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Title Redox active tyrosines in photosystem II: role in proton coupled electron transfer reactions
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Degree PhD
Discipline/Department Chemistry and Biochemistry
Degree Level doctoral
University/Publisher Georgia Tech
Abstract Proton coupled electron transfer reactions often involve tyrosine residues, because when oxidized, the phenolic side chain deprotonates. Tyrosine Z (YZ) is responsible for extracting electrons in a stepwise fashion from the oxygen evolving-complex in order to build enough potential to oxidize water. This process requires that each step YZ must deprotonate and reprotonate in order to maintain the high midpoint potential that is necessary to oxidize the oxygen-evolving complex, which makes YZ highly involved in proton coupled electron transfer reactions. In this thesis YZ has been studied within oxygen-evolving photosystem II utilizing electron paramagnetic resonance spectroscopy to monitor the tyrosyl radical that is formed upon light excitation. Kinetic analysis of YZ has shed light on the factors that are important for PSII to carry out water oxidation at the oxygen-evolving complex. Most notably the strong hydrogen-bonding network and the midpoint potential of YZ have been shown to be integral aspects of the water splitting reactions of PSII. By studying YZ within oxygen-evolving PSII, conclusions are readily applied to the native system.
Subjects/Keywords Photosystem II; Proton coupled electron transfer reactions; Tyrosine Z; Tyrosine D; YZ; YD; Water oxidation; Photosynthesis; Power resources Research; Photosynthetic reaction centers
Contributors Bridgette A. Barry (Committee Chair); Adegboyega K. Oyelere (Committee Member); Facundo Fernandez (Committee Member); Ingeborg Schmidt-Krey (Committee Member); Mostafa El-Sayed (Committee Member)
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Record ID handle:1853/47738
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Date Indexed 2020-05-13
Issued Date 2013-01-07 00:00:00
Note [degree] PhD; [advisor] Committee Chair: Bridgette A. Barry; Committee Member: Adegboyega K. Oyelere; Committee Member: Facundo Fernandez; Committee Member: Ingeborg Schmidt-Krey; Committee Member: Mostafa El-Sayed;

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