Rademaker H, Hoff A J
Biophys J. 1981 May;34(2):325-44. doi: 10.1016/S0006-3495(81)84852-7.
The temperature dependence of the bacteriochlorophyll fluorescence and reaction center triplet yield in while cells of Rhodopseudomonas sphaeroides strain 2.4.1 and of the magnetic field-induced fluorescence increase are calculated, taking into account rate constants of losses in the antenna system and of charge separation and recombination in the reaction center. Triplet and singlet yield after recombination in the reaction center are described by the radical pair mechanism. Good fits of the theoretically calculated temperature dependence with published experimental results could be obtained, assuming that ks, the rate constant for recombination of the charges on the primary donor P+ and the reduced intermediate acceptor I- to the lowest excited singlet state PI of the reaction center bacteriochlorophyll, is temperature-dependent via the Boltzmann factor Kso exp(-delta E/kT), where delta E is the energy difference between PI and P+I- and kso is the frequency factor. kg and/or kt, the rate constants for recombination to the singlet ground and triplet states, respectively, were assumed to be temperature-independent, or temperature-dependent via their exothermicity factors ki = CiT-1/2 exp(-Ei/kT) with i = g, t. Depending on the particular choice for the temperature dependence of kg and kt, best fits were obtained for delta E = 45-75 meV and recombination rate constants at 300 K of ks = 0.4-0.8 ns-1, kg = 0.08-0.12 ns-1, and kt = 0.3-0.5 ns-1. The model predicts a lifetime of the radical pair P+I- that is somewhat larger than that of delayed fluorescence; a magnetic field increases both.
考虑到天线系统中的损失速率常数以及反应中心中的电荷分离和复合速率常数,计算了球形红假单胞菌2.4.1菌株白色细胞中细菌叶绿素荧光和反应中心三重态产率的温度依赖性以及磁场诱导的荧光增加。反应中心复合后的三重态和单重态产率由自由基对机制描述。假设反应中心细菌叶绿素的初级供体P⁺和还原的中间受体I⁻上的电荷复合到最低激发单重态PI的速率常数ks通过玻尔兹曼因子Kso exp(-ΔE/kT)与温度相关,其中ΔE是PI和P⁺I⁻之间的能量差,kso是频率因子,则理论计算的温度依赖性与已发表的实验结果能很好地拟合。分别复合到单重基态和三重态的速率常数kg和/或kt被假定为与温度无关,或者通过它们的放热因子ki = CiT⁻¹/² exp(-Ei/kT)(i = g, t)与温度相关。根据kg和kt对温度依赖性的特定选择,对于ΔE = 45 - 75 meV以及300 K时的复合速率常数ks = 0.4 - 0.8 ns⁻¹、kg = 0.08 - 0.12 ns⁻¹和kt = 0.3 - 0.5 ns⁻¹,能获得最佳拟合。该模型预测自由基对P⁺I⁻的寿命略大于延迟荧光的寿命;磁场会使两者都增加。