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缺失初始细菌叶绿素电子受体的细菌光合作用反应中心的光化学。

Photochemistry of a bacterial photosynthetic reaction center missing the initial bacteriochlorophyll electron acceptor.

机构信息

Department of Chemistry, Stanford University, Stanford, California 94305-5080, USA.

出版信息

J Phys Chem B. 2012 Aug 23;116(33):9971-82. doi: 10.1021/jp305276m. Epub 2012 Aug 9.

Abstract

A novel chromophore composition of the bacterial photosynthetic reaction center (RC) has been discovered: RCs lacking the L-side monomeric bacteriochlorophyll chromophore result from mutation of the native isoleucine at M204 to glutamine in Rhodobacter capsulatus . This conclusion is obtained from 77 K UV-vis spectroscopy and pigment extractions of the I(M204)Q mutant and seven variants containing the I(M204)Q plus other mutations. The oxidation potential of the primary electron donor P (a dimer of bacteriochlorophylls) was measured for three of the mutants and found to be 50-65 mV lower than in wild-type RCs. Ultrafast transient absorption measurements reveal (minimally) two subpopulations of P* that have distinct lifetimes and photochemical outcomes for all mutants containing I(M204)Q. In one subpopulation P* decays solely by internal conversion to the ground state. In the other subpopulation P* decays by electron transfer to the normally inactive M-side bacteriopheophytin (H(M)) in competition with internal conversion to the ground state. When a Tyr residue is substituted for the native Phe at L181 near the M-side monomeric bacteriochlorophyll (B(M)), the rate of electron transfer to H(M) is increased about 4-fold.

摘要

一种新型的细菌光合作用反应中心(RC)发色团组成已被发现:RC 缺失 L-侧单体细菌叶绿素发色团是由于 Rhodobacter capsulatus 中天然异亮氨酸突变为谷氨酰胺所致。这一结论是通过对 I(M204)Q 突变体和包含 I(M204)Q 以及其他突变的七种变体的 77 K UV-vis 光谱和色素提取得出的。三种突变体的初级电子供体 P(细菌叶绿素的二聚体)的氧化电位进行了测量,发现比野生型 RC 低 50-65 mV。超快瞬态吸收测量显示(最小)两个 P亚群,对于包含 I(M204)Q 的所有突变体,它们具有不同的寿命和光化学结果。在一个亚群中,P仅通过内部转换回到基态而衰减。在另一个亚群中,P*通过电子转移到正常不活跃的 M-侧细菌脱镁叶绿素(H(M))与内部转换回到基态竞争而衰减。当在 L181 附近的 M-侧单体细菌叶绿素(B(M))处用 Tyr 取代天然 Phe 时,电子转移到 H(M)的速率增加约 4 倍。

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