonance

A novel nanosystem of polydopamine-coated gold nanorods (AuNR@PDA) immobilised with molecules of hairpin DNA-conjugated distyryl boron dipyrromethene (DSBDP) was designed and fabricated for detection of microRNA-21 (miR-21). By using this oncogenic stimulus, the photodynamic effect of the DSBDP-based photosensitiser was also activated. In the presence of miR-21, the fluorescence intensity of the nanosystem was increased due to the dissociation of the conjugate from AuNR@PDA upon hybridisation. The intracellular fluorescence intensity triggered by intracellular miR-21 was in the order: MCF-7 > HeLa > HEK-293, which was in accordance with their miR-21 expression levels. The specificity was demonstrated by comparing the results with those of an analogue with a scrambled DNA sequence. The nanosystem could also result in miR-21-mediated photodynamic eradication of miR-21-overexpressed MCF-7 cells. After intravenous injection of the nanosystem into HeLa tumour-bearing nude mice, the fluorescence intensity of the tumour was increased over 24 h and was about 3-fold stronger than that of the scrambled analogue. Upon irradiation, the nanosystem could also greatly reduce the size of the tumour without causing significant tissue damage in the major organs. The overall results showed that this nanoplatform can serve as a specific and potent theranostic agent for simultaneous miR-21 detection and miR-21-mediated photodynamic therapy.

Topics: Animals; Boron; DNA; Gold; HEK293 Cells; Humans; Indoles; Mice; Mice, Nude; MicroRNAs; Nanotubes; Photochemotherapy; Polymers; Porphobilinogen

Constructing bioactive materials remains a big challenge through the aggregates of molecules. Herein, a boron dipyrromethene (BODIPY) derivative containing three nitro groups (BDP-(NO

Topics: Boron; Nanoparticles; Phototherapy; Photothermal Therapy; Polymers; Porphobilinogen

The development of activatable photosensitizers (PSs) is of particular interest for achieving tumor photodynamic therapy (PDT) with minimal side effects. However, the in vivo applications of PSs are limited by complex physiological and biological delivery barriers. Herein, boron dipyrromethene (BDP)-based nanoparticles are developed through the self-assembly of a multifunctional "one-for-all" building block for enhanced tumor penetration and activatable PDT. The nanoparticles show excellent colloidal stability and long circulation lifetime in blood. Once they reach the tumor site, the first-stage size reduction occurs due to the hydrolysis of the Schiff base bond between polyethylene glycol and the cyclic Arg-Gly-Asp peptide in the acidic tumor microenvironment (pH~6.5), facilitating tumor penetration and specific recognition by cancer cells overexpressing integrin α

Topics: Boron; Cell Line, Tumor; Nanoparticles; Photochemotherapy; Photosensitizing Agents; Porphobilinogen

Topics: Boron; Boron Compounds; Luminescence; Porphobilinogen

The combination of photodynamic therapy (PDT) and photothermal therapy (PTT) has emerged as a promising strategy for complete tumor ablation therapy. Herein, a boron dipyrromethene (BODIPY)-conjugated hyaluronic acid polymer that can self-assemble to form the nanoparticles (BODIPY-HA NPs) was prepared for combined cancer PDT and PTT. The fluorescence emission and reactive oxygen species (ROS) generation of BODIPY-HA NPs were inhibited because of the π-π stacking behavior of BODIPY, resulting in photothermal effect under 808 nm light irradiation. Upon the internalization by cancer cells, the BODIPY-HA NPs could disassemble into BODIPY-HA molecules, with the recovery of the fluorescence and ROS generation for PDT. Importantly,

Topics: Boron; Cell Line, Tumor; Hyaluronic Acid; Nanoparticles; Photochemotherapy; Photothermal Therapy; Porphobilinogen

A new chiral BODIPY-based fluorescent compound, 5-bromo-4,4-difluoro-3(S)-1-phenylethyl)amino) BODIPY,

Topics: Anti-Bacterial Agents; Anti-Infective Agents; Antioxidants; Boron; Fluorescent Dyes; Molecular Docking Simulation; Porphobilinogen

A series of fluorescent boron-dipyrromethene (BODIPY, 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene) dyes have been designed to participate, as aglycons, in synthetic oligosaccharide protocols. As such, they served a dual purpose: first, by being incorporated at the beginning of the process (at the reducing-end of the growing saccharide moiety), they can function as fluorescent glycosyl tags, facilitating the detection and purification of the desired glycosidic intermediates, and secondly, the presence of these chromophores on the ensuing compounds grants access to fluorescently labeled saccharides. In this context, a sought-after feature of the fluorescent dyes has been their chemical robustness. Accordingly, some BODIPY derivatives described in this work can withstand the reaction conditions commonly employed in the chemical synthesis of saccharides; namely, glycosylation and protecting-group manipulations. Regarding their photophysical properties, the BODIPY-labeled saccharides obtained in this work display remarkable fluorescence efficiency in water, reaching quantum yield values up to 82 %, as well as notable lasing efficiencies and photostabilities.

Topics: Boron; Boron Compounds; Fluorescence; Fluorescent Dyes; Glycosylation; Light; Porphobilinogen

Herein we report on a straightforward access method for boron dipyrromethene dyes (BODIPYs)-coumarin hybrids linked through their respective 8- and 6- positions, with wide functionalization of the coumarin fragment, using salicylaldehyde as a versatile building block. The computationally-assisted photophysical study unveils broadband absorption upon proper functionalization of the coumarin, as well as the key role of the conformational freedom of the coumarin appended at the

Topics: Boron; Coumarins; Fluorescence; Fluorescent Dyes; Molecular Conformation; Porphobilinogen; Spectrometry, Fluorescence

Senescence-associated diseases have severely diminished the quality of life and health of patients. However, a sensitive assay of these diseases remains limited due to a lack of straightforward methods. Considering that senescence-associated β-galactosidase (SA-β-Gal) is overexpressed in senescent cells, the detection of SA-β-Gal in senescent cells and tissues might be a feasible strategy for the early diagnosis of SA diseases. In this study, a β-galactosidase-activatable nanoprobe

