Spectroscopic and Electrical Properties of Polymeric Donor—Acceptor Complexes
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Abstract:
The spectroscopic and electrical properties of poly (p-dimethylaminostyrene) complexes with a variety of electron acceptors have been measured. Weak electron acceptors yield charge-transfer complexes, whereas strong electron acceptors are partially converted into radical anions. As may be concluded from measurements of the Seebeck coefficient, charge transport is caused by electrons. The electrical conductivity of the complexes is critically dependent on acceptor concentration and is attributed to hopping processes between radical anions and neutral acceptor molecules.Keywords:
Acceptor
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Electron donor
Electron acceptor
Reactivity
Acceptor
Photoexcitation
Electron donor
Radical ion
Photoinduced electron transfer
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A light-activated electron-transfer chain was assembled using solubilized cyanobacterial photosystem I as photoactive enzyme, cytochrome c(6) (also from cyanobacteria) as electron donor, and methyl viologen as electron acceptor. The photocatalytic activity of the ensemble was measured by direct and reversible electrochemistry of cytochrome c(6) at a surface-modified gold electrode. Analysis of the electrochemical response with an appropriate model for the reaction mechanism allowed the relation of the overall catalytic reaction rate to the individual steps of the catalytic cycle. Second-order rate constants were determined for the first time under steady-state conditions. The results validate this approach as an efficient method for the study of electron transfer between photoactive enzymes and their redox partners.
Electron acceptor
Cytochrome b6f complex
Catalytic cycle
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Aiming at exploring the relationship between the spacer and fluorescence switch properties, we synthesized a series of new photoactive triads, in which one perylenetetracarboxylic diimide unit acting as the electron acceptor was attached to two ferrocene moieties through different spacers. This kind of donor−spacer−acceptor structure allows for tuning one of the key factors that governs photoinduced electron transfer, the distance between the electron donor and acceptor units. The excited-state electron-transfer processes were monitored by both steady-state and time-resolved emission as well as transient absorption techniques. It was found that fluorescence intensity of the solution of all triads 1−3 can be reversibly modulated by the electrochemical oxidation and reduction sequentially. More importantly, as the length of the spacer between the donor and acceptor increases, the background fluorescence increased proportionally, but the contrast ratio of the fluorescence decreases. Together these two factors determine the assay sensitivity, and therefore this work is helpful to provide a basis for the rational design of fluorescence switch by optimizing these factors above.
Photoinduced electron transfer
Acceptor
Electron acceptor
Electron donor
Diimide
Rational design
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Acceptor
Electron acceptor
Electron donor
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Flash photolysis
Photoinduced electron transfer
Acceptor
Electron acceptor
Electron donor
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Semiquinone
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