Electron−Nuclear Spin Dynamics in a Bacterial Photosynthetic Reaction Center

Abstract

The solid-state photo-CIDNP effect is known to occur in natural photosynthetic reaction centers (RCs) where it can be observed by magic-angle spinning (MAS) NMR as strong modification of signal intensities under illumination compared to experiments performed in the dark. The origin of the effect has been debated. In this paper, we report time-resolved photo-CIDNP MAS NMR data of reaction centers of quinone depleted Rhodobacter sphaeroides. It is demonstrated that the build-up of nuclear polarization on the primary donor and the bacteriopheophytin acceptor depends on the presence and lifetimes of the molecular triplet states of the donor and carotenoid. Analysis of the data proves that up to three electron−nuclear spin-coupling mechanisms and two transient effects are working concomitantly in the spin-chemical machinery of the reaction center.