Direct Electrochemical Generation of Catalytically Competent Oxyferryl Species of Classes I and P Dye Decolorizing Peroxidases

MARTINS, L. O.; SCOCOZZA, MAGALI F.; MURGIDA, D.H.

INTERNATIONAL JOURNAL OF MOLECULAR SCIENCES

MOLECULAR DIVERSITY PRESERVATION INTERNATIONAL-MDPI

Lugar: Basel; Año: 2021 vol. 22

1422-0067

This work introduces a novel way to obtain catalytically competent oxyferryl species fortwo different dye-decolorizing peroxidases (DyPs) in the absence of H2O2 or any other peroxideby simply applying a reductive electrochemical potential under aerobic conditions. UV-vis andresonance Raman spectroscopies show that this method yields long-lived compounds II and I for theDyPs from Bacillus subtilis (BsDyP; Class I) and Pseudomonas putida (PpDyP; Class P), respectively.Both electrochemically generated high valent intermediates are able to oxidize ABTS at both acidicand alkaline pH. Interestingly, the electrocatalytic efficiencies obtained at pH 7.6 are very similar tothe values recorded for regular catalytic ABTS/H2O2 assays at the optimal pH of the enzymes, ca.3.7. These findings pave the way for the design of DyP-based electrocatalytic reactors operable in anextended pH range without the need of harmful reagents such as H2O2.