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Shedding light on biocatalysis: photoelectrochemical platforms for solar-driven biotransformation
摘要： Redox biocatalysis has come to the forefront because of its excellent catalytic efficiency, stereoselectivity, and environmental benignity. The green and sustainable biotransformation can be driven by photoelectrochemical (PEC) platforms where redox biocatalysis is coupled with photoelectrocatalysis. The main challenge is how to transfer photoexcited electrons to (or from) the enzyme redox centers for effective biotransformation using solar energy. This review commences with a conceptual discussion of biocatalytic PEC platforms and highlights recent advances in PEC-based biotransformation through cofactor regeneration or direct transfer of charge carriers to (or from) oxidoreductases on enzyme-conjugated electrodes. Finally, we address future perspectives and potential next steps in the vibrant field of biocatalytic photosynthesis.
关键词： photoelectrochemical,cofactor regeneration,biotransformation,redox enzymes,solar-driven,biocatalysis,direct electron transfer
更新于2025-09-23 15:22:29
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Photoinduced electron transfer in non-covalent free-base octaethylporphyrin and 2-nitrofluorene donor-acceptor system: A combined experimental and quantum chemical study
摘要： Photosynthetic reaction center functions through non-covalent incorporation into a well-defined transmembrane proteins. In the context of exploring photoinduced electron transfer (PET) in non-covalent donor-acceptor systems, we have investigated electron transfer from free-base octaethylporphyrin (OEP) donor to 2-nitrofluorene (2NF) acceptor in acetonitrile (ACN), a polar solvent. Steady-state and time-resolved emission spectroscopic studies in conjunction with density functional theory (DFT) calculations were employed to explore the electron transfer process. Quenching of the fluorescence emission intensity as well as fluorescence lifetime of the OEP upon excitation at the Q band of OEP at 300 K, is attributed to the PET from OEP to 2NF. Our DFT [wB97XD functional and 6-31G (d,p) basis set] calculations also support the interaction between donor and acceptor and also reveals the co-facial π-π interaction energy of ?24.6 kcal/mol with intermolecular distance b4 ?. Our results are expected to shed light on PET in non-covalent donor acceptor systems.
关键词： Marcus theory,Photoinduced electron transfer,Octaethylporphyrin,Second-order bimolecular fluorescence quenching constant,2-Nitrofluorene,DFT study by wB97XD/6-31G(d,p),Time-resolved emission spectroscopy
更新于2025-09-23 15:22:29
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A Signal-On Fluorosensor Based on Quench-Release Principle for Sensitive Detection of Antibiotic Rapamycin
摘要： An antibiotic rapamycin is one of the most commonly used immunosuppressive drugs, and also implicated for its anti-cancer activity. Hence, the determination of its blood level after organ transplantation or tumor treatment is of great concern in medicine. Although there are several rapamycin detection methods, many of them have limited sensitivity, and/or need complicated procedures and long assay time. As a novel fluorescent biosensor for rapamycin, here we propose “Q’-body”, which works on the fluorescence quench-release principle inspired by the antibody-based quenchbody (Q-body) technology. We constructed rapamycin Q’-bodies by linking the two interacting domains FKBP12 and FRB, whose association is triggered by rapamycin. The fusion proteins were each incorporated position-specifically with one of fluorescence dyes ATTO520, tetramethylrhodamine, or ATTO590 using a cell-free translation system. As a result, rapid rapamycin dose-dependent fluorescence increase derived of Q’-bodies was observed, especially for those with ATTO520 with a lowest detection limit of 0.65 nM, which indicates its utility as a novel fluorescent biosensor for rapamycin.
