The Multicopper Oxidases (MCOs) are the family of enzymes that couple the 4-electron reduction of dioxygen to water to the four 1-electron oxidations of substrate. The MCOs contain a Type 1 (T1) or blue Cu center where substrate is oxidized. The electrons from substrate are then transferred through a protein derived Cys-His pathway to a trinuclear cluster (TNC), composed of a Type 3 Cu pair and a Type 2 Cu, where O2 is reduced. It is found that the rates at which electrons are transferred from the T1 to the TNC vary by > 3 orders of magnitude depending on the state of the TNC. The molecular origin of rapid versus slow electron transfer is discussed in the context of the catalytic mechanism of these enzymes.

Molecular insights into the rates of intramolecular electron transfer in the multicopper oxidases

248th National Meeting (2014)

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