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| - Electrochemical Behavior of Nitrate ReductaseImmobilized in Self-Assembled Structures with RedoxPolyviologen
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| - We report on a novel bioelectrode based on self-assembled multilayers of nitrate reductase (NR)intercalated with a cationic viologen-functionalized polyvinylpyridinium (PV) polymer specially synthesizedfor this purpose. Different samples of polymer proved to have varying substitution ratios, according toNMR experiments. The electrostatic self-assemblies were built up on a thiol-modified gold surface usinga strategy previously described by Hodak et al. The electrochemical behavior of PV and the response ofthe electrodes toward nitrate were followed by cyclic voltammetry. The catalytic currents obtained wereproportional to the number of NR-immobilized layers, as well as to the polymer substitution degree,proving that the enzyme remained active under immobilization conditions and that it can be regeneratedby PV redox moieties. Experiments with quartz crystal microbalance electroacoustic impedance werecarried out to follow quantitatively the multilayer film formation. The kinetics of the adsorption processesand the influence of the ionic strength are investigated. The evaluation of water and ion exchange duringthe reduction of PV is also achieved from electroacoustic and electrochemical experiments. Results indicatean important water exchange associated with the polymer redox behavior.
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