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Influence of pigment substitution on the electrochemical properties of Rhodobacter sphaeroides 601 reaction centers
Authors:ZOU Yonglong ZHAO Jiequan  CHEN ZhilongKONG Jilie ZENG Xiaohua XU Chunhe
Institution:ZOU Yonglong ZHAO Jiequan,CHEN ZhilongKONG Jilie ZENG Xiaohua XU ChunheShanghai Institute of Plant Physiology,Shanghai Institutes of Life Science,Chinese Academy of Sciences,Shanghai 200032,China,Department of Chemistry,Fudan University,Shanghai 200433,China,Faculty of Naval Medicine,Second Military Medical University,Shanghai 200433,China
Abstract:With the help of pigment substitution, self-assembled monolayer film and square wave voltammetry, the influence of pigment substitution on the electrochemical properties of Rhodobac-ter sphaeroides 601 reaction centers was investigated. Results showed that the charge separation could also be driven by externally electric field, similar to the primary photochemical reaction in purple bacterial reaction center. On the surface of Au electrode, a self-assembled monolayer film (the RC-PDDA-DMSA film) was made up of 2,3-dimercaptosuccinic acid (DMSA), poly-dimeth-yldiallylammonium chloride (PDDA) and reaction center (RC). When square wave voltammetry was used to study the RC-PDDA-DMSA film, four redox pairs in the photochemical reaction of RC were observed by changing frequency. With nonlinear fitting, the standard potential of P/P+ and the corresponding electrode reaction rate constant were determined to be 0.522 V and 13.04 S-1, respectively. It was found that the redox peak at -0.02 V changed greatly when bacteriopheophytin was substituted by plant pheophytin in the reaction center. Further studies indicated that this change resulted from the decrease in electron transfer rate between Bphe7Bphe (Phe7Phe) and QA-/QA after pigment substitution. After investigations of spectra and electrochemical properties of different RCs and comparisons of different function groups of pigments, it was indicated that the phytyl tail, similar to other substituted groups of pheophytin, affected the efficiencies of pigment substitution.
Keywords:pheophytin substitution  monolayer film  square wave voltammetry  primary photochemical reaction  redox pair  phytyl  
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