N-aryl-N-hydroxy urethanes as peroxidase substrates

J. Kulys, H. J. Deussen, K. Krikstopaitis, P. Schneider, A. Ziemys

Research output: Contribution to journalArticle

3 Scopus citations

Abstract

N-Aryl-N-hydroxy urethanes (AHUs), which are promising N-OH mediators for oxidoreductase catalysis, are electrochemically active redox compounds with a redox potential of 0.35-0.40 V vs. SCE (0.59-0.64 V vs. NHE). Alkyl substituents in the carbamic acid residue have, as expected, only little influence on the redox potential. The highest potential was noticed for N-hydroxy-N-(4-cyanophenyl)-carbamic acid methyl ester. Recombinant Coprinus cinereus peroxidase (rCiP) catalyzes oxidation of the AHUs with apparent bimolecular constants kox of 2.5 · 104-7.5 · 104 M-1 s-1 at pH = 8.5 and 25°C. Structure-function connectivities of the substrates were analysed within the framework of the Marcus cross relationship and by using ab initio quantum chemical calculations. An excellent correlation of the redox potentials and the HOMO energies could be found. However, no correlation of log(kox) with redox potential and HOMO energy was indicated as predicted by theory. This was explained by specific docking of the substrates in the active center of rCiP.

Original languageEnglish (US)
Pages (from-to)295-304
Number of pages10
JournalMonatshefte fur Chemie
Volume132
Issue number2
DOIs
StatePublished - 2001

Keywords

  • Ab initio Calculations
  • Fungal peroxidase
  • Reactivity
  • Redox potential
  • Substrate docking

ASJC Scopus subject areas

  • Chemistry(all)

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