Abstract
Water oxidation in Photosystem II is dependent on a particular amino acid residue, TyrosineZ. This is a redox intermediate in steady state oxygen evolution and transfers electrons from the water splitting CaMn 4 cluster to the central chlorophyll radical P680 +. This Perspective discusses the functional principles of TyrosineZ as a proton-coupled redox active link, as well as mechanistic studies of synthetic model systems and implications for artificial photosynthesis. Experimental studies of temperature dependence and kinetic isotope effects are important tools to understand these reactions. We emphasize the importance of proton transfer distance and hydrogen bond dynamics that are responsible for variation in the rate of PCET by several orders of magnitude. The mechanistic principles discussed and their functional significance are not limited to tyrosine and biological systems, but are important to take into account when constructing artificial photosynthetic systems. Of particular importance is the role of proton transfer management in water splitting and solar fuel catalysis.
| Original language | English |
|---|---|
| Pages (from-to) | 2379-2388 |
| Number of pages | 10 |
| Journal | Energy and Environmental Science |
| Volume | 4 |
| Issue number | 7 |
| DOIs | |
| Publication status | Published - Jul 2011 |
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ASJC Scopus subject areas
- Renewable Energy, Sustainability and the Environment
- Environmental Chemistry
- Pollution
- Nuclear Energy and Engineering
Cite this
Proton-coupled electron transfer of tyrosines in Photosystem II and model systems for artificial photosynthesis : The role of a redox-active link between catalyst and photosensitizer. / Hammarström, Leif; Styring, Stenbjörn.
In: Energy and Environmental Science, Vol. 4, No. 7, 07.2011, p. 2379-2388.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Proton-coupled electron transfer of tyrosines in Photosystem II and model systems for artificial photosynthesis
T2 - The role of a redox-active link between catalyst and photosensitizer
AU - Hammarström, Leif
AU - Styring, Stenbjörn
PY - 2011/7
Y1 - 2011/7
N2 - Water oxidation in Photosystem II is dependent on a particular amino acid residue, TyrosineZ. This is a redox intermediate in steady state oxygen evolution and transfers electrons from the water splitting CaMn 4 cluster to the central chlorophyll radical P680 +. This Perspective discusses the functional principles of TyrosineZ as a proton-coupled redox active link, as well as mechanistic studies of synthetic model systems and implications for artificial photosynthesis. Experimental studies of temperature dependence and kinetic isotope effects are important tools to understand these reactions. We emphasize the importance of proton transfer distance and hydrogen bond dynamics that are responsible for variation in the rate of PCET by several orders of magnitude. The mechanistic principles discussed and their functional significance are not limited to tyrosine and biological systems, but are important to take into account when constructing artificial photosynthetic systems. Of particular importance is the role of proton transfer management in water splitting and solar fuel catalysis.
AB - Water oxidation in Photosystem II is dependent on a particular amino acid residue, TyrosineZ. This is a redox intermediate in steady state oxygen evolution and transfers electrons from the water splitting CaMn 4 cluster to the central chlorophyll radical P680 +. This Perspective discusses the functional principles of TyrosineZ as a proton-coupled redox active link, as well as mechanistic studies of synthetic model systems and implications for artificial photosynthesis. Experimental studies of temperature dependence and kinetic isotope effects are important tools to understand these reactions. We emphasize the importance of proton transfer distance and hydrogen bond dynamics that are responsible for variation in the rate of PCET by several orders of magnitude. The mechanistic principles discussed and their functional significance are not limited to tyrosine and biological systems, but are important to take into account when constructing artificial photosynthetic systems. Of particular importance is the role of proton transfer management in water splitting and solar fuel catalysis.
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U2 - 10.1039/c1ee01348c
DO - 10.1039/c1ee01348c
M3 - Article
VL - 4
SP - 2379
EP - 2388
JO - Energy and Environmental Science
JF - Energy and Environmental Science
SN - 1754-5692
IS - 7
ER -