developing-photosensitizer-cobaloxime-hybrids-for-solar-driven-h2

Developing Photosensitizer-Cobaloxime Hybrids for Solar-Driven H<sub>2</sub> Production in Aqueous Aerobic Conditions

Developing photocatalytic H2 production devices is the one of the key steps for constructing a global H2-based renewable energy infrastructure. A number ...

Indian Institute of Technology Gandhinagar

A series of ortho-, meta- and para-substituted trans-nitro aryl (phenyl and pyridyl) butadienes have been synthesized and characterized. The effect of substitution and positional selectivity on their fluorescence and photoisomerization were systematically investigated. Among all dienes, meta- and para-nitro phenyl-substituted derivatives exhibit remarkable solvatochromic emission shifts due to intramolecular charge transfer. On the other hand, ortho derivatives undergo regioselective isomerization upon photoexcitation in contrast to inefficient isomerization of para and meta nitro-substituted dienes. Single crystal X-ray analysis revealed existence of intramolecular hydrogen bonding between the nitro group and the hydrogen of the proximal double bond. This restricts the rotation of the proximal double bond thereby allowing regioselective isomerization. The observations were also supported by NMR spectroscopic studies.

Photoisomerization of Trans Ortho-, Meta-, Para-Nitro Diarylbutadienes: A Case of Regioselectivity.

Neutral and cationic diarylbutadienes with pyridine and pyridinium groups as electron acceptors with dimethylamine and diphenylamine as electron donors were synthesized. The absorption and emission properties of these dienes were investigated in homogeneous organic solvents and in sodium cholate media. In strongly polar solvents, both neutral and cationic fluorophores exhibit a bathochromic shift of emission characteristics of intramolecular charge transfer (ICT) excited states. The presence of a strongly electron withdrawing pyridinium group induces large absorption (∼480 nm) and emission wavelength shifts (near ∼680 nm) in polar solvents. This solvatochromic behavior is utilized as a tool to examine the fluorophore-sodium cholate interaction. Significant hypsochromic emission shifts (up to ∼66 nm) and concomitant intensity enhancement (up to 32-fold) are seen for these fluorophores in the presence of increasing concentrations of sodium cholate. Fluorescence lifetime measurements reveal biexponential decay patterns indicating the binding of molecules in distinct cholate environments. 

Neutral and cationic pyridylbutadienes: solvatochromism and fluorescence response with sodium cholate.

Styrylisoxazoles bearing a nitro group linked to bulky aromatic rings have been synthesized and examined for their absorption and emission studies in organic solvents and water. The molecules showed emission in the visible region with significant solvatochromic emission shifts influenced by the extended conjugation of aromatic rings and intramolecular charge transfer. These absorption and emission changes were used for the efficient and sensitive detection of trace concentrations of hydrogen sulfide (HS) through the reduction of the nitro group to the amine group in the presence of aqueous sodium sulfide. The experimental results indicated that the probes exhibit an excellent emission response with large shifts in the emission and sensitivity with a micromolar detection limit.

Styrylisoxazole-based fluorescent probes for the detection of hydrogen sulfide.

A series of α-cyanostyrenes bearing anthracene and electron withdrawing trifluoromethyl units were designed and synthesized. The α-cyanostyrene skeleton favors aggregation induced enhanced emission behavior due to the restriction of intramolecular rotations. Remarkably, the anthryl cyanostyrenes bearing simple trifluoromethyl (CF3) substituents form stable organogels with enhanced fluorescence emission compared to their solution state. In water, the CF3 substituted anthrylstyrenes self-assemble into entangled fibrous nano/microstructures through intermolecular H-bonding, π-π stacking and cyano substituent interactions. The morphological features of the aggregates and the gels were substantiated using scanning electron microscopy, TEM, and powder XRD measurements. The stability of the gels was assessed using rheology investigations.

Organogels composed of trifluoromethyl anthryl cyanostyrenes: enhanced emission and self-assembly.

A simple fluorophore bearing a diethylaminocoumarin donor and a pyridinium acceptor was synthesized and utilized for the ultra-sensitive detection of heparin. The synthesized dicationic push-pull coumarin derivative emits strongly in the red-region (665 nm) and detects nanomolar concentrations (14.8 nM to 148 nM) of heparin in HEPES buffer and FBS serum solutions. The dication exhibits excellent fluorescence selectivity and sensitivity towards heparin over its analogues such as chondroitin 4-sulfate (CS), hyaluronic acid (HA) and dextran. This fluorescence assay is a convenient, sensitive method for monitoring heparin levels in biological samples. These findings were confirmed using coarse-grained Monte Carlo simulations, which provide us with a rationale for the selective binding of heparin.