Topics: Animals; Atherosclerosis; beta-Galactosidase; Boron; Cellular Senescence; Fluorescent Dyes; Male; Mice; Mice, Inbred C57BL; Molecular Structure; Nanoparticles; Porphobilinogen; Rats; Rats, Sprague-Dawley

This study focuses on the behavior of a new fluorescent marker for labeling individual biomolecules and staining cell organelles developed on a

Topics: Boron; Boron Compounds; Candida albicans; Cell Line, Tumor; Crystallography, X-Ray; Diagnostic Imaging; Doxorubicin; Electrons; Fusarium; Humans; Porphobilinogen; Solvents; Spectrometry, Fluorescence; Subcellular Fractions; Ultraviolet Rays

We investigated the intramolecular charge transfer characteristics in the S

Topics: Animals; Boron; Cells, Cultured; Density Functional Theory; Mice; Molecular Structure; Photochemical Processes; Porphobilinogen; Spectrophotometry, Ultraviolet

A ferrocenyl boron dipyrromethene (BODIPY) has been developed and utilized as a dark quencher to construct a cathepsin B-responsive fluorescent probe and photosensitizer. The smart fluorescent probe and photosensitizer (Pc-FcQ) contains a zinc(II) phthalocyanine as the fluorescent and photosensitizing unit which is conjugated to the ferrocenyl BODIPY dark quencher via a cathepsin B-cleavable peptide substrate [Gly-Phe-Leu-Gly-Lys]. The photosensitizing properties of Pc-FcQ, including fluorescence and singlet oxygen generation, are significantly quenched through energy transfer to the BODIPY unit and subsequently by the photoinduced electron transfer from the nearby ferrocenyl moiety. Upon exposure of cathepsin B in human hepatocellular carcinoma HepG cells, the fluorescence emission of Pc-FcQ could be restored, indicating the cleavage of the peptide substrate and the separation of the phthalocyanine and ferrocenyl BODIPY unit. However, the intracellular fluorescence intensity of Pc-FcQ was largely diminished after the cells were pre-treated with cathepsin B inhibitor. Its intracellular fluorescence intensity was comparable to that of the control compound in which the peptide substrate was replaced by the non-cleavable one [Gly-Gly-Gly-Gly-Lys]. The singlet oxygen generation of Pc-FcQ was also examined in HepG2 cells as reflected by the cytotoxicity assay. The Pc-FcQ exhibited higher potency when compared with the non-cleavable analogue due to the cleavage of peptide substrate and the detachment of the BODIPY dark quencher from the phthalocyanine. The activation of the Pc-FcQ was also demonstrated in tumor-bearing nude mice. After intratumoral injection of Pc-FcQ, the fluorescence intensity at the tumor region increased gradually over 10 h as a result of the detachment of the dark quencher upon the action of cathepsin B. All the results suggest that this ferrocenyl BODIPY could serve as an efficient dark quencher and the resulting Pc-FcQ could act as the cathepsin B-responsive fluorescent probe and activatable photosensitizer.

Topics: Animals; Boron; Cathepsin B; Cell Survival; Dose-Response Relationship, Drug; Female; Ferrous Compounds; Fluorescent Dyes; Hep G2 Cells; HT29 Cells; Humans; Mice; Mice, Inbred BALB C; Mice, Nude; Molecular Structure; Optical Imaging; Photosensitizing Agents; Porphobilinogen; Structure-Activity Relationship; Tumor Cells, Cultured

Two advanced boron dipyrromethene (BODIPY) based photosensitizers have been synthesized and characterized. With a glibenclamide analogous moiety, these compounds can localize in the endoplasmic reticulum (ER) of HeLa human cervical carcinoma cells and HepG2 human hepatocarcinoma cells. The BODIPY π skeleton is conjugated with two styryl or carbazolylethenyl groups, which can substantially red-shift the Q-band absorption and fluorescence emission and impart two-photon absorption (TPA) property to the chromophores. The TPA cross section of the carbazole-containing analogue reaches a value of 453 GM at 1010 nm. These compounds also behave as singlet oxygen generators with high photostability. Upon irradiation at λ > 610 nm, these photosensitizers cause photocytotoxicity to these two cell lines with IC

Topics: Absorption, Radiation; Boron; Endoplasmic Reticulum; HeLa Cells; Hep G2 Cells; Humans; Photochemotherapy; Photons; Photosensitizing Agents; Porphobilinogen; Reactive Oxygen Species; Singlet Oxygen; Structure-Activity Relationship

In this study, we demonstrate a novel H₂O₂ activatable photosensitizer (compound

Topics: Biological Transport; Boron; Cell Line; Humans; Hydrogen Peroxide; Molecular Structure; Photochemistry; Photochemotherapy; Photosensitizing Agents; Porphobilinogen; Reactive Oxygen Species; Spectrometry, Fluorescence

Boron dipyrromethene (BODIPY) and its derivatives are known to be efficient photon-harvesting chromophores. However, their study as active materials in bulk heterojunction (BHJ) solar cells is still scarce. In this study, the development of new synthetic ways to design original BODIPY-based dumbbell-shape molecules, including a first 2,3,5,6-tetravinyl aromatic BODIPY molecule, is reported. High fill factors can be obtained in BHJ solar cells when blended with a fullerene derivative, leading to a new record BODIPY-based power conversion efficiency of 5.8 %.

Topics: Boron; Chemical Engineering; Electric Power Supplies; Fluorescent Dyes; Fullerenes; Indoles; Molecular Conformation; Porphobilinogen; Solar Energy

Boron-dipyrromethene (BODIPY) chromophores have a wide range of applications, spanning areas from biological imaging to solar energy conversion. Understanding the ultrafast dynamics of electronically excited BODIPY chromophores could lead to further advances in these areas. In this work, we characterize and compare the ultrafast dynamics of halogenated BODIPY chromophores through applying two-dimensional electronic spectroscopy (2DES). Through our studies, we demonstrate a new data analysis procedure for extracting the dynamic Stokes shift from 2DES spectra revealing an ultrafast solvent relaxation. In addition, we extract the frequency of the vibrational modes that are strongly coupled to the electronic excitation, and compare the results of structurally different BODIPY chromophores. We interpret our results with the aid of DFT calculations, finding that structural modifications lead to changes in the frequency, identity, and magnitude of Franck-Condon active vibrational modes. We attribute these changes to differences in the electron density of the electronic states of the structurally different BODIPY chromophores.

