Kondo Toru, Itoh Shigeru, Matsuoka Masahiro, Azai Chihiro, Oh-oka Hirozo
§Department of Biological Sciences, Graduate School of Science, Osaka University, Osaka 560-0043, Japan.
J Phys Chem B. 2015 Jul 9;119(27):8480-9. doi: 10.1021/acs.jpcb.5b03723. Epub 2015 Jun 30.
The type I photosynthetic reaction center (RC) of heliobacteria (hRC) is a homodimer containing cofactors almost analogous to those in the plant photosystem I (PS I). However, its three-dimensional structure is not yet clear. PS I uses phylloquinone (PhyQ) as a secondary electron acceptor (A1), while the available evidence has suggested that menaquinone (MQ) in hRC has no function as A1. The present study identified a new transient electron spin-polarized electron paramagnetic resonance (ESP-EPR) signal, arising from the radical pair of the oxidized electron donor and the reduced electron acceptor (P800(+)MQ(-)), in the hRC core complex and membranes from Heliobacterium modesticaldum. The ESP signal could be detected at 5-20 K upon flash excitation only after prereduction of the iron-sulfur center, F(X), and was selectively lost by extraction of MQ with diethyl ether. MQ was suggested to be located closer to F(X) than PhyQ in PS I based on the simulation of the unique A/E (A, absorption; E, emission) ESP pattern, the reduction/oxidation rates of MQ, and the power saturation property of the static MQ(-) signal. The result revealed the quinone usage as the secondary electron acceptor in hRC, as in the case of PS I.
嗜盐菌的I型光合反应中心(hRC)是一种同型二聚体,其辅因子几乎与植物光系统I(PS I)中的辅因子类似。然而,其三维结构尚不清楚。PS I使用叶醌(PhyQ)作为次级电子受体(A1),而现有证据表明hRC中的甲萘醌(MQ)不具有A1的功能。本研究在中度嗜盐栖热菌的hRC核心复合物和膜中鉴定出一种新的瞬态电子自旋极化电子顺磁共振(ESP-EPR)信号,该信号由氧化电子供体和还原电子受体的自由基对(P800(+)MQ(-))产生。仅在铁硫中心F(X)预还原后,在5-20 K的闪光激发下才能检测到ESP信号,并且通过用乙醚萃取MQ可选择性地消除该信号。基于独特的A/E(A,吸收;E,发射)ESP模式的模拟、MQ的还原/氧化速率以及静态MQ(-)信号的功率饱和特性,表明MQ在PS I中比PhyQ更靠近F(X)。结果揭示了hRC中醌作为次级电子受体的用途,与PS I的情况相同。