Electrochemistry of catechol terminated monolayers with Cu(II), Ni(II) and, Fe(III) cations: A model for the marine adhesive interface

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2008

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Brooksby, P.
Schiel, D.
Abell, A.

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Langmuir: the ACS journal of surfaces and colloids, 2008; 24(16):9074-9081

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Paula A. Brooksby, David R. Schiel and Andrew D. Abell

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Abstract

The redox electrochemistry of hydroquinone and Cu2+-, Ni2+-, and Fe3+-hydroquinone complexes immobilized at the SAM interface has been studied in aqueous solutions with pH 5 to 12 using cyclic voltammetry. Self-assembled monolayers were constructed with terminal hydroquinone residues designed to model marine adhesive proteins that use the DOPA (3,4-dihydroxyphenylalanine) moiety. Coordination of metal to the hydroquinone group results in a shift to the ligand oxidation potential, with the value for Delta E p,a dependent on the solution pH and identity of the metal. Cu2+ shifts the hydroquinone oxidation by -285 mV (pH 8.8), and Ni2+ by -194 mV (pH 9.16). The hydroquinone oxidation was shifted by -440 mV at pH 5 for Fe3+ solutions examined up to pH 7. By contrast, reduction of the quinone is unperturbed by the presence of Cu2+, Ni2+, and Fe3+ ions. Implications of these results to the mechanism of marine adhesion are discussed.

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Copyright © 2008 American Chemical Society

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