15N photo-CIDNP MAS NMR analysis of reaction centers of Chloracidobacterium thermophilum

Photochemically induced dynamic nuclear polarization (photo-CIDNP) has been observed in the homodimeric, type-1 photochemical reaction centers (RCs) of the acidobacterium, Chloracidobacterium ( Cab .) thermophilum , by 15 N magic-angle spinning (MAS) solid-state NMR under continuous white-light illumination. Three light-induced emissive (negative) signals are detected. In the RCs of Cab. thermophilum , three types of (bacterio)chlorophylls have previously been identified: bacteriochlorophyll a (BChl a ), chlorophyll a (Chl a ), and Zn-bacteriochlorophyll a ′ (Zn-BChl a ′) (Tsukatani et al. in J Biol Chem 287:5720–5732, 2012). Based upon experimental and quantum chemical 15 N NMR data, we assign the observed signals to a Chl a cofactor. We exclude Zn-BChl because of its measured spectroscopic properties. We conclude that Chl a is the primary electron acceptor, which implies that the primary donor is most likely Zn-BChl a ′. Chl a and 8 1 -OH Chl a have been shown to be the primary electron acceptors in green sulfur bacteria and heliobacteria, respectively, and thus a Chl a molecule serves this role in all known homodimeric type-1 RCs.