Ishikita Hiroshi, Knapp Ernst-Walter
Institute of Chemistry, Free University of Berlin, Takustrasse 6, D-14195 Berlin, Germany.
J Am Chem Soc. 2005 Feb 16;127(6):1963-8. doi: 10.1021/ja045058i.
Electron transfer (ET) processes in reaction centers (RC) of photosystem II (PSII) are prerequisites of oxygen generation. They are promoted by energy transfer from antenna to RC. Here, we calculated the redox potentials of chlorophylla/beta-carotene (Chla/Car) in PSII CP43/CP47 antenna complexes, solving the linearized Poisson-Boltzmann (LPB) equation based on the PSII crystal structure. The majority of antenna Chla redox potentials for reduction/oxidation were lower than those of RC Chla. Hence, ET events with excess electrons remain localized in the RC. Simultaneously antenna Chla can serve as an efficient cation sink to rereduce RC Chla if normal PSII function is inhibited. Especially three antenna Chla (Chl-47, Chl-18, and Chl-12) and two Car bridging the space between Chl(Z(D1)) and cytochrome (cyt) b559 have the same level of oxidation redox potential. Together with Chl(Z(D2)) they form an electron hole transfer pathway and temporary storage device guiding from the oxidized P680(+.) Chla to the cyt b559. This path may play a photoprotective role as efficient electron hole quencher.
光系统II(PSII)反应中心(RC)中的电子转移(ET)过程是氧气生成的前提条件。它们由从天线到RC的能量转移所促进。在此,我们基于PSII晶体结构求解线性化泊松-玻尔兹曼(LPB)方程,计算了PSII CP43/CP47天线复合物中叶绿素a/β-胡萝卜素(Chla/Car)的氧化还原电位。大多数天线Chla还原/氧化的氧化还原电位低于RC Chla的氧化还原电位。因此,带有多余电子的ET事件仍局限于RC中。同时,如果正常的PSII功能受到抑制,天线Chla可作为有效的阳离子汇来重新还原RC Chla。特别是三个天线Chla(Chl-47、Chl-18和Chl-12)以及两个在Chl(Z(D1))和细胞色素(cyt)b559之间架桥的Car具有相同水平的氧化还原电位。它们与Chl(Z(D2))一起形成一条电子空穴转移途径和临时存储装置,从氧化的P680(+.) Chla引导至cyt b559。这条途径可能作为有效的电子空穴猝灭剂发挥光保护作用。