Topics: Boron; Boron Compounds; Electrons; Porphobilinogen; Quantum Theory; Solubility; Solvents; Spectrum Analysis; Vibration

Helically chiral N,N,O,O-boron chelated dipyrromethenes showed solution-phase circularly polarized luminescence (CPL) in the red region of the visible spectrum (λem (max) from 621 to 663 nm). The parent dipyrromethene is desymmetrised through O chelation of boron by the 3,5-ortho-phenolic substituents, inducing a helical chirality in the fluorophore. The combination of high luminescence dissymmetry factors (|glum | up to 4.7 ×10(-3) ) and fluorescence quantum yields (ΦF up to 0.73) gave exceptionally efficient circularly polarized red emission from these simple small organic fluorophores, enabling future application in CPL-based bioimaging.

Topics: Boron; Chelating Agents; Circular Dichroism; Fluorescent Dyes; Luminescence; Luminescent Measurements; Molecular Structure; Porphobilinogen; Solutions; Stereoisomerism

Two closely related phenyl selenyl based boron-dipyrromethene (BODIPY) turn-on fluorescent probes for the detection of hypochlorous acid (HOCl) were synthesized for studies in chemical biology; emission intensity is modulated by a photoinduced electron-transfer (PET) process. Probe 2 intrinsically shows a negligible background signal; however, after reaction with HOCl, chemical oxidation of selenium forecloses the PET process, which evokes a significant increase in fluorescence intensity. The fluorescence intensity of probes 1 and 2 with HOCl involves an ∼18 and ∼50-fold enhancement compared with the respective responses from other reactive oxygen/nitrogen species (ROS/RNS) and low detection limits (30.9 nm for 1 and 4.5 nm for 2). Both probes show a very fast response with HOCl; emission intensity reached a maximum within 1 s. These probes show high selectivity for HOCl, as confirmed by confocal microscopy imaging when testing with RAW264.7 and MCF-7 cells.

Topics: Boron; Cell Line; Fluorescence; Fluorescent Dyes; Humans; Hypochlorous Acid; Limit of Detection; MCF-7 Cells; Microscopy, Confocal; Oxidation-Reduction; Porphobilinogen; Selenium

We synthesized benzimidazole substituted boron-dipyrromethene 1 (BODIPY 1) by treating 3,5-diformyl BODIPY 2 with o-phenylenediamine under mild acid catalyzed conditions and characterized by using various spectroscopic techniques. The X-ray structure analysis revealed that the benzimidazole NH group is involved in intramolecular hydrogen bonding with fluoride atoms which resulted in a coplanar geometry between BODIPY and benzimidazole moiety. The presence of benzimidazole moiety at 3-position of BODIPY siginificantly altered the electronic properties, which is clearly evident in bathochromic shifts of absorption and fluorescence bands, improved quantum yields, increased lifetimes compared to BODIPY 2. The anion binding studies indicated that BODIPY 1 showed remarkable selectivity and specificity toward F(-) ion over other anions. Addition of F(-) ion to BODIPY 1 resulted in quenching of fluorescence accompanied by a visual detectable color change from fluorescent pink to nonfluorescent blue. The recognition mechanism is attributed to a fluoride-triggered disruption of the hydrogen bonding between BODIPY and benzimidazole moieties leading to (i) noncoplanar geometry between BODIPY and benzimidazole units and (ii) operation of photoinduced electron transfer (PET) from benzimidazole moiety to BODIPY unit causing quenching of fluorescence. Interestingly, when we titrated the nonfluorescent blue 1-F(-) solution with TFA resulted in a significant enhancement of fluorescence intensity (15-fold) because the PET quenching is prevented due to protonation of benzimidazole group. Furthermore, the reversibility and reusability of sensor 1 for the detection of F(-) ion was tested for six cycles indicating the sensor 1 is stable and can be used in reversible manner.

Topics: Benzimidazoles; Boron; Boron Compounds; Crystallography, X-Ray; Fluorescent Dyes; Fluorides; Models, Molecular; Phenylenediamines; Porphobilinogen; Spectrometry, Fluorescence

Caged compounds are useful tools for precise spatiotemporal modulation of cell functions, but in most cases uncaging requires ultraviolet (UV) light, which is cytotoxic and has limited tissue penetration. Therefore, caged compounds that can be activated by longer-wavelength light are required. Here we describe a novel photoelimination reaction of 4-aryloxy boron dipyrromethene (BODIPY) derivatives and show that BODIPY can function as a caging group for phenol groups. We developed a novel BODIPY-caged histamine compound, which is photoactivatable with blue-green visible light to stimulate cultured HeLa cells in a spatiotemporally well-controlled manner. This caging strategy is expected to be widely applicable to develop tools for probing various cellular functions.

Topics: Boron; Boron Compounds; Fluorescent Dyes; HeLa Cells; Humans; Light; Molecular Structure; Photons; Porphobilinogen

Photodynamic therapy (PDT) combines the use of organic dyes (photosensitizers, PSs) and visible light in order to elicit a photo-oxidative stress which causes bacterial death. GD11, a recently synthesized PS belonging to the boron-dipyrromethene (BODIPY) class, was demonstrated to be efficient against planktonic cultures of Pseudomonas aeruginosa, causing a 7 log unit reduction of viable cells when administered at 2.5 μM. The effectiveness of GD11 against P. aeruginosa biofilms grown in flow-cells and microtiter trays was also demonstrated. Confocal laser scanning microscopy of flow-cell-grown biofilms suggests that the treatment has a biocidal effect against bacterial biofilm cells.

