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Molecular and Biological Catalysts Coimmobilization on Electrode by Combining Diazonium Electrografting and Sequential Click Chemistry
Author(s) -
Zhang Lin,
Vilà Neus,
Walcarius Alain,
Etienne Mathieu
Publication year - 2018
Publication title -
chemelectrochem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.182
H-Index - 59
ISSN - 2196-0216
DOI - 10.1002/celc.201800258
Subject(s) - click chemistry , azide , cycloaddition , alkene , chemistry , ferrocene , redox , catalysis , biomolecule , cyclic voltammetry , surface modification , combinatorial chemistry , electrochemistry , electrocatalyst , photochemistry , organic chemistry , electrode , biochemistry
A generic approach has been developed for sequential heterogeneous surface modification of electrodes. The strategy, which is applicable for a wide range of functional groups, involves two main steps. In the first one, azide‐alkene bifunctionalized electrodes are obtained by electrochemical reduction of a mixture of diazonium salts generated in situ from the corresponding 4‐azidoaniline and 4‐vinylaniline. In that way, we provide reactive sites that are available for further selective functionalization in a sequential process based on ‘click reactions’, in which subsequent immobilization of the targeted molecules is achieved by the azide‐alkyne cycloaddition Huisgen reaction and alkene‐thiol coupling. Feasibility of the method has been first demonstrated for the coimmobilization of two distinct redox moieties (cobaltocenium and ferrocene) as evidenced by cyclic voltammetry and X‐ray photoelectron spectroscopy measurements. The versatility of the sequential method has then been exploited for the coimmobilization of a molecular electrocatalyst [Cp*Rh(bpy) Cl] + and a biological catalyst, a NAD‐dependent dehydrogenase, that were proved to act in cascade in the electroenzymatic reduction of D‐fructose to D‐sorbitol. Such simple combination of diazonium chemistry and robust chemical reactions (‘click chemistry’) is promising for the environmentally friendly heterogeneous modification of electrodes with multiple chemical and biological catalysts.