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Title: Hydrogen Tunneling in Enzymes and Biomimetic Models

Hydrogen transfer reactions play an important role throughout chemistry and biology. In general, hydrogen transfer reactions encompass proton and hydride transfer, which are associated with the transfer of a positively or negatively charged species, respectively, and proton-coupled electron transfer (PCET), which corresponds to the net transfer of one electron and one proton in the simplest case. Such PCET reactions can occur by either a sequential mechanism, in which the proton or electron transfers first, or a concerted mechanism, in which the electron and proton transfer in a single kinetic step with no stable intermediate. Furthermore, concerted PCET reactions can be subdivided into hydrogen atom transfer (HAT), which corresponds to the transfer of an electron and proton between the same donor and acceptor (i.e., the transfer of a predominantly neutral species), and electron-proton transfer (EPT), which corresponds to the transfer of an electron and proton between different donors and acceptors, possibly even in different directions. In all of these types of hydrogen transfer reactions, hydrogen tunneling could potentially play a signficant role. The theoretical development portion of this Review was supported by the National Science Foundation under CHE-10-57875. The biological portion of this Review was funded by NIH Grant No. GM056207.more » The biomimetic portion was supported as part of the Center for Molecular Electro-catalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences.« less
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Report Number(s):
Journal ID: ISSN 0009-2665; KC0307010
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Resource Type:
Journal Article
Resource Relation:
Journal Name: Chemical Reviews; Journal Volume: 114; Journal Issue: 7
American Chemical Society
Research Org:
Pacific Northwest National Laboratory (PNNL), Richland, WA (US)
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Country of Publication:
United States