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| Content Provider | PubMed Central |
|---|---|
| Author | Jenson, David L. Barry, Bridgette A. |
| Abstract | Photosystem II (PSII) catalyzes the light driven oxidation of water and the reduction of plastoquinone. PSII is a multisubunit membrane protein; the D1 and D2 polypeptides form the heterodimeric core of the PSII complex. Water oxidation occurs at a manganese-containing oxygen evolving complex (OEC). PSII contains two redox active tyrosines, YZ and YD, which form the neutral tyrosyl radicals, Yz • and YD •. YD has been assigned as tyrosine 160 in the D2 polypeptide through isotopic labeling and site-directed mutagenesis. While YD is not directly involved in the oxidation of water, it has been implicated in the formation and stabilization of the OEC. PSII structures have shown YD to be within hydrogen bonding distance of histidine 189 in the D2 polypeptide. Spectroscopic studies have suggested that a proton is transferred between YD and histidine 189 when YD is oxidized and reduced. In our previous work, we used 2H2O solvent exchange to demonstrate that the mechanism of YD proton-coupled electron transfer (PCET) differs at high and low pH (Jenson, D. L.; Evans, A.; Barry, B. A. J. Phys. Chem. B 2007, 111, 12599–12604). In this paper, we utilize the proton inventory technique to obtain more information concerning the PCET mechanism at high pH. The hypercurvature of the proton inventory data provides evidence for the existence of multiple, proton donation pathways to YD •. In addition, at least one of these pathways must involve the transfer of more than one proton. |
| Related Links | http://dx.doi.org/10.1021/ja902896e |
| Ending Page | 10573 |
| Page Count | 7 |
| Starting Page | 10567 |
| File Format | |
| ISSN | 00027863 |
| e-ISSN | 15205126 |
| Journal | Journal of the American Chemical Society |
| Issue Number | 30 |
| Volume Number | 131 |
| Language | English |
| Publisher Date | 2009-08-05 |
| Access Restriction | Open |
| Subject Keyword | Colloid and Surface Chemistry Biochemistry Chemistry(all) Catalysis Research in Higher Education |
| Content Type | Text |
| Resource Type | Article |
| Subject | Chemistry Colloid and Surface Chemistry Biochemistry Catalysis |
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