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Issue 1, 2003
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Promoting laccase activity towards non-phenolic substrates: a mechanistic investigation with some laccase–mediator systems

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Abstract

The oxidation of benzyl alcohols with the enzyme laccase, under mediation by appropriate mediator compounds, yields carbonylic products, whereas laccase can not oxidise these non-phenolic substrates directly. The oxidation step is performed by the oxidised form of the mediator (Medox), generated on its interaction with laccase. The Medox can follow either an electron transfer (ET) or a radical hydrogen atom transfer (HAT) route of oxidation of the substrates. Experimental evidence is reported that enables unambiguous assessment of the occurrence of either one the oxidation routes with each of the investigated mediators, namely, ABTS, HBT, HPI and VLA. Support to the conclusions is provided by (i) investigating the intermolecular selectivity of oxidation with appropriate substrates, (ii) attempting Hammett correlations for the oxidation of a series of 4-X-substituted benzyl alcohols, (iii) measuring the kinetic isotope effect, (iv) investigating the product pattern with suitable probe precursors. Based on these points, a HAT mechanism results to be followed by the laccase–HBT, laccase–HPI and laccase–VLA systems, whereas an ET route appears feasible in the case of the laccase–ABTS system.

Graphical abstract: Promoting laccase activity towards non-phenolic substrates: a mechanistic investigation with some laccase–mediator systems

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Publication details

The article was received on 12 Sep 2002, accepted on 21 Oct 2002 and first published on 29 Nov 2002


Article type: Paper
DOI: 10.1039/B208951C
Citation: Org. Biomol. Chem., 2003,1, 191-197
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    Promoting laccase activity towards non-phenolic substrates: a mechanistic investigation with some laccase–mediator systems

    P. Baiocco, A. M. Barreca, M. Fabbrini, C. Galli and P. Gentili, Org. Biomol. Chem., 2003, 1, 191
    DOI: 10.1039/B208951C

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