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Title: Nitric oxide is an obligate bacterial nitrification intermediate produced by hydroxylamine oxidoreductase

Authors:
; ORCiD logo
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1371603
Grant/Contract Number:
SC0013997
Resource Type:
Journal Article: Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 114; Journal Issue: 31; Related Information: CHORUS Timestamp: 2017-09-05 16:54:23; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Country of Publication:
United States
Language:
English

Citation Formats

Caranto, Jonathan D., and Lancaster, Kyle M. Nitric oxide is an obligate bacterial nitrification intermediate produced by hydroxylamine oxidoreductase. United States: N. p., 2017. Web. doi:10.1073/pnas.1704504114.
Caranto, Jonathan D., & Lancaster, Kyle M. Nitric oxide is an obligate bacterial nitrification intermediate produced by hydroxylamine oxidoreductase. United States. doi:10.1073/pnas.1704504114.
Caranto, Jonathan D., and Lancaster, Kyle M. 2017. "Nitric oxide is an obligate bacterial nitrification intermediate produced by hydroxylamine oxidoreductase". United States. doi:10.1073/pnas.1704504114.
@article{osti_1371603,
title = {Nitric oxide is an obligate bacterial nitrification intermediate produced by hydroxylamine oxidoreductase},
author = {Caranto, Jonathan D. and Lancaster, Kyle M.},
abstractNote = {},
doi = {10.1073/pnas.1704504114},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 31,
volume = 114,
place = {United States},
year = 2017,
month = 7
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1073/pnas.1704504114

Citation Metrics:
Cited by: 8works
Citation information provided by
Web of Science

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  • A H{sub 2}-NO fuel cell was designed for the synthesis of hydroxylamine in the gas phase. The hydroxylamine produced was trapped in an aqueous solution of H{sub 2}SO{sub 4} held in a silica-wool disk used as an electrolyte barrier for H{sub 2} and NO. Among the cathode electrocatalysts tested, iron-phthalocyanine (Fe-Pc) impregnated in graphite was the most favorable one for selective synthesis of hydroxylamine. Active carbon and carbon whiskers used to support the Fe-Pc enhanced the formation of hydroxylamine remarkably. The carbon itself slightly catalyzed the formation of N{sub 2}O and NH{sub 3}. Excluding the effects of the support, Fe-Pcmore » catalyzed the electrochemical synthesis of hydroxylamine with high selectivity ({approx} 100%). Applied voltage across the cell did not appreciably enhance the formation of hydroxylamine. The reaction under short-circuit conditions was most favorable for the synthesis of hydroxylamine. It is suggested that the reduction of NO occurs on the Fe{sup 2+} site of Fe-Pc with protons and electrons transferred from the anode. The very selective synthesis of hydroxylamine over Fe-Pc must be ascribed to an Fe{sup 2+} site isolated by phthalocyanine ring. This isolation prohibits both the formation of N{sub 2}O through the intramolecular elimination of H{sub 2}O from the adjacent NHO intermediates and the formation of N{sub 2} and NH{sub 3} through the breaking of N-O bonds.« less
  • The reaction of nitric oxide with hydroxylamine conforms to the rate law -dP/sub NO//dt = k/sub 2/(NH/sub 2/O/sup -/)P/sub NO/ in the pH range 7.29-13.14, confirming the rate-determining abstraction of an N-bound H atom by NO. Measured kinetic quantities: k/sub 2/ = 6.68 x 10/sup -3/ M/sup -1/ s/sup -1/ at 25/sup 0/C; ..delta.. H double dagger = 29.6 kJ mol/sup -1/; ..delta.. S double dagger = -189 J K/sup -1/ mol/sup -1/. Thermodynamic values have been obtained for the pK/sub a/ of NH/sub 2/OH at several temperatures; ..delta.. H of dissociation = 55.29 kJ mol/sup -1/. The presence ofmore » trace amounts of O/sub 2/ in the NO-NH/sub 2/OH reaction system catalyzes the reaction and leads to a reduced molar product ratio n/sub N/sub 2/O/, effects that are ascribed at least in part to reactive N/sub 2/O/sub 3/. The difference in reactivity between the NO/sup -/ intermediate formed in this reaction and that produced in trioxodinitrate decomposition is discussed.« less
  • The reactions between NO and the hydroxylamines CH/sub 3/NHOH, NH/sub 2/OCH/sub 3/, and CH/sub 3/NHOCH/sub 3/ proceed by N-bound H atom abstraction to form HNO. In the case of the dialkyl compounds (CH/sub 3/)/sub 2/NOH and (C/sub 2/H/sub 5/)/sub 2/NOH, abstraction occurs at the ..cap alpha..-carbon. The reaction is inhibited by O-methylation since no reactive anion can form. The ratio of reactivities of NH/sub 2/O/sup -/ to NH/sub 2/OH is determined to be at least 3.38 x 10/sup 5/. In the reaction between NO and CH/sub 3/NHOH, unlike that with NH/sub 2/OH, a stable nitrosohydroxylamine product remains in solution andmore » does not release N/sub 2/O. Release of N/sub 2/ product in this case is delayed, an observation that is interpreted in terms of an intermediate N-nitrosomethylamine species on the pathway of reduction of HNO. Release of N/sub 2/ from this species is facilitated by Cl/sup -/ with formation of CH/sub 3/Cl. The N/sub 2/O product of reaction with the N,O- and N,N-dialkyl compounds arises largely from HNO dimerization, even at very high pH, indicating formation of stable nitrosohydroxylamine products. In the latter case an apparent competition with a nitrone-forming reaction occurs, leading to further reduction of NO to NO/sup -/.« less