The S1 split signal of photosystem II; a tyrosine-manganese coupled interaction

Detailed optical and EPR analyses of states induced in dark-adapted PS II membranes by cryogenic illumination permit characterization and quantification of all pigment derived donors and acceptors, as well as optically silent (in the visible, near infrared) species which are EPR active. Near complete turnover formation of Q(A)(-) is seen in all centers, but with variable efficiency, depending on the donor species. In minimally detergent-exposed PS II membranes, negligible (<5%) oxidation of chlorophyll or carotenoid centers occurs for illumination temperatures 5-20 K. An optically silent electron donor to P680(+) is observed with the same decay kinetics as the S-1 split signal. Cryogenic donors to P680(+) seen are: (i) transient (t(1/2)similar to 150 s) tyrosine related species, including 'split signals' (similar to 15% total centers), (ii) reduced cytochrome b(559) (similar to 30-50% centers), and (iii) an organic donor, possibly an amino acid side chain, (similar to 30% centers). (C) 2009 Elsevier B.V. All rights reserved.