期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 21, 期 4, 页码 1743-1748出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.201405159
关键词
cerium; density functional calculations; metalloenzymes; quinones; redox chemistry
资金
- U.S. National Science Foundation EAGER Program [CHE-1449246]
- University of Pennsylvania
- National Science Foundation [OCI-1053575]
Rare-earth metal cations have recently been demonstrated to be essential co-factors for the growth of the methanotrophic bacterium Methylacidiphilum fumariolicum SolV. A crystal structure of the rare-earth-dependent methanol dehydrogenase (MDH) includes a cerium cation in the active site. Herein, the Ce-MDH active site has been analyzed through DFT calculations. The results show the stability of the Ce-III-pyrroloquinoline quinone (PQQ) semiquinone configuration. Calculations on the active oxidized form of this complex indicate a 0.81 eV stabilization of the PQQ(0) LUMO at cerium versus calcium, supporting the observation that the cerium cation in the active site confers a competitive advantage to Methylacidiphilum fumariolicum SolV. Using reported aqueous electrochemical data, a semi-empirical correlation was established based on cerium(IV/III) redox potentials. The correlation allowed estimation of the cerium oxidation potential of +1.35 V versus saturated calomel electrode (SCE) in the active site. The results are expected to guide the design of functional model complexes and alcohol-oxidation catalysts based on lanthanide complexes of biologically relevant quinones.
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