A "turn-off" red-emitting fluorophore for nanomolar detection of heparin.

Guanine (G) quadruplexes (G4) are nucleic acid secondary structures formed by G-rich sequences, commonly found in human telomeric and oncogene-promoter regions, have emerged as targets for regulation of multiple biological processes. Considering their importance, targeting the G-quadruplex structure with small molecular binders is extremely pertinent. In this work, red emitting water soluble fluorophores bearing push-pull substituents were synthesized and examined for their interaction with human telomeric G4 and duplex (ds) -DNAs. The presence of a strong electron donating (dimethylamino) and electron withdrawing (cationic pyridinium) groups linked through a conjugated double bond helps in water solubility and enabling the emission in the near IR region (>700-nm). Binding of this cationic dye to the G4-DNA yields multiple-fold emission enhancement (~70 fold with G4-DNA vs. ~7 fold with ds-DNA) along with hypsochromic wavelength shifts (35 nm with G4-DNA and 8 nm with ds-DNA). The remarkable emission changes, ~2-4 fold enhanced binding efficiency noted with the antiparallel conformation of G4-DNA indicates preferential selectivity over ds-DNA. The molecular docking and dynamics studies of the ligands with duplex and G4-DNA were performed, and they provide insights into the mode of binding of these dyes with G4-DNA and supplement the experimental observations.

Cationic red emitting fluorophore: A light up NIR fluorescent probe for G4-DNA.

White-light-emitting diodes are energy efficiency replacement of conventional lighting sources. Herein, we report the luminescent behavior of three simple cyanostilbenes with triphenylamine-donating groups bearing different electron-withdrawing groups (phenyl, pyridyl, and -nitrophenyl) in a common donor (D)-π-acceptor (A) α-cyanostilbene construct along with their thermal and electrochemical properties. The density functional theory (DFT) studies reveal that aggregation-induced emission characteristic feature of the D-π-A dyes is inversely proportional to the intramolecular charge transfer (ICT) effect, that is, phenyl-and pyridyl-substituted compounds show characteristic aggregation-induced emission in water, whereas the ICT effect is dominant for the nitro derivative. The extent of ICT and the solvatochromic emission shifts, from blue to red, depend on the strength of the electron-withdrawing group. White luminescence and tunable emission colors are obtained by careful admixtures of these cyanostilbenes bearing triphenylamines. The results rationalized through DFT and time-dependent DFT calculations follow a consistent trend with the energy levels measured from the electrochemical and optical studies. Thermogravimetric analysis and differential scanning calorimetry studies showed excellent thermal stability of the compounds. The scanning electron microscopy and dynamic light scattering measurements were performed to reveal the formation of aggregates. This strategy involving synthetically simple and structurally similar molecules with different emission properties has potential applications in the fabrication of multicolor and white-light-emitting materials.

Article	Year
Photoisomerization of Trans Ortho-, Meta-, Para-Nitro Diarylbutadienes: A Case of Regioselectivity. Photochemistry and photobiology\| PubMed ID: 26249312	2015
Neutral and cationic pyridylbutadienes: solvatochromism and fluorescence response with sodium cholate. Photochemical & photobiological sciences : Official journal of the European Photochemistry Association and the European Society for Photobiology\| PubMed ID: 26366991	2015
Styrylisoxazole-based fluorescent probes for the detection of hydrogen sulfide. Photochemical & photobiological sciences : Official journal of the European Photochemistry Association and the European Society for Photobiology\| PubMed ID: 29167856	2018
Organogels composed of trifluoromethyl anthryl cyanostyrenes: enhanced emission and self-assembly. Photochemical & photobiological sciences : Official journal of the European Photochemistry Association and the European Society for Photobiology\| PubMed ID: 29411824	2018
A "turn-off" red-emitting fluorophore for nanomolar detection of heparin. Physical chemistry chemical physics : PCCP\| PubMed ID: 29423470	2018
Cationic red emitting fluorophore: A light up NIR fluorescent probe for G4-DNA. Journal of photochemistry and photobiology. B, Biology\| PubMed ID: 30529810	2019
Emission and Color Tuning of Cyanostilbenes and White Light Emission. ACS omega\| PubMed ID: 31458345	2018

Sriram Kanvah

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