With the help of pigment substitution, self-assembled monolayer film and square wave voltammetry, the influence of pigment substitution on the electrochemical properties of Rhodobacter sphaeroides 601 reaction centers...With the help of pigment substitution, self-assembled monolayer film and square wave voltammetry, the influence of pigment substitution on the electrochemical properties of Rhodobacter 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 Bphe-/Bphe (Phe-/Phe) 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.展开更多
基金the National Natural Science Foundation of China (Grant No.29872055 for Chen Z. L., Grant Nos. 39970195 and 29905001 for Zhao J. Q. et al., Grant No.39870161 for Zou Y. L. et al.) and the State Key Basic and Development Plan (G1998010100).
文摘With the help of pigment substitution, self-assembled monolayer film and square wave voltammetry, the influence of pigment substitution on the electrochemical properties of Rhodobacter 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 Bphe-/Bphe (Phe-/Phe) 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.
