Yakovlev Andrei G, Shkuropatova Tatiana A, Vasilieva Lyudmila G, Shkuropatov Anatoli Ya, Shuvalov Vladimir A
Department of Photobiophysics, Belozersky Institute of Chemical and Physical Biology, Moscow State University, Moscow 119991, Russian Federation.
J Bioinform Comput Biol. 2008 Aug;6(4):643-66. doi: 10.1142/s0219720008003680.
Transient absorption difference spectroscopy with approximately 20 femtosecond (fs) resolution was applied to study the time and spectral evolution of low-temperature (90 K) absorbance changes in isolated reaction centers (RCs) of Chloroflexus (C.) aurantiacus. In RCs, the composition of the B-branch chromophores is different with respect to that of purple bacterial RCs by occupying the B(B) binding site of accessory bacteriochlorophyll by bacteriopheophytin molecule (Phi(B)). It was found that the nuclear wave packet motion induced on the potential energy surface of the excited state of the primary electron donor P* by approximately 20 fs excitation leads to a coherent formation of the states P+Phi(B)(-) and P+B(A)(-) (B(A) is a bacteriochlorophyll monomer in the A-branch of cofactors). The processes were studied by measuring coherent oscillations in kinetics of the absorbance changes at 900 nm and 940 nm (P* stimulated emission), at 750 nm and 785 nm (Phi(B) absorption bands), and at 1,020-1028 nm (B(A)(-) absorption band). In RCs, the immediate bleaching of the P band at 880 nm and the appearance of the stimulated wave packet emission at 900 nm were accompanied (with a small delay of 10-20 fs) by electron transfer from P* to the B-branch with bleaching of the Phi(B) absorption band at 785 nm due to Phi(B)(-) formation. These data are consistent with recent measurements for the mutant HM182L Rb. sphaeroides RCs (Yakovlev et al., Biochim Biophys Acta 1757:369-379, 2006). Only at a delay of 120 fs was the electron transfer from P* to the A-branch observed with a development of the B(A)(-) absorption band at 1028 nm. This development was in phase with the appearance of the P* stimulated emission at 940 nm. The data on the A-branch electron transfer in C. aurantiacus RCs are consistent with those observed in native RCs of Rb. sphaeroides. The mechanism of charge separation in RCs with the modified B-branch pigment composition is discussed in terms of coupling between the nuclear wave packet motion and electron transfer from P* to Phi(B) and B(A) primary acceptors in the B-branch and A-branch, respectively.
采用分辨率约为20飞秒(fs)的瞬态吸收差分光谱,研究嗜热绿弯菌(C. aurantiacus)分离反应中心(RCs)在低温(90K)下吸光度变化的时间和光谱演化。在反应中心,B-分支发色团的组成与紫色细菌反应中心不同,细菌脱镁叶绿素分子(Phi(B))占据了辅助细菌叶绿素的B(B)结合位点。研究发现,约20飞秒的激发在初级电子供体P的激发态势能面上诱导的核波包运动,导致P+Phi(B)(-)和P+B(A)(-)态的相干形成(B(A)是辅因子A-分支中的细菌叶绿素单体)。通过测量900nm和940nm(P受激发射)、750nm和785nm(Phi(B)吸收带)以及1020 - 1028nm(B(A)(-)吸收带)处吸光度变化动力学中的相干振荡来研究这些过程。在反应中心,880nm处P带的立即漂白以及900nm处受激发射波包的出现,伴随着(有10 - 20飞秒的小延迟)电子从P转移到B-分支,由于Phi(B)(-)的形成,785nm处Phi(B)吸收带出现漂白。这些数据与最近对突变体HM182L球形红细菌反应中心的测量结果一致(Yakovlev等人,《生物化学与生物物理学报》1757:369 - 379,2006)。仅在120飞秒的延迟时,观察到电子从P转移到A-分支,同时1028nm处B(A)(-)吸收带出现。这种变化与940nm处P受激发射的出现同相。嗜热绿弯菌反应中心A-分支电子转移的数据与在球形红细菌天然反应中心观察到的数据一致。从核波包运动与分别从P到B-分支中的Phi(B)和A-分支中的B(A)初级受体的电子转移之间的耦合角度,讨论了具有修饰的B-分支色素组成的反应中心中的电荷分离机制。