TY - JOUR
T1 - Theoretical studies of proton-coupled electron transfer
T2 - Models and concepts relevant to bioenergetics
AU - Hammes-Schiffer, Sharon
AU - Hatcher, Elizabeth
AU - Ishikita, Hiroshi
AU - Skone, Jonathan H.
AU - Soudackov, Alexander V.
N1 - Funding Information:
We are grateful for support of this work by NSF grant CHE-05-01260 and NIH grant GM56207.
PY - 2008/2
Y1 - 2008/2
N2 - Theoretical studies of proton-coupled electron transfer (PCET) reactions for model systems provide insight into fundamental concepts relevant to bioenergetics. A dynamical theoretical formulation for vibronically nonadiabatic PCET reactions has been developed. This theory enables the calculation of rates and kinetic isotope effects, as well as the pH and temperature dependences, of PCET reactions. Methods for calculating the vibronic couplings for PCET systems have also been developed and implemented. These theoretical approaches have been applied to a wide range of PCET reactions, including tyrosyl radical generation in a tyrosine-bound rhenium polypyridyl complex, phenoxyl/phenol and benzyl/toluene self-exchange reactions, and hydrogen abstraction catalyzed by the enzyme lipoxygenase. These applications have elucidated some of the key underlying physical principles of PCET reactions. The tools and concepts derived from these theoretical studies provide the foundation for future theoretical studies of PCET in more complex bioenergetic systems such as Photosystem II.
AB - Theoretical studies of proton-coupled electron transfer (PCET) reactions for model systems provide insight into fundamental concepts relevant to bioenergetics. A dynamical theoretical formulation for vibronically nonadiabatic PCET reactions has been developed. This theory enables the calculation of rates and kinetic isotope effects, as well as the pH and temperature dependences, of PCET reactions. Methods for calculating the vibronic couplings for PCET systems have also been developed and implemented. These theoretical approaches have been applied to a wide range of PCET reactions, including tyrosyl radical generation in a tyrosine-bound rhenium polypyridyl complex, phenoxyl/phenol and benzyl/toluene self-exchange reactions, and hydrogen abstraction catalyzed by the enzyme lipoxygenase. These applications have elucidated some of the key underlying physical principles of PCET reactions. The tools and concepts derived from these theoretical studies provide the foundation for future theoretical studies of PCET in more complex bioenergetic systems such as Photosystem II.
KW - Electron transfer
KW - Hydrogen transfer
KW - Proton transfer
KW - Proton-coupled electron transfer
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U2 - 10.1016/j.ccr.2007.07.019
DO - 10.1016/j.ccr.2007.07.019
M3 - Review article
AN - SCOPUS:38049058298
VL - 252
SP - 384
EP - 394
JO - Coordination Chemistry Reviews
JF - Coordination Chemistry Reviews
SN - 0010-8545
IS - 3-4
ER -