Interfacial and mass transport enhancement effects on rates of styrene epoxidation catalyzed by myoglobin films in microemulsions

Abstract

Biocatalytic surfaces hold promise for future clean methods of chemical synthesis. Biocatalyst films utilizing inexpensive redox proteins can operate in low-toxicity microemulsions with high capacities to dissolve nonpolar reactants. Crosslinked films of myoglobin (Mb) and poly(L-lysine) (PLL) attached to oxidized carbon cathodes gave up to 40-fold larger turnover rates in bicontinuous microemulsions compared to o/w microemulsions and micelles. Larger synthetic turnover rates are correlated with up to 10-fold faster diffusion of solutes in oil phases of the bicontinuous fluids, as measured by voltammetry. Visible and circular dichroism spectra suggest that myoglobin resides in the film in a largely aqueous environment. The reactant sites in films monitored by a fluorescent probe were more polar when films were in CTAB than in SDS microemulsions. These combined results suggest that larger mass transport rates in the bicontinuous fluids is a major factor for enhanced turnover rates. Electrostatic interactions between the charged films and oppositely charged surfactants may significantly influence turnover rates when reactant mass transport is not fast enough.