Examination of the photophysical processes of chlorophyll d leading to a clarification of proposed uphill energy transfer processes in cells of Acaryochloris marinas.

A comprehensive study of the photophysical properties of chlorophyll (Chl) d in 1:40 acetonitrile-methanol solution is performed over the temperature range 170-295 K. From comparison of absorption and emission spectra, time-dependent density-functional calculations and homologies with those of Chl a, we assign the key features of the absorption and fluorescence spectra. Possible photophysical energy relaxation mechanisms are summarized, and thermal equilibration processes are studied in detail by monitoring the observed emission profiles and quantum yields as a function of excitation energy. In particular, we concentrate on emission subsequent to excitation in the extreme far-red tail of the Qy absorption spectrum, with this emission partitioned into contributions from hot-band absorptions as well as uphill energy transfer processes that occur subsequent to absorption. No unusual photophysical processes are detected for Chl d; it appears that all intramolecular relaxation processes reach thermal equilibration on shorter timescales than the fluorescence lifetime even at 170 K. The results from these studies are used to reinterpret a previous study of photochemical processes observed in intact cells and their acetone extracts of the photosynthetic system of Acaryochloris marina. In the study of Mimuro et al., light absorbed by Chl d at 736 nm is found to give rise to emission by another species, believed to also be Chl d, at 703 nm; this uphill energy transfer process is easily rationalized in terms of the thermal equilibration processes that we deduced for Chl d. However, no evidence is found in the experimental results of Mimuro et al. to support claims that (nonequilibrium) uphill energy transfer is additionally observed to Chl a species that emit at 670-680 nm. This finding is relevant to broader issues concerning the nature of the special pair in photosystem II of A. marina because suggestions that it is comprised of Chl a can only be correct if nonthermal uphill energy transfer processes from Chl d are operative.