Understanding the geometry and electronics of metal-oxygen intermediate species formed during catalysis is an important step towards elucidating the catalytic mechanism. X-ray absorption spectroscopy and EXAFS are powerful spectroscopic techniques for local-geometric and electronic structure determination and can be applied to both single-crystal and solution samples. A combination of X-ray absorption spectroscopy with density functional theory calculations can present a holistic picture of the intermediates and overall catalytic mechanism. A combination of XAS, EXAFS and DFT techniques have been applied to the heme containing dye-decolorizing peroxidase DypB and its mutants in solution phase to comprehensively characterize the high valent Fe(IV)=O intermediate compound I. The studies have been extended to intermediates formed in-crystallo. The results indicate that the distal pocket mutants play an important role in the formation and stability of the compound I intermediate.

Solution and single crystal X-ray absorption spectroscopic studies on the dye-decolorizing peroxidase DypB

248th National Meeting (2014)

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