title: Electrochemical Control of Rapid Bioorthogonal Tetrazine Ligations for Selective Functionalization of Microelectrodes.
abstract: We demonstrate that bioorthogonal tetrazine ligations can be utilized to rapidly modify electrode surfaces, both with redox probes and enzymes. Furthermore, we show that the redox-active nature of 1,2,4,5-tetrazines can be exploited to gain electrochemical control over surface modification. To our knowledge this is the first demonstration of controlling a tetrazine ligation by changing the redox state of one of the reactants. We utilize the redox-switchable feature of tetrazine ligations for the site-selective functionalization of a 10 μm spaced interdigitated array of microelectrodes. In addition, we were able to achieve potential controlled ligation of the redox enzyme horseradish peroxidase to a macroscopic planar electrode. The rapid kinetics, bioorthogonal reactivity, and electrochemical control provided by tetrazine ligations should lead to numerous applications related to electrode functionalization.
authors.affiliation: Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093, United States.
authors.forename: Fabian
authors.initials: F
authors.lastname: Ehret
authors.affiliation: Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093, United States.
authors.forename: Haoxing
authors.initials: H
authors.lastname: Wu
authors.affiliation: Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093, United States.
authors.forename: Seth C
authors.initials: SC
authors.lastname: Alexander
authors.affiliation: Department of Chemistry and Biochemistry, University of California, San Diego, La Jolla, California 92093, United States.
authors.forename: Neal K
authors.initials: NK
authors.lastname: Devaraj
mesh_terms: D031215:Armoracia / Q000737:chemistry / Q000201:enzymology; D055664:Electrochemical Techniques / Q000295:instrumentation / Q000379:methods*; D004800:Enzymes, Immobilized / Q000737:chemistry; D004867:Equipment Design; D006573:Heterocyclic Compounds, 1-Ring / Q000737:chemistry*; D006735:Horseradish Peroxidase / Q000737:chemistry; D008839:Microelectrodes; D008958:Models, Molecular; D010084:Oxidation-Reduction; D013499:Surface Properties
chemical_list: D004800:Enzymes, Immobilized; D006573:Heterocyclic Compounds, 1-Ring; D006735:Horseradish Peroxidase