Ab initio molecular orbital calculations have been used to study the effects of the molecular environment on the oxidation of thiolate and selenolate by hydrogen peroxide. The reaction was first examined in vacuo at the QCISD(T)/6-311+G(2df,2pd)//MP2/6-311+G(d,p) level of theory. It was found for both thiolate and selenolate that a reactant aggregate is formed, which has a dissociation rate constant comparable to the activation rate constant (about 10(-3) s(-1) for thiolate and 10(-1) s(-1) for selenolate). Using the polarizable continuum model (PCM) it was then found that the dissociation barrier energy decreases dramatically in water giving a dissociation rate constant of the order of 10(9) s(-1). In this case, the predicted overall rate constant of the thiolate reaction was about 10.2 mol(-1) dm3 s(-1), which is in good agreement with the experimental rate constant of cysteine oxidation in aqueous solution. The calculated rate constant for the selenolate reaction was somewhat higher (about 35.4 mol(-1) dm3 s(-1)). However, this value is several orders of magnitude smaller than the experimental value reported for the oxidation of selenocysteine in glutathione peroxidase. By considering the effect of the PCM dielectric constant on the reaction rate constant it was concluded that the high reactivity of the selenocysteine in glutathione peroxidase, as compared with cysteine, could be mainly due to the molecular environment of the selenocysteine residue.
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