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细菌反应中心中核波包运动与电荷分离的耦合

Coupling of nuclear wavepacket motion and charge separation in bacterial reaction centers.

作者信息

Shuvalov V A, Yakovlev A G

机构信息

Laboratory of Photobiophysics, Belozersky Institute of Chemical and Physical Biology of Moscow State University, Moscow 119992, Russia.

出版信息

FEBS Lett. 2003 Apr 10;540(1-3):26-34. doi: 10.1016/s0014-5793(03)00237-0.

Abstract

The mechanism of the charge separation and stabilization of separated charges was studied using the femtosecond absorption spectroscopy. It was found that nuclear wavepacket motions on potential energy surface of the excited state of the primary electron donor P* leads to a coherent formation of the charge separated states P(+)B(A)(-), P(+)H(A)(-) and P(+)H(B)(-) (where B(A), H(B) and H(A) are the primary and secondary electron acceptors, respectively) in native, pheophytin-modified and mutant reaction centers (RCs) of Rhodobacter sphaeroides R-26 and in Chloroflexus aurantiacus RCs. The processes were studied by measurements of coherent oscillations in kinetics at 890 and 935 nm (the stimulated emission bands of P*), at 800 nm (the absorption band of B(A)) and at 1020 nm (the absorption band of B(A)(-)) as well as at 760 nm (the absorption band of H(A)) and at 750 nm (the absorption band of H(B)). It was found that wavepacket motion on the 130-150 cm(-1) potential surface of P* is accompanied by approaches to the intercrossing region between P* and P(+)B(A)(-) surfaces at 120 and 380 fs delays emitting light at 935 nm (P*) and absorbing light at 1020 nm (P(+)B(A)(-)). In the presence of Tyr M210 (Rb. sphaeroides) or M195 (C. aurantiacus) the stabilization of P(+)B(A)(-) is observed within a few picosseconds in contrast to YM210W. At even earlier delay (approximately 40 fs) the emission at 895 nm and bleaching at 748 nm are observed in C. aurantiacus RCs showing the wavepacket approach to the intercrossing between the P* and P(+)H(B)(-) surfaces at that time. The 32 cm(-1) rotation mode of HOH was found to modulate the electron transfer rate probably due to including of this molecule in polar chain connecting P(B) and B(A) and participating in the charge separation. The mechanism of the charge separation and stabilization of separated charges is discussed in terms of the role of nuclear motions, of polar groups connecting P and acceptors and of proton of OH group of TyrM210.

摘要

利用飞秒吸收光谱研究了电荷分离及分离电荷稳定化的机制。研究发现,初级电子供体P激发态势能面上的核波包运动导致在球形红杆菌R-26的天然、脱镁叶绿素修饰和突变反应中心(RCs)以及橙黄嗜热栖热菌RCs中,电荷分离态P(+)B(A)(-)、P(+)H(A)(-)和P(+)H(B)(-)(其中B(A)、H(B)和H(A)分别为初级和次级电子受体)的相干形成。通过测量890和935 nm(P的受激发射带)、800 nm(B(A)的吸收带)、1020 nm(B(A)(-)的吸收带)以及760 nm(H(A)的吸收带)和750 nm(H(B)的吸收带)处动力学中的相干振荡来研究这些过程。研究发现,P在130 - 150 cm(-1)势能面上的波包运动伴随着在120和380 fs延迟时接近P和P(+)B(A)(-)表面之间的交叉区域,在935 nm处发光(P*)并在1020 nm处吸收光(P(+)B(A)(-))。与YM210W相比,在存在Tyr M210(球形红杆菌)或M195(橙黄嗜热栖热菌)的情况下,在几皮秒内观察到P(+)B(A)(-)的稳定化。在更早的延迟(约40 fs)时,在橙黄嗜热栖热菌RCs中观察到895 nm处的发射和748 nm处的漂白,表明此时波包接近P*和P(+)H(B)(-)表面之间的交叉。发现HOH的32 cm(-1)旋转模式可能由于该分子包含在连接P(B)和B(A)的极性链中并参与电荷分离而调节电子转移速率。从核运动、连接P和受体的极性基团以及TyrM210的OH基团质子的作用方面讨论了电荷分离及分离电荷稳定化的机制。

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