Kinetics of Ion-Exchange Binding of Redox Metal Cations to Thiolate−DNA Monolayers on Gold

Abstract
The ion-exchange kinetics of metal cation binding to and dissociation from thiolate−DNA monolayers on gold can be monitored by a simple electrochemical protocol. The apparent first-order rate constants were obtained by analyzing the time-dependent voltammetric behavior of the redox cation [Ru(NH3)6]3+. It was found that the binding kinetics is dominated by the structural nature of the film; i.e., the apparent first-order rate constant (kapp) decreases significantly upon increasing the surface density of DNA strands. Dissociation rate constants were obtained by transferring the incubated electrode into redox-free buffer solution. The kinetic data augment our fundamental understanding of metal ion−DNA interactions and are critical to ensure the accuracy and reliability of experimental DNA detection protocols.

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