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-1 tanto em eletrodo de carbono vitreo (GC) nao modificado quanto em eletrodo GC modificado com nanotubos de carbono de paredes multiplas foi investigado por voltametria ciclica e eletrolise a potencial controlado. Os resultados obtidos permitiram inferir um mecanismo de eletroreducao complexo com etapas quimicas e eletroquimicas, acopladas a reacao inicial de transferencia de eletron. Citrinina apresentou pico catodico unico que corresponde no minimo a duas etapas de reducao envolvendo um eletron e duas reacoes quimicas homogeneas, segundo mecanismo de autoprotonacao do tipo ECEC (transferencia de eletron acoplada com aceitacao de proton). As reacoes quimicas se originam nas transferencias de proton intermolecular do substrato para os seus produtos intermedios basicos de reducao, caracterizando um mecanismo de autoprotonacao. Analise cinetica por procedimentos de simulacao de resultados voltametricos permitiu uma caracterizacao completa do mecanismo de reducao heterogeneo de citrinina. Electrochemical reduction mechanism of citrinin in acetonitrile plus 0.1 mol L -1 (C4H9)4NClO4 at both bare and modified with multi-walled carbon nanotube glassy carbon (GC) electrodes was investigated by cyclic voltammetry and controlled potential electrolysis. Results allowed to infer a complex electroreduction mechanism with chemical and electrochemical steps coupled to the initial electron transfer reaction. Citrinin shows a single cathodic peak that corresponds at least to two electron reduction steps and two homogeneous chemical reactions, conforming to an ECEC (electron-transfer coupled with proton acceptance) self-protonation mechanism. The chemical reactions are originated in the intermolecular proton transfers from the substrate to its basic reduction intermediates, featuring a self-protonation mechanism. Kinetics analysis by simulation procedures of voltammetric results permitted a fully characterization of the mechanism of citrinin heterogeneous reduction.

journal of the brazilian chemical society

Electrochemical reduction of the mycotoxin citrinin at bare and modified with multi-walled carbon nanotubes glassy carbon electrodes in a non-aqueous reaction medium