Influences of the heme-lysine crosslink in cytochrome P460 over redox catalysis and nitric oxide sensitivity
Abstract
Ammonia (NH3)-oxidizing bacteria (AOB) derive total energy for life from the multi-electron oxidation of NH3 to nitrite (NO2-). One obligate intermediate of this metabolism is hydroxylamine (NH2OH), which can be oxidized to the potent greenhouse agent nitrous oxide (N2O) by the AOB enzyme cytochrome (cyt) P460. We have now spectroscopically characterized a 6-coordinate (6c) {FeNO}7 intermediate on the NH2OH oxidation pathway of cyt P460. This species has two fates: it can either be oxidized to the {FeNO}6 that then undergoes attack by NH2OH to ultimately generate N2O, or it can lose its axial His ligand, thus generating a stable, off-pathway 5-coordinate (5c) {FeNO}7 species. We show that the wild type (WT) cyt P460 exhibits a slow nitric oxide (NO)-independent conversion (kHis-off = 2.90 × 10-3 s-1), whereas a cross-link-deficient Lys70Tyr cyt P460 mutant protein underwent His dissociation via both a NO-independent (kHis-off = 3.8 × 10-4 s-1) and a NO-dependent pathway [kHis-off(NO) = 790 M-1 s-1]. Eyring analyses of the NO-independent pathways for these two proteins revealed a significantly larger (ca. 27 cal mol-1 K-1) activation entropy (ΔS‡) in the cross-link-deficient mutant. Our results suggest that the Lys–heme cross-link confers rigidity to the positioning of the heme P460 cofactor tomore »
- Authors:
-
- Department of Chemistry and Chemical Biology, Baker Laboratory, Cornell University, Ithaca, USA
- Publication Date:
- Research Org.:
- Cornell Univ., Ithaca, NY (United States); Stanford Univ., CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1415513
- Alternate Identifier(s):
- OSTI ID: 1505565
- Grant/Contract Number:
- AC02-76SF00515; SC0013997
- Resource Type:
- Published Article
- Journal Name:
- Chemical Science
- Additional Journal Information:
- Journal Name: Chemical Science Journal Volume: 9 Journal Issue: 2; Journal ID: ISSN 2041-6520
- Publisher:
- Royal Society of Chemistry (RSC)
- Country of Publication:
- United Kingdom
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Vilbert, Avery C., Caranto, Jonathan D., and Lancaster, Kyle M. Influences of the heme-lysine crosslink in cytochrome P460 over redox catalysis and nitric oxide sensitivity. United Kingdom: N. p., 2018.
Web. doi:10.1039/C7SC03450D.
Vilbert, Avery C., Caranto, Jonathan D., & Lancaster, Kyle M. Influences of the heme-lysine crosslink in cytochrome P460 over redox catalysis and nitric oxide sensitivity. United Kingdom. https://doi.org/10.1039/C7SC03450D
Vilbert, Avery C., Caranto, Jonathan D., and Lancaster, Kyle M. Mon .
"Influences of the heme-lysine crosslink in cytochrome P460 over redox catalysis and nitric oxide sensitivity". United Kingdom. https://doi.org/10.1039/C7SC03450D.
@article{osti_1415513,
title = {Influences of the heme-lysine crosslink in cytochrome P460 over redox catalysis and nitric oxide sensitivity},
author = {Vilbert, Avery C. and Caranto, Jonathan D. and Lancaster, Kyle M.},
abstractNote = {Ammonia (NH3)-oxidizing bacteria (AOB) derive total energy for life from the multi-electron oxidation of NH3 to nitrite (NO2-). One obligate intermediate of this metabolism is hydroxylamine (NH2OH), which can be oxidized to the potent greenhouse agent nitrous oxide (N2O) by the AOB enzyme cytochrome (cyt) P460. We have now spectroscopically characterized a 6-coordinate (6c) {FeNO}7 intermediate on the NH2OH oxidation pathway of cyt P460. This species has two fates: it can either be oxidized to the {FeNO}6 that then undergoes attack by NH2OH to ultimately generate N2O, or it can lose its axial His ligand, thus generating a stable, off-pathway 5-coordinate (5c) {FeNO}7 species. We show that the wild type (WT) cyt P460 exhibits a slow nitric oxide (NO)-independent conversion (kHis-off = 2.90 × 10-3 s-1), whereas a cross-link-deficient Lys70Tyr cyt P460 mutant protein underwent His dissociation via both a NO-independent (kHis-off = 3.8 × 10-4 s-1) and a NO-dependent pathway [kHis-off(NO) = 790 M-1 s-1]. Eyring analyses of the NO-independent pathways for these two proteins revealed a significantly larger (ca. 27 cal mol-1 K-1) activation entropy (ΔS‡) in the cross-link-deficient mutant. Our results suggest that the Lys–heme cross-link confers rigidity to the positioning of the heme P460 cofactor to avoid the fast NO-dependent His dissociation pathway and subsequent formation of the off-pathway 5c {FeNO}7 species. The relevance of these findings to NO signaling proteins such as heme-nitric oxide/oxygen binding (H-NOX) is also discussed.},
doi = {10.1039/C7SC03450D},
journal = {Chemical Science},
number = 2,
volume = 9,
place = {United Kingdom},
year = {Mon Jan 01 00:00:00 EST 2018},
month = {Mon Jan 01 00:00:00 EST 2018}
}
https://doi.org/10.1039/C7SC03450D
Web of Science
Figures / Tables:
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