关键词： rapamycin,fluorescent biosensor,fluorescence quenching,photoinduced electron transfer,antibiotics
更新于2025-09-23 15:22:29
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Electron transfer during binding processes between thiolate molecules and Au nano-islands
摘要： We investigated electron transfer during the time-dependent binding processes between thiolate molecules and Au nano-islands by observing tunneling current with an interdigitated microelectrode supporting the sputtered Au nano-islands (IME@AuNI). The time-dependent optical and electrical signal variation during the binding process was examined for five kinds of thiolates. As the immersion time was prolonged, the optical absorbance increased, whereas the current passing through the IME@AuNI decreased. Importantly, the spectral and current characteristics depended on the thiolate structure, because of the formation of capping layer in accordance with thiolate structure. These results are mainly attributed to synergistic effects of electron transfer from Au nano-islands to thiolate molecules and bridging effects of thiolate molecules among Au nano-islands.
关键词： Au nano-islands,Thiolate molecules,Electron transfer,Localized surface plasmon resonance,Tunneling current
更新于2025-09-23 15:22:29
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Visible Light Driven Reductive (Cyclo)Dimerization of Chalcones Over Heterogeneous Carbon Nitride Photocatalyst
摘要： Single electron reduction of chalcones to the respective radical anions is a useful technique to activate these molecules toward subsequent transformations. Herein, a metal free photocatalytic version of chalcones reduction in the presence of triethanolamine as a convenient electron donor and using heterogeneous carbon nitride visible light photocatalyst is presented. The reaction proceeds via a long lived radical species of the heterogeneous organic semiconductor. The scope of the reaction was studied and regioselectivity of the chalcone radicals coupling was investigated. (1) Ten chalcones gave selectively poly substituted cyclopentanoles with 31-73% isolated yield; (2) Two chalcones bearing electron-donor groups, 4-MeOC6H4 and 2-thienyl, gave selectively the β-ketodienes in 42% and 53% isolated yield, respectively; (3) Pentafluorophenyl substituted chalcone gave exclusively the product of the radicals coupling followed by hydrogen transfer from triethanolamine – hexane-1,6-dione in 65% isolated yield. Reductive cross cyclodimerization of a mixture of two different chalcones proceeded regioselectively with the formation of one product out of four possible. The mechanism was investigated by cyclic voltammetry and linear sweep voltammetry and suggests that the reaction proceed through proton coupled electron transfer.
关键词： cyclopetanole,organic photoredox catalysis,chalcone,carbon nitride,proton coupled electron transfer
更新于2025-09-23 15:22:29
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Resolving orbital pathways for intermolecular electron transfer
摘要： Over 60 years have passed since Taube deduced an orbital-mediated electron transfer mechanism between distinct metal complexes. This concept of an orbital pathway has been thoroughly explored for donor–acceptor pairs bridged by covalently bonded chemical residues, but an analogous pathway has not yet been conclusively demonstrated for formally outer-sphere systems that lack an intervening bridge. In our present study, we experimentally resolve at an atomic level the orbital interactions necessary for electron transfer through an explicit intermolecular bond. This finding was achieved using a homologous series of surface-immobilized ruthenium catalysts that bear different terminal substituents poised for reaction with redox active species in solution. This arrangement enabled the discovery that intermolecular chalcogen?iodide interactions can mediate electron transfer only when these interactions bring the donor and acceptor orbitals into direct contact. This result offers the most direct observation to date of an intermolecular orbital pathway for electron transfer.
关键词： electron transfer kinetics,Marcus equation,ruthenium catalysts,intermolecular interactions,orbital-mediated electron transfer
更新于2025-09-23 15:21:21
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Quantitative Sequential Photoenergy Conversion Process from Singlet Fission to Intermolecular Two-Electron Transfers Utilizing Tetracene Dimer
摘要： Singlet fission (SF) theoretically enables to perform the sequential photoenergy conversion process starting from the singlet state and leading to electron transfer (ET) with the radical ion pair quantum yield approaching 200%. Additionally, the long lifetime of the triplet state opens possibility for intermolecular ET process in diffusion-limited reaction. However, the quantitative two-electron transfer process through SF has yet to be reported. Herein we demonstrated the quantitative sequential process involving SF and leading to intermolecular two-electron transfers using 2,2’-biphenyl-bridged tetracene dimer (Tet-BP-Tet: SF and electron donor) and chloranil (Ch: electron acceptor). The high-yield and long-lived individual triplet excited states of Tet-BP-Tet by SF (ΦT = 175 ± 5% and τT = 0.29 ms) resulted in the quantitative two-electron transfer process (ΦET = 173 ± 5%) with Ch in benzonitrile.
