Direct Electrochemical Bioconjugation on Metal Surfaces.

DNA has unique capabilities for molecular recognition and self-assembly, which have fostered its widespread incorporation into devices that are useful in science and medicine. Many of these platforms rely on thiol groups to tether DNA to gold surfaces, but this method is hindered by a lack of control over monolayer density and by secondary interactions between the nucleotide bases and the metal. In this work, we report an electrochemically activated bioconjugation reaction as a mild, reagent-free strategy to attach oligonucleotides to gold surfaces. Aniline-modified DNA was coupled to catechol-coated electrodes that were oxidized to o-quinones using an applied potential. High levels of coupling could be achieved in minutes. By changing the reaction time and the underlying catechol content, the final DNA surface coverage could be specified. The advantages of this method were demonstrated through the electrochemical detection of the endocrine disruptor bisphenol A, as well as the capture of living nonadherent cells on electrode surfaces by DNA hybridization. This method not only improves the attachment of DNA to metal surfaces but also represents a new direction for the site-specific attachment of biomolecules to device platforms.