ArticleProceedings of the National Academy of Sciences of the United States of America2015
Heme-thiolate ferryl of aromatic peroxygenase is basic and reactive.
Article in Proceedings of the National Academy of Sciences of the United States of America, 2015. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 43 papers.
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Who cites it
43 citing papers in PubMed, 93 citations in OpenAlex.
- Discovery of noncanonical cytochrome P450 enzymes in nature.Nature chemical biology · 2026Article
- Exploiting the Intrinsic Peroxidase Activity of Unspecific Peroxygenase for the Oxidative Cyclization of Ortho-Substituted Phenols.Chemistry (Weinheim an der Bergstrasse, Germany) · 2026Article
- Structure, characterisation and application of an unspecific peroxygenase fromRSC chemical biology · 2026Article
- Enhanced secretion of an Agrocybe aegerita peroxygenase variant in K. phaffii using the native signal peptide.AMB Express · 2026Article
- Regulation of ferryl reactivity by the cytochrome P450 decarboxylase OleT.Journal of inorganic biochemistry · 2025Article
- Non-Canonical Cytochrome P450 Enzymes in Nature.bioRxiv : the preprint server for biology · 2024Article
- Axial Ligation Impedes Proton-Coupled Electron-Transfer Reactivity of a Synthetic Compound-I Analogue.Journal of the American Chemical Society · 2024Article
- Functional Model of Compound II of Cytochrome P450: Spectroscopic Characterization and Reactivity Studies of a FeJACS Au · 2024Article
- Heme-copper and Heme OJournal of inorganic biochemistry · 2023Review
- Factors controlling the reactivity of synthetic compound-I Analogs.Journal of porphyrins and phthalocyanines · 2023Article
- Dimer-assisted mechanism of (un)saturated fatty acid decarboxylation for alkene production.Proceedings of the National Academy of Sciences of the United States of America · 2023Article
- Comparing the Catalytic and Structural Characteristics of a 'Short' Unspecific Peroxygenase (UPO) Expressed in Pichia pastoris and Escherichia coli.Chembiochem : a European journal of chemical biology · 2023Article
- Article
- Peroxide-Mediated Oxygenation of Organic Compounds by Fungal Peroxygenases.Antioxidants (Basel, Switzerland) · 2022Review
- Hemoprotein Catalyzed Oxygenations: P450s, UPOs, and Progress toward Scalable Reactions.JACS Au · 2021Review
- A Noncanonical Tryptophan Analogue Reveals an Active Site Hydrogen Bond Controlling Ferryl Reactivity in a Heme Peroxidase.JACS Au · 2021Article
- Molecular Dynamics Simulations of a Cytochrome P450 fromMolecules (Basel, Switzerland) · 2021Article
- Molecular Rationale for Partitioning between C-H and C-F Bond Activation in Heme-Dependent Tyrosine Hydroxylase.Journal of the American Chemical Society · 2021Article
- Mapping and Exploiting the Promiscuity of OxyB toward the Biocatalytic Production of Vancomycin Aglycone Variants.ACS catalysis · 2020Article
- M[TPP]Cl (M = Fe or Mn)-Catalyzed Oxidative Amination of Phenols by Primary and Secondary Anilines.Organic letters · 2020Article
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Authors and funding
4 authors at 3 institutions in 2 countries.
Funding
Abstract
A kinetic and spectroscopic characterization of the ferryl intermediate (APO-II) from APO, the heme-thiolate peroxygenase from Agrocybe aegerita, is described. APO-II was generated by reaction of the ferric enzyme with metachloroperoxybenzoic acid in the presence of nitroxyl radicals and detected with the use of rapid-mixing stopped-flow UV-visible (UV-vis) spectroscopy. The nitroxyl radicals served as selective reductants of APO-I, reacting only slowly with APO-II. APO-II displayed a split Soret UV-vis spectrum (370 nm and 428 nm) characteristic of thiolate ligation. Rapid-mixing, pH-jump spectrophotometry revealed a basic pKa of 10.0 for the Fe(IV)-O-H of APO-II, indicating that APO-II is protonated under typical turnover conditions. Kinetic characterization showed that APO-II is unusually reactive toward a panel of benzylic C-H and phenolic substrates, with second-order rate constants for C-H and O-H bond scission in the range of 10-10(7) M(-1)⋅s(-1). Our results demonstrate the important role of the axial cysteine ligand in increasing the proton affinity of the ferryl oxygen of APO intermediates, thus providing additional driving force for C-H and O-H bond scission.
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