[O.sub.2] and [N.sub.2]O activation by bi-, tri-, and tetranuclear Cu clusters in biology
Article Abstract:
The copper-clusters site represent exchange coupling between oxidized Cu's and [e.sup.-] delocalization in mixed valent sites, which play a significant role in oxygen binding and activation for electrophilic aromatic attack and H-atom abstraction, the 4[e.sup.-]/4[H.sup.+] reduction of [O.sub.2] to [H.sub.2]O, and in the 2[e.sup.-]/2[H.sup.+] reduction of [N.sub.2]O. A spectroscopic/electronic structural analysis on the intermediates and model complexes of copper proteins and reactivity correlations is described.
Publication Name: Accounts of Chemical Research
Subject: Science and technology
ISSN: 0001-4842
Year: 2007
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Mononuclear Cu-[O.sub.2] complexes: geometries, spectroscopic properties, electronic structures, and reactivity
Article Abstract:
An in-depth analysis, applying interwoven empirical and theoretical techniques, of many structurally defined 1:1 Cu-[O.sub.2] complexes, is done to study the nature of intermediates occupied in aerobic oxidations in synthetic and enzymatic copper-mediated catalysis. The parameters that affect the mode of oxygen coordination (end-on vs side-on) and the electronic structure, which can change between Cu (II)-superoxo and Cu(III)-peroxo extremes, are better understood.
Publication Name: Accounts of Chemical Research
Subject: Science and technology
ISSN: 0001-4842
Year: 2007
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Shall we dance? How a multicopper oxidase chooses its electron transfer partner
Article Abstract:
The structure-activity features of multicopper oxidases that determine their relative substrate specificity were analyzed. It was shown that while binding and orienting the substrate these metallo-oxidases also tune the reduction potential of the protein-bound metal ion and provide the electron coupling pathways for its oxidation.
Publication Name: Accounts of Chemical Research
Subject: Science and technology
ISSN: 0001-4842
Year: 2007
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