Direct Electrochemical Generation of Catalytically Competent Oxyferryl Species of Classes I and P Dye Decolorizing Peroxidases
This work introduces a novel way to obtain catalytically competent oxyferryl species for two different dye-decolorizing peroxidases (DyPs) in the absence of H<sub>2</sub>O<sub>2</sub> or any other peroxide by simply applying a reductive electrochemical potential under aerobic...
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2021
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oai:doaj.org-article:dd972741cbe34ac985f49ef4c528795d2021-11-25T17:57:33ZDirect Electrochemical Generation of Catalytically Competent Oxyferryl Species of Classes I and P Dye Decolorizing Peroxidases10.3390/ijms2222125321422-00671661-6596https://doaj.org/article/dd972741cbe34ac985f49ef4c528795d2021-11-01T00:00:00Zhttps://www.mdpi.com/1422-0067/22/22/12532https://doaj.org/toc/1661-6596https://doaj.org/toc/1422-0067This work introduces a novel way to obtain catalytically competent oxyferryl species for two different dye-decolorizing peroxidases (DyPs) in the absence of H<sub>2</sub>O<sub>2</sub> or any other peroxide by simply applying a reductive electrochemical potential under aerobic conditions. UV-vis and resonance Raman spectroscopies show that this method yields long-lived compounds II and I for the DyPs from <i>Bacillus subtilis</i> (BsDyP; Class I) and <i>Pseudomonas putida</i> (PpDyP; Class P), respectively. Both electrochemically generated high valent intermediates are able to oxidize ABTS at both acidic and alkaline pH. Interestingly, the electrocatalytic efficiencies obtained at pH 7.6 are very similar to the values recorded for regular catalytic ABTS/H<sub>2</sub>O<sub>2</sub> 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 an extended pH range without the need of harmful reagents such as H<sub>2</sub>O<sub>2</sub>.Magalí F. ScocozzaLígia O. MartinsDaniel H. MurgidaMDPI AGarticledye-decolorizing peroxidasescompound Icompound IIRaman spectroscopyspectroelectrochemistryBiology (General)QH301-705.5ChemistryQD1-999ENInternational Journal of Molecular Sciences, Vol 22, Iss 12532, p 12532 (2021) |
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dye-decolorizing peroxidases compound I compound II Raman spectroscopy spectroelectrochemistry Biology (General) QH301-705.5 Chemistry QD1-999 |
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dye-decolorizing peroxidases compound I compound II Raman spectroscopy spectroelectrochemistry Biology (General) QH301-705.5 Chemistry QD1-999 Magalí F. Scocozza Lígia O. Martins Daniel H. Murgida Direct Electrochemical Generation of Catalytically Competent Oxyferryl Species of Classes I and P Dye Decolorizing Peroxidases |
description |
This work introduces a novel way to obtain catalytically competent oxyferryl species for two different dye-decolorizing peroxidases (DyPs) in the absence of H<sub>2</sub>O<sub>2</sub> or any other peroxide by simply applying a reductive electrochemical potential under aerobic conditions. UV-vis and resonance Raman spectroscopies show that this method yields long-lived compounds II and I for the DyPs from <i>Bacillus subtilis</i> (BsDyP; Class I) and <i>Pseudomonas putida</i> (PpDyP; Class P), respectively. Both electrochemically generated high valent intermediates are able to oxidize ABTS at both acidic and alkaline pH. Interestingly, the electrocatalytic efficiencies obtained at pH 7.6 are very similar to the values recorded for regular catalytic ABTS/H<sub>2</sub>O<sub>2</sub> 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 an extended pH range without the need of harmful reagents such as H<sub>2</sub>O<sub>2</sub>. |
format |
article |
author |
Magalí F. Scocozza Lígia O. Martins Daniel H. Murgida |
author_facet |
Magalí F. Scocozza Lígia O. Martins Daniel H. Murgida |
author_sort |
Magalí F. Scocozza |
title |
Direct Electrochemical Generation of Catalytically Competent Oxyferryl Species of Classes I and P Dye Decolorizing Peroxidases |
title_short |
Direct Electrochemical Generation of Catalytically Competent Oxyferryl Species of Classes I and P Dye Decolorizing Peroxidases |
title_full |
Direct Electrochemical Generation of Catalytically Competent Oxyferryl Species of Classes I and P Dye Decolorizing Peroxidases |
title_fullStr |
Direct Electrochemical Generation of Catalytically Competent Oxyferryl Species of Classes I and P Dye Decolorizing Peroxidases |
title_full_unstemmed |
Direct Electrochemical Generation of Catalytically Competent Oxyferryl Species of Classes I and P Dye Decolorizing Peroxidases |
title_sort |
direct electrochemical generation of catalytically competent oxyferryl species of classes i and p dye decolorizing peroxidases |
publisher |
MDPI AG |
publishDate |
2021 |
url |
https://doaj.org/article/dd972741cbe34ac985f49ef4c528795d |
work_keys_str_mv |
AT magalifscocozza directelectrochemicalgenerationofcatalyticallycompetentoxyferrylspeciesofclassesiandpdyedecolorizingperoxidases AT ligiaomartins directelectrochemicalgenerationofcatalyticallycompetentoxyferrylspeciesofclassesiandpdyedecolorizingperoxidases AT danielhmurgida directelectrochemicalgenerationofcatalyticallycompetentoxyferrylspeciesofclassesiandpdyedecolorizingperoxidases |
_version_ |
1718411835908030464 |