Topics: Anti-Bacterial Agents; Biofilms; Boron; Microscopy, Confocal; Photosensitizing Agents; Porphobilinogen; Pseudomonas aeruginosa

A new boron-dipyrromethene-based lysosome tracker, Lyso-NIR, is facilely synthesized. Besides the intensive near-infrared (NIR) fluorescence and high photostability, Lyso-NIR shows the capability to stably localize in lysosomes, which is independent of the local pH. Lyso-NIR does not have the problematic alkalization effect suffered by the commonly used lysotrackers; thus, it shows ignorable cytotoxicity and slightly affects normal physiological functions of lysosomes. The above advantages of Lyso-NIR make it feasible to track lysosomes' dynamic changes in a relatively long time during the full cellular processes such as apoptosis, heavy metal stimulation, and endocytosis, as is demonstrated in this work. Moreover, Lyso-NIR's narrow NIR emission at 740 nm with a full width at half-maximum smaller than 50 nm makes it easy to avoid the crosstalk with the emissions from other common fluorescent probes, which strengthens Lyso-NIR's competitiveness as a standard lysosome tracker for multicolor bioimaging.

Topics: Boron; Cell Tracking; Diagnostic Imaging; Fluorescent Dyes; Humans; Lysosomes; Porphobilinogen; Spectroscopy, Near-Infrared

A silicon(IV) phthalocyanine with two axial p-phenylene-linked boron dipyrromethene and monostyryl boron dipyrromethene moieties has been prepared. The resulting pentad absorbs strongly in most of the UV-visible region and serves as an artificial photosynthetic antenna-reaction centre model.

Topics: Biomimetic Materials; Boron; Energy Transfer; Indoles; Organosilicon Compounds; Photosynthetic Reaction Center Complex Proteins; Porphobilinogen; Spectrophotometry

Boron dipyrromethenes (BDPs) are excellent building blocks for design of artificial light harvesting and charge separation systems. In the present work, we report the results of photophysical studies of a novel dyad, in which a BDP and a mono-styryl BDP (MSBDP) are covalently linked to each other at the meso-position via a p-phenylene unit. It was found that the photophysical properties of the dyad dissolved in polar as well as nonpolar solvents are strongly affected by two different types of interactions between the BDP and MSBDP parts, namely excitation energy transfer and photoinduced electron transfer. The first process delivers the excitation energy to the first excited singlet state of the MSBDP-part upon excitation of the BDP unit. The direct or indirect (via excitation energy transfer) population of the first excited singlet state of the MSBDP moiety is followed by hole transfer to generate the charge-separated state. In non-polar toluene, the probability of charge separation is low, whereas in polar acetonitrile the charge separation quantum yield is close to unity, resulting in strong quenching of the MSBDP fluorescence.

Topics: Boron; Porphobilinogen; Solvents; Spectrophotometry, Ultraviolet; Thermodynamics

A self-calibrating bipartite viscosity sensor 1 for cellular mitochondria, composed of coumarin and boron-dipyrromethene (BODIPY) with a rigid phenyl spacer and a mitochondria-targeting unit, was synthesized. The sensor showed a direct linear relationship between the fluorescence intensity ratio of BODIPY to coumarin or the fluorescence lifetime ratio and the media viscosity, which allowed us to determine the average mitochondrial viscosity in living HeLa cells as ca. 62 cP (cp). Upon treatment with an ionophore, monensin, or nystatin, the mitochondrial viscosity was observed to increase to ca. 110 cP.

Topics: Biosensing Techniques; Boron; Coumarins; Fluorescent Dyes; HeLa Cells; Humans; Mitochondria; Porphobilinogen; Spectrometry, Fluorescence; Viscosity

An efficient functional mimic of the photosynthetic antenna-reaction center has been designed and synthesized. The model contains a near-infrared-absorbing aza-boron-dipyrromethene (ADP) that is connected to a monostyryl boron-dipyrromethene (BDP) by a click reaction and to a fullerene (C60 ) using the Prato reaction. The intramolecular photoinduced energy and electron-transfer processes of this triad as well as the corresponding dyads BDP-ADP and ADP-C60 have been studied with steady-state and time-resolved absorption and fluorescence spectroscopic methods in benzonitrile. Upon excitation, the BDP moiety of the triad is significantly quenched due to energy transfer to the ADP core, which subsequently transfers an electron to the fullerene unit. Cyclic and differential pulse voltammetric studies have revealed the redox states of the components, which allow estimation of the energies of the charge-separated states. Such calculations show that electron transfer from the singlet excited ADP ((1) ADP*) to C60 yielding ADP(.+) -C60 (.-) is energetically favorable. By using femtosecond laser flash photolysis, concrete evidence has been obtained for the occurrence of energy transfer from (1) BDP* to ADP in the dyad BDP-ADP and electron transfer from (1) ADP* to C60 in the dyad ADP-C60 . Sequential energy and electron transfer have also been clearly observed in the triad BDP-ADP-C60 . By monitoring the rise of ADP emission, it has been found that the rate of energy transfer is fast (≈10(11)  s(-1) ). The dynamics of electron transfer through (1) ADP* has also been studied by monitoring the formation of C60 radical anion at 1000 nm. A fast charge-separation process from (1) ADP* to C60 has been detected, which gives the relatively long-lived BDP-ADP(.+) C60 (.-) with a lifetime of 1.47 ns. As shown by nanosecond transient absorption measurements, the charge-separated state decays slowly to populate mainly the triplet state of ADP before returning to the ground state. These findings show that the dyads BDP-ADP and ADP-C60 , and the triad BDP-ADP-C60 are interesting artificial analogues that can mimic the antenna and reaction center of the natural photosynthetic systems.

Topics: Aza Compounds; Biocompatible Materials; Boron; Electron Transport; Electrons; Energy Transfer; Fullerenes; Photosynthetic Reaction Center Complex Proteins; Porphobilinogen; Quantum Theory

Photocurrent generation in organic solar cells requires that excitons, which are formed upon light absorption, dissociate into free carriers at the interface of electron acceptor and donor materials. The high exciton binding energy, arising from the low permittivity of organic semiconductor films, generally causes low exciton separation efficiency and subsequently low power conversion efficiency. We demonstrate here, for the first time, that the exciton binding energy in B,O-chelated azadipyrromethene (BO-ADPM) donor films is reduced by increasing the film permittivity by blending the BO-ADPM donor with a high dielectric constant small molecule, camphoric anhydride (CA). Various spectroscopic techniques, including impedance spectroscopy, photon absorption and emission spectroscopies, as well as X-ray spectroscopies, are applied to characterize the thin film electronic and photophysical properties. Planar heterojunction solar cells are fabricated with a BO-ADPM:CA film as the electron donor and C60 as the acceptor. With an increase in the dielectric constant of the donor film from ∼4.5 to ∼11, the exciton binding energy is reduced and the internal quantum efficiency of the photovoltaic cells improves across the entire spectrum, with an ∼30% improvement in the BO-ADPM photoactive region.

