色素置换影响紫细菌601光合反应中心的电化学性质及其机理

运用色素置换、单分子复合膜技术及方波伏安法测定, 研究了色素置换对紫细菌Rhodobacter sphaeroides 601光合反应中心电化学性质的影响, 并探讨了相关机理. 研究发现, 紫细菌光反应中心在外加电位驱动下也可以产生电荷分离, 其效果等同于照光条件下的原初光化学反应. 在金电极表面上, 由2,3-二巯基丁二酸(DMSA)、聚二甲基二丙烯氯化铵(PDDA)与紫细菌光合反应中心(RC)组装而成单分子层复合膜(RC-PDDA-DMSA膜). 利用方波伏安法对RC-PDDA-DMSA膜进行了研究, 用低频率和高频率方波分别检测到紫细菌反应中心光化学反应不同的4个氧化还原电位对的参数. 通过非线性拟合, 获得了P/P⁺的标准电位(0.522 V)和电极反应速率常数(13.04 s^-1). 植物去镁叶绿素(Phe)置换细菌去镁叶绿素(Bphe)后反应中心在- 0.02 V的氧化还原峰显著变化, 进一步分析后认为是色素置换降低了Bphe^- / Bphe(Phe^- / Phe)和Q_A^-/Q_A电位对之间电子转移速率. 分析不同色素置换后的光谱及电化学性质, 并对不同的色素分子的功能基团进行比较, 结果表明, 叶绿醇尾同卟啉环上的其他取代基团一样明显影响了色素置换的位点和效率.     

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 ofRhodobacter 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-dimethyldiallylammonium 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 Q_A ^-/Q_A 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.     

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 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 b