关键词： chloranil,photoenergy conversion,tetracene dimer,electron transfer,Singlet fission
更新于2025-09-23 15:21:21
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Photoinduced Electron Transfer in Carbon Dots with Long Wavelength Photoluminescence
摘要： Carbon dots have often been studied to investigate their unique optical properties such as excitation wavelength-independence emission. Carbon dots have also been shown to undergo electron transfer in different situations. This study endeavors to investigate the properties of carbon dots photoluminescence and electron transfer. Herein, the preparation and characterization of carbon dots which exhibit long wavelength photoluminescence has been reported. These carbon dots exhibit quenching when exposed to metal ions in proportion to the reduction potential of the metal, which experimental evidence has shown for the first time. This property of metal ion reduction potential-dependent quenching has been studied to show the collisional electron transfer from amine groups in carbon dots to the metal ions. Therefore, the photoluminescence in these carbon dots are directly related to organic functional groups on the surface of the carbon dots.
关键词： Quenching,Electron transfer,Photoluminescence,Carbon dots,Metal ions
更新于2025-09-23 15:21:21
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Quantification of DNA by a Thermal-Durable Biosensor Modified with Conductive Poly(3,4-ethylenedioxythiophene)
摘要： The general clinical procedure for viral DNA detection or gene mutation diagnosis following polymerase chain reaction (PCR) often involves gel electrophoresis and DNA sequencing, which is usually time-consuming. In this study, we have proposed a facile strategy to construct a DNA biosensor, in which the platinum electrode was modified with a dual-film of electrochemically synthesized poly(3,4-ethylenedioxythiophene) (PEDOT) resulting in immobilized gold nanoparticles, with the gold nanoparticles easily immobilized in a uniform distribution. The DNA probe labeled with a SH group was then assembled to the fabricated electrode and employed to capture the target DNA based on the complementary sequence. The hybridization efficiency was evaluated with differential pulse voltammetry (DPV) in the presence of daunorubicin hydrochloride. Our results demonstrated that the peak current in DPV exhibited a linear correlation the concentration of target DNA that was complementary to the probe DNA. Moreover, the electrode could be reused by heating denaturation and re-hybridization, which only brought slight signal decay. In addition, the addition of the oxidized form of nicotinamide adenine dinucleotide (NAD+) could dramatically enhance the sensitivity by more than 5.45-fold, and the limit-of-detection reached about 100 pM.
关键词： poly(3,4-ethylenedioxythiophene),gold nanoparticle,electron transfer mediate,DNA biosensor
更新于2025-09-23 15:21:21
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Photocatalytic nucleophilic addition of alcohols to styrenes in Markovnikov and anti-Markovnikov orientation
摘要： The nucleophilic addition of methanol and other alcohols to 1,1-diphenylethylene (1) and styrene (6) into the Markovnikov- and anti-Markovnikov-type products was selectively achieved with 1-(N,N-dimethylamino)pyrene (Py) and 1,7-dicyanoperylene-3,4:9,10-tetracarboxylic acid bisimide (PDI) as photoredox catalysts. The regioselectivity was controlled by the photocatalyst. For the reductive mode towards the Markovnikov-type regioselectivity, Py was applied as photocatalyst and triethylamine as electron shuttle. This approach was also used for intramolecular additions. For the oxidative mode towards the anti-Markovnikov-type regioselectivety, PDI was applied together with Ph–SH as additive. Photocatalytic additions of a variety of alcohols gave the corres- ponding products in good to excellent yields. The proposed photocatalytic electron transfer mechanism was supported by detection of the PDI radical anion as key intermediate and by comparison of two intramolecular reactions with different electron density. Representative mesoflow reactor experiments allowed to significantly shorten the irradiation times and to use sunlight as “green” light source.
关键词： perylene bisimide,photochemistry,pyrene,photocatalysis,electron transfer
更新于2025-09-23 15:21:21