ArticleScience (New York, N.Y.)2013
Iron(IV)hydroxide pK(a) and the role of thiolate ligation in C-H bond activation by cytochrome P450.
Article in Science (New York, N.Y.), 2013. The graph could read no effect estimate from its abstract, so it casts no vote on the map. Cited by 152 papers.
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Who cites it
152 citing papers in PubMed, 326 citations in OpenAlex.
- Article
- Benchmark Study for Calculations of pKa Values of Metal Ligands in Proteins.Journal of chemical theory and computation · 2026Article
- Anchoring mechanism-inspired discovery of a bacterial P450 gene conferring resistance to auxin herbicides.Nature communications · 2026Article
- An assessment of the cytochrome P450 2-hydroxyisoflavanone synthase (2-HIS) crystal structure.Communications biology · 2026Article
- High-Valent Late Transition Metal-Oxo Complexes: Breaking Boundaries at the Oxo Wall and Beyond.Chemical reviews · 2026Review
- Review
- Can ferric-oxyl excited states explain elongated iron-oxygen bonds in heme peroxidase catalytic intermediates?Nature communications · 2026Article
- Oxidizable amino acids around cytochrome P450 hemes.Journal of inorganic biochemistry · 2026Article
- Manipulating Terminal Iron-Hydroxide Nucleophilicity through Redox.Journal of the American Chemical Society · 2026Article
- Electronic Structure Contributions to the Reactivity of Mononuclear FeAccounts of chemical research · 2026Article
- Hole migration in cytochrome P450.QRB discovery · 2026Article
- Regulation of ferryl reactivity by the cytochrome P450 decarboxylase OleT.Journal of inorganic biochemistry · 2025Article
- Design and characterization of a tunable open TEJournal of magnetic resonance (San Diego, Calif. : 1997) · 2025Article
- Basicity-Controlled C-H Bond Activation by a Structurally Characterized Ni(III)-Hydroxo Complex.Journal of the American Chemical Society · 2025Article
- Intramolecular Oxo Atom Migration to theJournal of the American Chemical Society · 2025Article
- Spectroscopic Interrogation of Thiolate Hydrogen Bonding in the CO Sensor Protein CooA: Implications for Thiolate Ligation Stability and Cytochrome P450 Function.Chemistry (Weinheim an der Bergstrasse, Germany) · 2025Article
- Modulation of heme peroxo nucleophilicities with axial ligands reveal key insights into the mechanistic landscape of nitric oxide synthase.Chemical science · 2025Article
- Stabilization of the Ferryl═Oxoheme Form ofJournal of the American Chemical Society · 2025Article
- Experimental electronic structures of the FeProceedings of the National Academy of Sciences of the United States of America · 2025Article
- Organic photoredox-catalyzed unimolecular PCET of benzylic alcohols.Chemical science · 2025Article
92 more citing papers are in PubMed but not listed here.
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Authors and funding
8 authors at 1 institution in 1 country.
Funding
Abstract
Cytochrome P450 enzymes activate oxygen at heme iron centers to oxidize relatively inert substrate carbon-hydrogen bonds. Cysteine thiolate coordination to iron is posited to increase the pK(a) (where K(a) is the acid dissociation constant) of compound II, an iron(IV)hydroxide complex, correspondingly lowering the one-electron reduction potential of compound I, the active catalytic intermediate, and decreasing the driving force for deleterious auto-oxidation of tyrosine and tryptophan residues in the enzyme's framework. Here, we report on the preparation of an iron(IV)hydroxide complex in a P450 enzyme (CYP158) in ≥90% yield. Using rapid mixing technologies in conjunction with Mössbauer, ultraviolet/visible, and x-ray absorption spectroscopies, we determine a pK(a) value for this compound of 11.9. Marcus theory analysis indicates that this elevated pK(a) results in a >10,000-fold reduction in the rate constant for oxidations of the protein framework, making these processes noncompetitive with substrate oxidation.
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Read under generation 80e0d062 · epoch 390. Bibliography from PubMed, PubMed Central and OpenAlex; grants from NIH RePORTER; trial links from ClinicalTrials.gov; estimates, votes and beliefs from the OpenQuestion graph.