Topics: Boron; Fullerenes; Oxygen; Porphobilinogen; Quantum Theory; Solar Energy

A boron dipyrromethene (BODIPY)-based fluorometric probe, HCS, has been successfully developed for the highly sensitive and selective detection of hypochlorous acid (HOCl). The probe is based on the specific HOCl-promoted oxidation of methyl phenyl sulfide. The reaction is accompanied by a 160-fold increase in the fluorescent quantum yield (from 0.003 to 0.480). The fluorescent turn-on mechanism is accomplished by suppression of photoinduced electron transfer (PET) from the methyl phenyl sulfide group to BODIPY. The fluorescence intensity of the reaction between HOCl and HCS shows a good linearity in the HOCl concentration range 1-10 μM. The detection limit is 23.7 nM (S/N=3). In addition, confocal fluorescence microscopy imaging using RAW264.7 macrophages demonstrates that the HCS probe could be an efficient fluorescent detector for HOCl in living cells.

Topics: Animals; Boron; Cell Line; Electron Transport; Fluorescent Dyes; Hypochlorous Acid; Mice; Microscopy, Confocal; Oxidation-Reduction; Porphobilinogen; Quantum Theory; Reactive Nitrogen Species; Reactive Oxygen Species; Sulfides

Bodipy derivatives containing excited state intramolecular proton transfer (ESIPT) chromophores 2-(2-hydroxyphenyl) benzothiazole and benzoxazole (HBT and HBO) subunits were prepared (7-10). The compounds show red-shifted UV-vis absorption (530-580 nm; ε up to 50000 M(-1) cm(-1)) and emission compared to both HBT/HBO and Bodipy. The new chromophores show small Stokes shift (45 nm) and high fluorescence quantum yields (Φ(F) up to 36%), which are in stark contrast to HBT and HBO (Stokes shift up to 180 nm and Φ(F) as low as 0.6%). On the basis of steady state and time-resolved absorption spectroscopy, as well as DFT/TDDFT calculations, we propose that 7-9 do not undergo ESIPT upon photoexcitation. Interestingly, nanosecond time-resolved transient absorption spectroscopy demonstrated that Bodipy-localized triplet excited states were populated for 7-10 upon photoexcitation; the lifetimes of the triplet excited states (τ(T)) are up to 195 μs. DFT calculations confirm the transient absorptions are due to the triplet state. Different from the previous report, we demonstrated that population of the triplet excited states is not the result of ESIPT. The compounds were used as organic triplet photosensitizers for photooxidation of 1,5-dihydroxylnaphthalene. One of the compounds is more efficient than the conventional [Ir(ppy)(2)(phen)][PF(6)] triplet photosensitizer. Our result will be useful for design of new Bodipy derivatives, ESIPT compounds, and organic triplet photosensitizers, as well as for applications of these compounds in photovoltaics, photocatalysis and luminescent materials, etc.

Topics: Benzothiazoles; Benzoxazoles; Boron; Molecular Structure; Oxidation-Reduction; Phenols; Photochemical Processes; Photosensitizing Agents; Porphobilinogen; Quantum Theory

We present polarization-resolved fluorescence measurements of fluorescent molecular rotors 9-(2-carboxy-2-cyanovinyl)julolidine (CCVJ), 9-(2,2-dicyanovinyl)julolidine (DCVJ), and a meso-substituted boron dipyrromethene (BODIPY-C(12)). The photophysical properties of these molecules are highly dependent on the viscosity of the surrounding solvent. The relationship between their quantum yields and the viscosity of the surrounding medium is given by an equation first described and presented by Förster and Hoffmann and can be used to determine the microviscosity of the environment around a fluorophore. Herein we evaluate the applicability of molecular rotors as probes of apparent viscosity on a microscopic scale based on their viscosity dependent fluorescence depolarization. We develop a theoretical framework, combining the Förster-Hoffmann equation with the Perrin equation and compare the dynamic ranges and usable working regimes for these dyes in terms of utilising fluorescence anisotropy as a measure of viscosity. We present polarization-resolved fluorescence spectra and steady-state fluorescence anisotropy imaging data for measurements of intracellular viscosity. We find that the dynamic range for fluorescence anisotropy for CCVJ and DCVJ is significantly lower than that of BODIPY-C(12) in the viscosity range 0.6<η<600 cP. Moreover, using steady-state anisotropy measurements to probe microviscosity in the low (<3 cP) viscosity regime, the molecular rotors can offer a better dynamic range in anisotropy compared with a rigid dye as a probe of microviscosity, and a higher total working dynamic range in terms of viscosity.

Topics: Boron; Fluorescence Polarization; Fluorescent Dyes; Models, Theoretical; Nitriles; Porphobilinogen; Quantum Theory; Quinolizines; Solvents; Spectrometry, Fluorescence; Viscosity

