title: Interaction between tyrosineZ and substrate water in active photosystem II.
abstract: In the field of photosynthetic water oxidation it has been under debate whether Tyrosine(Z) (Tyr(Z)) acts as a hydrogen or an electron acceptor from water. In the former concept, direct contact of Tyr(Z) with substrate water has been assumed. However, there is no direct evidence for the interaction between Tyr(Z) and substrate water in active Photosystem II (PSII), instead most experiments have been performed on inhibited PSII. Here, this problem is tackled in active PSII by combining low temperature EPR measurements and quantum chemistry calculations. EPR measurements observed that the maximum yield of Tyr(Z) oxidation at cryogenic temperature in the S(0) and S(1) states was around neutral pH and was essentially pH-independent. The yield of Tyr(Z) oxidation decreased at acidic and alkaline pH, with pKs at 4.7-4.9 and 7.7, respectively. The observed pH-dependent parts at low and high values of pH can be explained as due to sample inactivation, rather than active PSII. The reduction kinetics of Tyr(Z)(.) in the S(0) and S(1) states were pH independent at pH range from 4.5 to 8. Therefore, the change of the pH in bulk solution probably has no effect on the Tyr(Z) oxidation and Tyr(Z)(.) reduction at cryogenic temperature in the S(0) and S(1) states of the active PSII. Theoretical calculations indicate that Tyr(Z) becomes more difficult to oxidize when a H(2)O molecule interacts directly with it. It is suggested that Tyr(Z) is probably located in a hydrophobic environment with no direct interaction with the substrate H(2)O in active PSII. These results provide new insights on the function and mechanism of water oxidation in PSII.
authors.affiliation: Service de Bioénergétique, CNRS URA 2096, Département de Biologie Joliot-Curie, CEA Saclay, Gif-Sur-Yvette, France. chunxizhang@iccas.ac.cn
authors.forename: Chunxi
authors.initials: C
authors.lastname: Zhang
mesh_terms: D000595:Amino Acid Sequence; D008956:Models, Chemical; D010084:Oxidation-Reduction; D045332:Photosystem II Protein Complex / Q000378:metabolism*; D011743:Pyrimidines; D014443:Tyrosine / Q000378:metabolism*; D014867:Water / Q000378:metabolism*
chemical_list: C097286:H 0294; D045332:Photosystem II Protein Complex; D011743:Pyrimidines; D014867:Water; D014443:Tyrosine