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Title: Decomposition of amino diazeniumdiolates (NONOates): Molecular mechanisms

Abstract

Although diazeniumdiolates (X[N(O)NO] -) are extensively used in biochemical, physiological, and pharmacological studies due to their ability to release NO and/or its congeneric nitroxyl, the mechanisms of these processes remain obscure. In this work, we used a combination of spectroscopic, kinetic, and computational techniques to arrive at a quantitatively consistent molecular mechanism for decomposition of amino diazeniumdiolates (amino NONOates: R 2N[N(O)NO] -, where R = —N(C 2H 5) 2(1), —N(C 3H 4NH 2) 2(2), or —N(C 2H 4NH 2) 2(3)). Decomposition of these NONOates is triggered by protonation of their [NN(O)NO] - group with the apparent pKa and decomposition rate constants of 4.6 and 1 s -1 for 1; 3.5 and 0.083 s -1 for 2; and 3.8 and 0.0033 s -1 for 3. Although protonation occurs mainly on the O atoms of the functional group, only the minor R 2N(H)N(O)NO tautomer (population ~ 10 -7, for 1) undergoes the N—N heterolytic bond cleavage (k d ~ 107 s -1 for 1) leading to amine and NO. Decompositions of protonated amino NONOates are strongly temperature-dependent; activation enthalpies are 20.4 and 19.4 kcal/mol for 1 and 2, respectively, which includes contributions from both the tautomerization and bond cleavage. Thus, the bondmore » cleavage rates exhibit exceptional sensitivity to the nature of R substituents which strongly modulate activation entropy. At pH < 2, decompositions of all three NONOates that have been investigated are subject to additional acid catalysis that occurs through di-protonation of the [NN(O)NO] - group.« less

Authors:
 [1];  [2];  [1]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1169029
Report Number(s):
BNL-107197-2014-JA
Journal ID: ISSN 0162-0134; R&D Project: CO004; KC0304030
Grant/Contract Number:
SC00112704
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Journal of Inorganic Biochemistry
Additional Journal Information:
Journal Volume: 141; Journal Issue: C; Journal ID: ISSN 0162-0134
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; diazeniumdiolates; NONOates; NO donor; mechanism; tautomerization; ab initio calculations

Citation Formats

Shaikh, Nizamuddin, Valiev, Marat, and Lymar, Sergei V. Decomposition of amino diazeniumdiolates (NONOates): Molecular mechanisms. United States: N. p., 2014. Web. doi:10.1016/j.jinorgbio.2014.08.008.
Shaikh, Nizamuddin, Valiev, Marat, & Lymar, Sergei V. Decomposition of amino diazeniumdiolates (NONOates): Molecular mechanisms. United States. doi:10.1016/j.jinorgbio.2014.08.008.
Shaikh, Nizamuddin, Valiev, Marat, and Lymar, Sergei V. Sat . "Decomposition of amino diazeniumdiolates (NONOates): Molecular mechanisms". United States. doi:10.1016/j.jinorgbio.2014.08.008. https://www.osti.gov/servlets/purl/1169029.
@article{osti_1169029,
title = {Decomposition of amino diazeniumdiolates (NONOates): Molecular mechanisms},
author = {Shaikh, Nizamuddin and Valiev, Marat and Lymar, Sergei V.},
abstractNote = {Although diazeniumdiolates (X[N(O)NO]-) are extensively used in biochemical, physiological, and pharmacological studies due to their ability to release NO and/or its congeneric nitroxyl, the mechanisms of these processes remain obscure. In this work, we used a combination of spectroscopic, kinetic, and computational techniques to arrive at a quantitatively consistent molecular mechanism for decomposition of amino diazeniumdiolates (amino NONOates: R2N[N(O)NO]-, where R = —N(C2H5)2(1), —N(C3H4NH2)2(2), or —N(C2H4NH2)2(3)). Decomposition of these NONOates is triggered by protonation of their [NN(O)NO]- group with the apparent pKa and decomposition rate constants of 4.6 and 1 s-1 for 1; 3.5 and 0.083 s-1 for 2; and 3.8 and 0.0033 s-1 for 3. Although protonation occurs mainly on the O atoms of the functional group, only the minor R2N(H)N(O)NO tautomer (population ~ 10-7, for 1) undergoes the N—N heterolytic bond cleavage (kd ~ 107 s-1 for 1) leading to amine and NO. Decompositions of protonated amino NONOates are strongly temperature-dependent; activation enthalpies are 20.4 and 19.4 kcal/mol for 1 and 2, respectively, which includes contributions from both the tautomerization and bond cleavage. Thus, the bond cleavage rates exhibit exceptional sensitivity to the nature of R substituents which strongly modulate activation entropy. At pH < 2, decompositions of all three NONOates that have been investigated are subject to additional acid catalysis that occurs through di-protonation of the [NN(O)NO]- group.},
doi = {10.1016/j.jinorgbio.2014.08.008},
journal = {Journal of Inorganic Biochemistry},
number = C,
volume = 141,
place = {United States},
year = {Sat Aug 23 00:00:00 EDT 2014},
month = {Sat Aug 23 00:00:00 EDT 2014}
}

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