A series of four novel 8-hydroxyquinoline-substituted boron-dipyrromethene derivatives, namely 4,4-difluoro-8-(5-(8-hydroxyquinoline))-3,5-dimethyl-4-bora-3a,4a-diaza-s-indacene (1), 4,4-difluoro-8-(5-(8-hydroxyquinoline))-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene (2), 4,4-difluoro-8-(5-azastyryl-(8-hydroxyquinoline))-3,5-dimethyl-4-bora-3a,4a-diaza-s-indacene (3), and 4,4-difluoro-8-(5-azastyryl-(8-hydroxyquinoline))-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene (4), have been synthesized and characterized by a series of spectroscopic methods. The molecular structures of 1 and 2 have been determined by single-crystal X-ray diffraction analyses. The two methyl substituents attached at C-1 and C-7 positions of boron-dipyrromethene (Bodipy) in compound 2 was revealed to prevent the free rotation of the 8-hydroxyquinoline (8-HQ) moiety, resulting in an almost vertical 8-HQ-Bodipy configuration of this compound. This is obviously different from those for 1 with the dihedral angle between 8-hydroxyquinoline and Bodipy moieties of 65.44 and 66.79° due to the lack of methyl substituents in the latter compound. The intense fluorescence from the Bodipy subunit of these compounds was revealed to gradually get diminished along with either decreasing or increasing the pH value under acidic and basic conditions, respectively, in particular for 1, 2, and 4 because of the photoinduced intramolecular electron transfer from excited Bodipy moiety to 8-HQ unit and just an opposite process. This renders these compounds the first OFF-ON-OFF type of pH-dependent fluorescent sensors. Nevertheless, both the intrinsic fluorescence of these compounds and their fluorescent quenching properties along with the change in the pH value have been found to depend on the steric configuration as well as the linking group between 8-hydroxyquinoline and Bodipy moieties, revealing the effect of molecular structure on their fluorescence properties.

Topics: Boron; Crystallography, X-Ray; Drug Design; Electron Transport; Fluorescent Dyes; Hydrogen-Ion Concentration; Models, Molecular; Molecular Conformation; Oxyquinoline; Photochemical Processes; Porphobilinogen

A series of boron dipyrromethene (BODIPY) dyes containing two aldehyde functional groups at the 3 and 5 positions have been synthesized in low-to-decent yields in two steps. In the first step, the meso-aryl dipyrromethanes were treated with POCl(3) in N,N-dimethylformamide to afford 1,9-diformylated dipyrromethanes. In the second step, the diformylated dipyrromethanes were first in situ oxidized with 2,3-dichloro-5,6-dicyano-1,4-benzoquinone and then reacted with BF(3)·OEt(2) to afford 3,5-diformylboron dipyrromethenes. The X-ray structural analysis indicated that the aldehyde groups are involved in intramolecular hydrogen bonding with fluoride atoms, which may be responsible for the stability of the diformylated BODIPY compounds. The presence of two formyl groups significantly alters the electronic properties, which is clearly evident in downfield shifts in the (1)H and (19)F NMR spectra, bathochromic shifts in the absorption and fluorescence spectra, better quantum yields, and increased lifetimes compared to 3,5-unsubstituted BODIPYs. Furthermore, 3,5-diformylboron dipyrromethenes are highly electron-deficient and undergo facile reductions compared to unsubstituted BODIPYs. These compounds exhibit pH-dependent on/off fluorescence and thus act as fluorescent pH sensors.

Topics: Benzoquinones; Biosensing Techniques; Boron; Boron Compounds; Crystallography, X-Ray; Dimethylformamide; Fluorescence; Fluorescent Dyes; Formamides; Hydrogen Bonding; Hydrogen-Ion Concentration; Magnetic Resonance Spectroscopy; Molecular Structure; Porphobilinogen; Pyrroles; Spectrometry, Fluorescence; Thermodynamics

A rapid synthetic route for polyarylated boron-dipyrromethenes using hexabromo boron-dipyrromethene as the key synthon is described. The X-ray structure revealed that the polyarylated BODIPY adopts a propeller-like conformation. These compounds exhibit red-shifted absorption and fluorescence bands with decent quantum yields and reversible oxidation and reduction waves when compared to unsubstituted boron-dipyrromethenes.

Topics: Boron; Boron Compounds; Crystallography, X-Ray; Fluorescence; Fluorescent Dyes; Magnetic Resonance Spectroscopy; Molecular Conformation; Molecular Imaging; Molecular Probes; Oxidation-Reduction; Porphobilinogen; Spectrometry, Fluorescence

BODIPY-Le, a colorimetric and ratiometric fluorescent probe based on boron-dipyrromethene for selective detection sulfite ion, was investigated. Boron-dipyrromethene levulinyl ester (BODIPY-Le) is composed of an indole-based BODIPY dye and the levulinyl protective group, which could be easily and selectively deprotected by sulfites. As a result, the absorption and emission spectra show a dramatic red shift, and the development of a colorimetric and ratiometric fluorescent sulfite probe could be achieved. Besides, BODIPY-Le also exhibited prominent turn-on or turn-off type fluorogenic signaling toward sulfite ions once excited at 510 and 620 nm, respectively.

Topics: Boron; Boron Compounds; Colorimetry; Fluorescent Dyes; Porphobilinogen; Spectrometry, Fluorescence; Sulfites

A series of compounds containing two boron dipyrromethene (Bodipy) units has been synthesized and fully characterized in which the spacer between the two Bodipy groups is varied from dibenzothiophene (BD1), to dibenzofuran (BD2), to 9,9-dimethylxanthene (BD3), and finally to diphenyl ether (BD4 and BD5). For BD1-BD4 the Bodipy units adopt, to varying degrees, cofacial conformations that allow for systematic variations of both the mutual orientation and the mean separation of the two Bodipy residues. In the remaining dimer, BD5, the Bodipy units are well-separated and cannot come into close proximity. Single-crystal X-ray structures have been determined for BD1-BD3 and reveal that the "bite angle" between the two Bodipy residues decreases progressively along the series with individual values of 41.33(5) degrees, 36.95(6) degrees, and 8.57(3) degrees. Detailed (1)H and (19)F NMR studies for BD3 and BD4 show the methylene protons to be diastereotopic due to restricted rotation of the two Bodipy groups. For BD4 conformational rocking is invoked to explain the variable-temperature NMR spectra, whereby the methyl and methylene groups become inequivalent. Cyclic voltammetry indicates reversible oxidation and reduction of the Bodipy groups. However, the close proximity of the Bodipy groups in BD3 and BD4 results in two well-resolved waves in the anodic region, and slight splitting of the cathodic wave. Peak splitting is attributed to charge delocalization. Spectroelectrochemical measurements at a fixed oxidative potential reveal an optical intervalence charge-transfer (IVCT) absorption band. This IVCT band is attributed to electron exchange between the cofacially arranged neutral and mono-oxidized Bodipy units. Various levels of exciton coupling are observed for BD1-BD4, but not BD5 since here the Bodipy groups remain isolated.

