화학공학소재연구정보센터
Journal of Physical Chemistry B, Vol.106, No.36, 9454-9462, 2002
Molecular dynamics of Q(A)(-center dot) and Q(B)(-center dot) in photosynthetic bacterial reaction centers studied by pulsed high-field EPR at 95 GHz
The anisotropic transverse relaxation times T-2 of the primary and secondary acceptor quinone radical anions Q(A)(-.) and Q(B)(-.) in Zn-substituted photosynthetic bacterial reaction centers of Rhodobacter sphaeroides R26 have been studied by means of 2D high-field/high-frequency (3.4 T/95 GHz, W-hand) electron spin-echo spectroscopy. The swept magnetic field is the first, and the pulse-separation time is the second variable. Because of the high magnetic field in W-band EPR, the anisotropic Zeeman interactions of quinone radical anions are resolved; therefore, the orientation dependence of the T-2 relaxation time can be investigated. For QA(-.) and Q(B)(-.), the monoexponential echo decays at 120 K have different orientation-dependent time constants. The anisotropy of the relaxation times is related to anisotropic stochastic fluctuations of the quinones in their protein-binding pockets, which are temperature-dependent. A model is proposed in which the orientation-dependent relaxation originates in reorientational fluctuations around the quinones' specific hydrogen bonds to surrounding amino acids in the binding sites.