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Light-Induced Electron Spin-Polarized (ESP) EPR Signal of the P800+ Menaquinone– Radical Pair State in Oriented Membranes of Heliobacterium modesticaldum: Role/Location of Menaquinone in the Homodimeric Type I Reaction Center
The Journal of Physical Chemistry B ( IF 3.3 ) Pub Date : 2018-02-08 00:00:00 , DOI: 10.1021/acs.jpcb.7b12171
Toru Kondo 1 , Masahiro Matsuoka 2 , Chihiro Azai 2 , Masami Kobayashi 3 , Shigeru Itoh 1 , Hirozo Oh-oka 2
Affiliation  

Function/location of menaquinone (MQ) was studied in the photosynthetic reaction center of Heliobacterium (Hbt.) modesticaldum (hRC), which is one of the most primitive homodimeric type I RCs. The spin-polarized electron paramagnetic resonance signals of light-induced radical pair species, which are made of oxidized electron donor bacteriochlorophyll g (P800+) and reduced menaquinone (MQ) or iron–sulfur cluster (FX), were measured in the oriented membranes of Hbt. modesticaldum at cryogenic temperature. The spectral shape of transient electron spin-polarized signal of P800+FX radical pair state varied little with respect to the direction of the external magnetic field. It suggested a dominant contribution of the spin evolution on the precursor primary radical pair P800+A0 state with the larger isotropic magnetic exchange interaction J than the anisotropic dipole interaction D. The pure P800+MQ signal was simulated by subtracting the effects of spin evolution during the electron-transfer process. It was concluded that the J value of the P800+MQ radical pair is negative with an amplitude almost comparable to |D|. It is in contrast to a positive and small J value of the P700+PhyQ state in photosystem I (PS I). The results indicate similar but somewhat different locations/binding sites of quinones between hRC and PS I.

中文翻译:

P800 + Menaquinone 自由基对模式的HeliobacteriumModesticaldum膜中的光诱导电子自旋极化(ESP)EPR信号:Menaquinone在同型I型反应中心中的作用/位置

在最原始的同型二聚体I型RCs之一的Heliobacter(modemicalticalum)(hRC)的光合反应中心研究了甲萘醌(MQ)的功能/位置。测量了由氧化电子给体细菌叶绿素g(P800 +)和还原性甲萘醌(MQ )或铁硫簇(F X )组成的光诱导自由基对物种的自旋极化电子顺磁共振信号。Hbt的定向膜低温下的modesticaldum。P800 + F X 的瞬态电子自旋极化信号的频谱形状自由基对状态相对于外部磁场的方向变化很小。它建议自旋演化对前体初级自由基对的主要贡献P800 +0 -状态具有较大的各向同性磁交换相互作用Ĵ比各向异性偶极相互作用d。通过减去电子转移过程中自旋演化的影响来模拟纯P800 + MQ 信号。结论是,P800 + MQ 自由基对的J值是负的,其幅度几乎可与|| | |相比较。d|。与光系统I(PS I)中P700 + PhyQ 状态的正J值和较小的J值相反。结果表明,hRC和PS I之间醌的位置相似/但有所不同。
更新日期:2018-02-08
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