Topics: Boron; Crystallography, X-Ray; Dimerization; Fluorescent Dyes; Magnetic Resonance Spectroscopy; Molecular Structure; Porphobilinogen

To understand the effects of substitution patterns on photosensitizing the ability of boron dipyrromethene (BODIPY), two structural variations that either investigate the effectiveness of various iodinated derivatives to maximize the "heavy atom effect" or focus on the effect of extended conjugation at the 4-pyrrolic position to red-shift their activation wavelengths were investigated. Compounds with conjugation at the 4-pyrrolic position were less photocytotoxic than the parent unconjugated compound, while those with an iodinated BODIPY core presented better photocytotoxicity than compounds with iodoaryl groups at the meso-positions. The potency of the derivatives generally correlated well with their singlet oxygen generation level. Further studies of compound 5 on HSC-2 cells showed almost exclusive localization to mitochondria, induction of G(2)/M-phase cell cycle block, and onset of apoptosis. Compound 5 also extensively occluded the vasculature of the chick chorioallantoic membrane. Iodinated BODIPY structures such as compound 5 may have potential as new photodynamic therapy agents for cancer.

Topics: Animals; Apoptosis; Biological Transport; Blood Vessels; Boron; Boron Compounds; Cell Cycle; Cell Line, Tumor; Chickens; Chorioallantoic Membrane; Humans; Intracellular Space; Photochemotherapy; Photosensitizing Agents; Porphobilinogen; Singlet Oxygen; Structure-Activity Relationship

This paper describes the preparation and characterization of an optical pH-sensing device using a H(+)-responsive fluoroionophore based on boron-dipyrromethene, immobilized to a mesoporous silica thin film. The fluoroionophore substituted with a silane coupling agent (KBH-01-Si) was successfully synthesized, and a mesoporous silica thin film was fabricated by the evaporation-induced-self-assembly (EISA) process. A pH optode was fabricated by attaching KBH-01-Si to the mesoporous silica thin film by covalent bonding via a sol-gel grafting method. The resulting pH optode shows single-excitation, dual-emission ratiometric response in aqueous buffer solutions of varying pH values. The sensor response was found to be reversible in the pH range from below 0.8 to 4.2, and showed good repeatability. The response times for a 95% signal change (t(95%)) were calculated to be 27 +/- 2 s (n = 5) for a sample change from pH 4.0 to 1.0, and 23 +/- 2 s (n = 5) for reverse change from pH 1.0 to 4.0. These results indicate that the novel pH optode allows for accurate and rapid measurements of pH values.

Topics: Boron; Fluorescent Dyes; Hydrogen-Ion Concentration; Membranes, Artificial; Porosity; Porphobilinogen; Silicon Dioxide; Surface Properties

Recently, significant advances have been made independently in electrogenerated chemiluminescence (ECL) analysis and supramolecular anion sensing. Herein, we demonstrate a new proof of concept for ECL-based pyrophosphate (PPi) sensing, where the emission intensity is changed by electrochemical turn-on. The ECL PPi sensor (1-2Zn) consists of two orthogonally bonded moieties: boron dipyrromethene (ECL reporter) and a phenoxo-bridged bis(Zn(2+)-dipicolylamine) complex (PPi receptor). The presence of PPi is confirmed from the change in the intensity of green ECL generated from the former when PPi is selectively recognized by the latter. During PPi recognition, changes are caused in the electronic states of the receptor, and this stimulates the attenuation of ECL intensity. The electrochemical "on-off" triggering of light emission upon anion binding forms the basis of a new anion sensing strategy. We expect that green-colored ECL sensing would offer an advantage to current ECL analysis.

Topics: Amines; Anions; Boron; Coordination Complexes; Diphosphates; Electrochemical Techniques; Luminescent Measurements; Picolinic Acids; Porphobilinogen; Thermodynamics; Zinc

Taking the high road: Highly efficient electronic energy transfer takes place from a set of appended aryl polycyclic hydrocarbons to an expanded boron dipyrromethene (Bodipy)-based dye (see figure) despite negligible spectral overlap with the lowest-energy excited state localised on the acceptor.A multi-component array has been constructed around an expanded boron dipyrromethene (Bodipy) dye that absorbs and emits in the far-red region. One of the appendages is a perylene-based moiety that is connected to the boron atom of the terminal Bodipy by a 1,4-diethynylphenylene connector. Despite the fact that there is almost negligible spectral overlap between fluorescence from the perylene unit and absorption by the Bodipy residue, electronic energy transfer is rapid and essentially quantitative. It is concluded that at least half of the photons absorbed by perylene are transferred to the upper-lying singlet excited state (S(2)) associated with the Bodipy-based acceptor. The second appendage is a pyrene unit that is covalently linked to fluorene, through an ethynylene spacer, and to the boron atom of the Bodipy terminus, through a 1,4-diethynylphenylene connector. Pyrene absorbs and emits at higher energy than perylene and there is strong spectral overlap with the Bodipy-based S(2) state, and none with the corresponding S(1) state. Electronic energy transfer is now very fast and exclusively to the S(2) state of the acceptor. It is difficult to compute reasonable estimates for the rates of Coulombic energy transfer, because of uncertainties in the orientation factor, but the principle mechanism is believed to arise from electron exchange. Comparison with an earlier array built around a conventional Bodipy dye indicates that there are comparable electronic coupling matrix elements for the two systems. It is notable that pyrene is more strongly coupled to the Bodipy unit than perylene in both arrays. These new arrays function as highly effective solar concentrators.

Topics: Boron; Electrons; Energy Transfer; Fluorescent Dyes; Hydrocarbons, Fluorinated; Perylene; Porphobilinogen; Spectrometry, Fluorescence

Complementary synthetic routes to a new class of near-IR fluorophores are described. These allow facile access (four synthetic steps) to the core fluorophore and substituted derivatives with emissions between 740 and 780 nm in good quantum yields.

Topics: Aza Compounds; Boron; Chelating Agents; Crystallography, X-Ray; Models, Molecular; Molecular Probes; Molecular Structure; Oxygen; Photochemistry; Porphobilinogen; Solvents; Spectrometry, Fluorescence; Spectroscopy, Near-Infrared

A light-harvesting system containing three kinds of BODIPY fluorophores was synthesized. It exhibited very strong absorption in the region from 300 to 700 nm, and the energy transfer within it was highly efficient.

