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2942751423
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note
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Any contribution of the direct reduction current of nitromethane in ddab is expected to be very small. Subtraction of voltammograms in ddab/PG at different concentrations of nitromethane from catalytic voltammograms recorded on Mb/ddab/PG would actually overestimate the direct contribution. In fact, under catalytic conditions, as described, the catalytic consumption of nitromethane is kinetically faster than direct reduction and is such that the substrate concentration is virtually zero at any moment at the electrode surface in the presence of myoglobin loaded in the film.
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25
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2942734525
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note
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(a) A voltammogram demonstrating this fact is given in Supporting Information.
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26
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2942701315
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note
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(b) The complex was formed by reaction of myoglobin with nitromethane in the presence of excess dithionite and was purified on size-exclusion column. The Mb-nitrosomethane was found to be very stable, which allowed us to modify PG electrodes as described in ref 11b. The stability of the preformed complex in the film was checked by UV-vis spectroscopy.
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27
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2942743842
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note
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(c) Also see Supporting Information for experimental evidence.
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28
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0034638627
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2942714403
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note
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Experiments to determine faradaic yields, as well as product distribution at different potentials, are underway.
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34
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