Chiou H C, Lin S, Blankenship R E
Department of Chemistry and Biochemistry, Arizona State University, Tempe 85287-1604, USA.
J Phys Chem B. 1997 May 15;101(20):4136-41. doi: 10.1021/jp963384h.
Transient absorption difference spectra in the Qy absorption band of bacteriochlorophyll (BChl) g and in the 670 nm absorption band of the primary acceptor A0 in membranes of Heliobacillus mobilis (Hc. mobilis) were measured at 20 K upon selective excitation at 668, 793, 810, and 815 nm with a 5 nm spectral bandwidth. When excited at 793 nm, the spectral equilibration of excitations from shorter to longer wavelength-absorbing pigments occurred within 3 ps and mostly localized at the band centered around 808 nm. When excited at 668 nm, the excitation energy transfer from the 670 nm absorbing pigment to the Qy band of BChl g took less than 0.5 ps, and the energy redistribution occurred and localized at 808 nm as in the case of the 793 nm excitation. All of the excitations were localized at the long wavelength pigment pool centered around 810 or 813 nm when excited at 810 or 815 nm. A slower energy transfer process with a time constant of 15 ps was also observed within the pool of long wavelength-absorbing pigments upon selective excitation at different wavelengths as has been observed by Lin et al. (Biophys. J. 1994, 67, 2479) when excited at 590 nm. Energy transfer from long wavelength antenna molecules to the primary electron donor P798 followed by the formation of P+ took place with a time constant of 55-70 ps for all excitations. Direct excitation of the primary electron acceptor A0, which absorbed at 670 nm, showed the same kinetic behavior as in the case when different forms of antenna pigments were excited in the Qy region. This observation generally supports the trapping-limited case of energy transfer in which the excitations have high escape probability from the reaction center (RC) until the charge separation takes place. Possible mechanisms to account for the apparent "uphill" energy transfer from the long wavelength antenna pigments to P798 are discussed.
在20 K下,使用5 nm光谱带宽,在668、793、810和815 nm处进行选择性激发,测量了运动性嗜盐杆菌(Hc. mobilis)膜中细菌叶绿素(BChl)g的Qy吸收带和初级受体A0在670 nm吸收带的瞬态吸收差光谱。当在793 nm激发时,激发从较短波长吸收色素到较长波长吸收色素的光谱平衡在3 ps内发生,并且大部分定位在以808 nm为中心的波段。当在668 nm激发时,激发能量从670 nm吸收色素转移到BChl g的Qy带的时间小于0.5 ps,并且能量重新分布发生并定位在808 nm,与793 nm激发的情况相同。当在810或815 nm激发时,所有激发都定位在以810或813 nm为中心的长波长色素池中。正如Lin等人(《生物物理杂志》,1994年,67卷,2479页)在590 nm激发时所观察到的那样,在不同波长的选择性激发下,在长波长吸收色素池中也观察到了一个时间常数为15 ps的较慢能量转移过程。从长波长天线分子到初级电子供体P798的能量转移随后形成P+,对于所有激发,其时间常数为55 - 70 ps。对在670 nm吸收的初级电子受体A0的直接激发显示出与在Qy区域激发不同形式的天线色素时相同的动力学行为。这一观察结果总体上支持了能量转移的俘获限制情况,即激发在电荷分离发生之前从反应中心(RC)具有很高的逃逸概率。讨论了可能解释从长波长天线色素到P798的明显“上坡”能量转移的机制。