Topics: Absorption; Boron; Energy Transfer; Light; Models, Molecular; Molecular Structure; Porphobilinogen; Solar Energy

Chromophore-assisted light inactivation is a promising technique to inactivate selected proteins with high spatial and temporal resolution in living cells, but its use has been limited because of the lack of a methodology to prevent nonspecific photodamage in the cell owing to reactive oxygen species generated by the photosensitizer. Here we present a design strategy for photosensitizers with an environment-sensitive off/on switch for singlet oxygen ((1)O(2)) generation, which is switched on by binding to the target, to improve the specificity of protein photoinactivation. (1)O(2) generation in the unbound state is quenched by photoinduced electron transfer, whereas (1)O(2) generation can occur in the hydrophobic environment provided by the target protein, after specific binding. Inositol 1,4,5-trisphosphate receptor, which has been suggested to have a hydrophobic pocket around the ligand binding site, was specifically inactivated by an environment-sensitive photosensitizer-conjugated inositol 1,4,5-trisphosphate receptor ligand without (1)O(2) generation in the cytosol of the target cells, despite light illumination, demonstrating the potential of environment-sensitive photosensitizers to allow high-resolution control of generation of reactive oxygen species in the cell.

Topics: Animals; Boron; Boron Compounds; Cell Line; Chickens; Cytosol; Fluorescent Dyes; Inositol 1,4,5-Trisphosphate Receptors; Light; Models, Biological; Oxygen; Photochemistry; Photosensitizing Agents; Porphobilinogen; Protein Binding; Singlet Oxygen

A new class of boron-dipyrromethene (BDP or BODIPY) dyes was obtained by phenanthrene fusion to the beta-pyrrole positions, absorbing in the wavelength range of important laser sources. Despite a 'propeller-like' distorted structure in the crystalline state, the chromophore absorbs (log epsilon > or = 5) and fluoresces (Phif > or = 0.8) strongly and can be easily turned into a fluorescence light-up probe. Incorporation into latex beads produces bright and photostable single-dye and Förster Resonance Energy Transfer (FRET) particles for microscopy applications.

Topics: Boron; Fluorescence Resonance Energy Transfer; Fluorescent Dyes; Magnetic Resonance Spectroscopy; Microscopy, Confocal; Models, Molecular; Phenanthrenes; Porphobilinogen

Boron dipyrromethene dyes (Bodipy) bearing a meso-phenyl substituent carrying a variety of functional groups can be prepared under mild conditions. A single-crystal X-ray structure determination for the 3,5-dinitrophenyl compound shows the phenyl ring to be almost orthogonal (dihedral angle 84 degrees) to the plane of the Bodipy core, with one nitro group almost coplanar with the ring and the other tilted by approximately 21 degrees. Nitro substituents at the 3-, 4-, and 5- positions of the phenyl group are readily reduced to the corresponding amino groups and then converted to isocyanato, isothiocyanato, urea, thiourea, and some polyimine derivatives, the last providing additional functionality (phenazine and pyridylindole units) suitable for chelation of metal ions. All compounds are redox active, the electron-transfer processes being assigned on the basis of comparisons with model compounds. Their fluorescence properties are sensitive to the phenyl group substituents. The Bodipy unit excited state appears to be a strong reductant (Eo approximately -1.4 V) and a modest oxidant (Eo approximately +1.0 V). Quenching processes in the nitro and phenazine derivatives appear to involve intramolecular photoinduced electron transfer.

Topics: Boron; Crystallography, X-Ray; Electrochemistry; Fluorescent Dyes; Isocyanates; Models, Molecular; Molecular Structure; Porphobilinogen; Solutions; Sulfhydryl Compounds; Temperature; Urea

Boron dipyrromethene dyes bearing nitro, amino, isocyanate and isothiocyanate functions were readily prepared under mild conditions. Various combinations allow to produce urea, diurea, thiourea, dithiourea in the 3, 4 and 5-substitution positions of the appended phenyl group. Condensation of the 3,4-substituted diamino derivative with 1,10-phenanthroline-5,6-dione and 6-formyl-2-methylpyridine allow to prepare dipyridophenazine and indole derivatives. The 3,5-dinitro-substituted indacene dye was characterized by an X-ray molecular structure showing a pronounced tilt angle of the dinitrophenyl group relative to the indacene core (approximately 84 degrees) whereas one nitro groups is basically coplanar with the phenyl ring and the second titled by approximately 21 degrees. The optical properties of these dyes reveals on/off switching of the fluorescence from the nitro to the amino compounds and further to the urea likely understood in the framework of an photoinduced electron transfer process.

Topics: Boron; Boron Compounds; Chemistry; Electrons; Fluorescence; Fluorescent Dyes; Light; Models, Chemical; Molecular Structure; Nitrobenzenes; Photochemistry; Porphobilinogen; X-Rays

Boron dipyrromethene (BODIPY), which is commonly used as an energy absorbing and transferring antenna molecule, has been modified to contain an electron donor moiety, 8-(2,4,5-trimethoxyphenyl)-4,4-difluoro-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene (MEOPHBDP). The photoinduced electron transfer from a 2,4,5-trimethoxyphenyl moiety to a BODIPY moiety of MEOPHBDP in acetonitrile was observed by femtosecond laser flash photolysis measurements. The lifetime of the charge-separated state of MEOPHBDP was 59 ps at 298 K. The dye-sensitized solar cells (DSSC) were prepared using MEOPHBDP with carboxylic acid (MEOPHBDP-COOH) and a reference BODIPY dye having no electron donor moiety. The photovoltaic measurements were performed using a standard two-electrode system consisting of a working electrode and a Pt sputtered electrode in methoxyacetonitrile containing 0.5 M iodide and 0.05 M I(2). The photoelectrochemical properties of DSSC with MEOPHBDP are compared with those with a reference BODIPY dye.

Topics: Boron; Coloring Agents; Electrochemistry; Electrons; Ions; Molecular Structure; Oxidation-Reduction; Photochemistry; Porphobilinogen; Spectrophotometry