Abstract
Solar-driven water-to-fuel conversion, analogous to natural photosynthesis, is an attractive energy conversion technology since it could provide an alternative to the current combustion of fossil fuels. Further understanding of catalysis in natural photosynthetics could benefit such technological developments. Photosynthetic organisms convert solar energy into NADPH and ATP (the biological fuels) through a process that is initiated at the oxygen evolving complex (OEC) of photosystem II (PSII). Such a catalytic site oxidizes water to generate the reducing equivalents for NADPH production and a pH gradient necessary for ATP biosynthesis. Water oxidation is a challenging four-electron reaction [2H2O → O2 + 4e- + 4H+] that is difficult to carry out efficiently in artificial photosynthetic systems. In this chapter, we review our recent studies of the OEC of PSII based on the recent X-ray diffraction model resolved at 1.9 Å resolution. We characterize the dark-adapted S1 state of the OEC and address the potential functional role of chloride during O2 evolution in PSII. These results are discussed in light of recent comparative studies on biomimetic oxomanganese complexes, revealing how Lewis base centers (such as carboxylate groups from the buffer solution, or surrounding environment) can play an important role as acid/base and redox cofactors in photosynthtetic water splitting. These findings have direct implications to catalytic water oxidation in photosystem II and provide useful information for the design of Mn-based biomimetic catalysts for artificial photosynthesis.
| Original language | English |
|---|---|
| Title of host publication | ACS Symposium Series |
| Publisher | American Chemical Society |
| Pages | 203-215 |
| Number of pages | 13 |
| Volume | 1133 |
| ISBN (Print) | 9780841228207 |
| DOIs | |
| Publication status | Published - 2013 |
Publication series
| Name | ACS Symposium Series |
|---|---|
| Volume | 1133 |
| ISSN (Print) | 00976156 |
| ISSN (Electronic) | 19475918 |
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ASJC Scopus subject areas
- Chemistry(all)
- Chemical Engineering(all)
Cite this
Computational studies of the oxygen-evolving complex of photosystem ii and biomimetic oxomanganese complexes for renewable energy applications. / Rivalta, Ivan; Brudvig, Gary W; Batista, Victor S.
ACS Symposium Series. Vol. 1133 American Chemical Society, 2013. p. 203-215 (ACS Symposium Series; Vol. 1133).Research output: Chapter in Book/Report/Conference proceeding › Conference contribution
}
TY - GEN
T1 - Computational studies of the oxygen-evolving complex of photosystem ii and biomimetic oxomanganese complexes for renewable energy applications
AU - Rivalta, Ivan
AU - Brudvig, Gary W
AU - Batista, Victor S.
PY - 2013
Y1 - 2013
N2 - Solar-driven water-to-fuel conversion, analogous to natural photosynthesis, is an attractive energy conversion technology since it could provide an alternative to the current combustion of fossil fuels. Further understanding of catalysis in natural photosynthetics could benefit such technological developments. Photosynthetic organisms convert solar energy into NADPH and ATP (the biological fuels) through a process that is initiated at the oxygen evolving complex (OEC) of photosystem II (PSII). Such a catalytic site oxidizes water to generate the reducing equivalents for NADPH production and a pH gradient necessary for ATP biosynthesis. Water oxidation is a challenging four-electron reaction [2H2O → O2 + 4e- + 4H+] that is difficult to carry out efficiently in artificial photosynthetic systems. In this chapter, we review our recent studies of the OEC of PSII based on the recent X-ray diffraction model resolved at 1.9 Å resolution. We characterize the dark-adapted S1 state of the OEC and address the potential functional role of chloride during O2 evolution in PSII. These results are discussed in light of recent comparative studies on biomimetic oxomanganese complexes, revealing how Lewis base centers (such as carboxylate groups from the buffer solution, or surrounding environment) can play an important role as acid/base and redox cofactors in photosynthtetic water splitting. These findings have direct implications to catalytic water oxidation in photosystem II and provide useful information for the design of Mn-based biomimetic catalysts for artificial photosynthesis.
AB - Solar-driven water-to-fuel conversion, analogous to natural photosynthesis, is an attractive energy conversion technology since it could provide an alternative to the current combustion of fossil fuels. Further understanding of catalysis in natural photosynthetics could benefit such technological developments. Photosynthetic organisms convert solar energy into NADPH and ATP (the biological fuels) through a process that is initiated at the oxygen evolving complex (OEC) of photosystem II (PSII). Such a catalytic site oxidizes water to generate the reducing equivalents for NADPH production and a pH gradient necessary for ATP biosynthesis. Water oxidation is a challenging four-electron reaction [2H2O → O2 + 4e- + 4H+] that is difficult to carry out efficiently in artificial photosynthetic systems. In this chapter, we review our recent studies of the OEC of PSII based on the recent X-ray diffraction model resolved at 1.9 Å resolution. We characterize the dark-adapted S1 state of the OEC and address the potential functional role of chloride during O2 evolution in PSII. These results are discussed in light of recent comparative studies on biomimetic oxomanganese complexes, revealing how Lewis base centers (such as carboxylate groups from the buffer solution, or surrounding environment) can play an important role as acid/base and redox cofactors in photosynthtetic water splitting. These findings have direct implications to catalytic water oxidation in photosystem II and provide useful information for the design of Mn-based biomimetic catalysts for artificial photosynthesis.
UR - http://www.scopus.com/inward/record.url?scp=84905384591&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84905384591&partnerID=8YFLogxK
U2 - 10.1021/bk-2013-1133.ch011
DO - 10.1021/bk-2013-1133.ch011
M3 - Conference contribution
AN - SCOPUS:84905384591
SN - 9780841228207
VL - 1133
T3 - ACS Symposium Series
SP - 203
EP - 215
BT - ACS Symposium Series
PB - American Chemical Society
ER -