Superoxide radical anion adduct of 5,5-dimethyl-1-Pyrroline N-oxide. 4. Conformational effects on the EPR hyperfine splitting constants

Frederick A. Villamena, Yangping Liu, Jay L. Zweier

Research output: Contribution to journalArticle

Abstract

Spin trapping has been commonly employed in the detection of superoxide radical anion in chemical and biological systems; hence, accurate interpretation of the hyperfine splitting constants (hfsc's) arising from the O 2•- adducts (also referred to as hydroperoxyl (HO2) radical adducts) of various nitrones is important. In this work, the nature of the relevant hfsc's was investigated by examining the effect of conformational changes in the hydroperoxyl moiety of the O2•- adducts of 5,5-dimethyl-l-pyrroline N-oxide (DMPO), 5-ethoxycarbonyl-5-methyl-1-pyrroline N-oxide (EMPO), 5-diethoxyphosphoryl-5-methyl-l-pyrroline N-oxide (DEPMPO), 5-carbamoyl-5- methyl-1-pyrroline N-oxide (AMPO), and 7-oxa-l-azaspiro[4.4]non-1-en-6-one N-oxide, (CPCOMPO) on the magnitude of aN, aβ-H, and aγ-H. Conformational change around the substituents and their effect on the hfsc's were also explored. Results indicate that a β-H is most sensitive to conformational changes of the hydroperoxyl and substituent groups relative to hfsc's of other nuclei. The orbital overlap between the C-H σ-orbital and the SOMO of the nitroxyl nitrogen plays a crucial factor in determining the magnitude of the a β-H. The hfsc values for the O2•- adducts were predicted with high accuracy by using a low-cost computational method at the PCM(water)/BHandHLYP/EPR-III//B3LYP/6-31G* level of theory without taking into account the explicit water interaction.

Original languageEnglish (US)
Pages (from-to)12607-12615
Number of pages9
JournalJournal of Physical Chemistry A
Volume112
Issue number49
DOIs
StatePublished - Dec 11 2008
Externally publishedYes

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inorganic peroxides
Superoxides
adducts
Anions
Paramagnetic resonance
anions
Oxides
oxides
Pulse code modulation
Water
Biological systems
Computational methods
Nitrogen
orbitals
Costs
water
trapping
5,5-dimethyl-1-pyrroline-1-oxide
nitrogen
nuclei

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry

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Superoxide radical anion adduct of 5,5-dimethyl-1-Pyrroline N-oxide. 4. Conformational effects on the EPR hyperfine splitting constants. / Villamena, Frederick A.; Liu, Yangping; Zweier, Jay L.

In: Journal of Physical Chemistry A, Vol. 112, No. 49, 11.12.2008, p. 12607-12615.

Research output: Contribution to journalArticle

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abstract = "Spin trapping has been commonly employed in the detection of superoxide radical anion in chemical and biological systems; hence, accurate interpretation of the hyperfine splitting constants (hfsc's) arising from the O 2•- adducts (also referred to as hydroperoxyl (HO2•) radical adducts) of various nitrones is important. In this work, the nature of the relevant hfsc's was investigated by examining the effect of conformational changes in the hydroperoxyl moiety of the O2•- adducts of 5,5-dimethyl-l-pyrroline N-oxide (DMPO), 5-ethoxycarbonyl-5-methyl-1-pyrroline N-oxide (EMPO), 5-diethoxyphosphoryl-5-methyl-l-pyrroline N-oxide (DEPMPO), 5-carbamoyl-5- methyl-1-pyrroline N-oxide (AMPO), and 7-oxa-l-azaspiro[4.4]non-1-en-6-one N-oxide, (CPCOMPO) on the magnitude of aN, aβ-H, and aγ-H. Conformational change around the substituents and their effect on the hfsc's were also explored. Results indicate that a β-H is most sensitive to conformational changes of the hydroperoxyl and substituent groups relative to hfsc's of other nuclei. The orbital overlap between the C-H σ-orbital and the SOMO of the nitroxyl nitrogen plays a crucial factor in determining the magnitude of the a β-H. The hfsc values for the O2•- adducts were predicted with high accuracy by using a low-cost computational method at the PCM(water)/BHandHLYP/EPR-III//B3LYP/6-31G* level of theory without taking into account the explicit water interaction.",
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AB - Spin trapping has been commonly employed in the detection of superoxide radical anion in chemical and biological systems; hence, accurate interpretation of the hyperfine splitting constants (hfsc's) arising from the O 2•- adducts (also referred to as hydroperoxyl (HO2•) radical adducts) of various nitrones is important. In this work, the nature of the relevant hfsc's was investigated by examining the effect of conformational changes in the hydroperoxyl moiety of the O2•- adducts of 5,5-dimethyl-l-pyrroline N-oxide (DMPO), 5-ethoxycarbonyl-5-methyl-1-pyrroline N-oxide (EMPO), 5-diethoxyphosphoryl-5-methyl-l-pyrroline N-oxide (DEPMPO), 5-carbamoyl-5- methyl-1-pyrroline N-oxide (AMPO), and 7-oxa-l-azaspiro[4.4]non-1-en-6-one N-oxide, (CPCOMPO) on the magnitude of aN, aβ-H, and aγ-H. Conformational change around the substituents and their effect on the hfsc's were also explored. Results indicate that a β-H is most sensitive to conformational changes of the hydroperoxyl and substituent groups relative to hfsc's of other nuclei. The orbital overlap between the C-H σ-orbital and the SOMO of the nitroxyl nitrogen plays a crucial factor in determining the magnitude of the a β-H. The hfsc values for the O2•- adducts were predicted with high accuracy by using a low-cost computational method at the PCM(water)/BHandHLYP/EPR-III//B3LYP/6-31G* level of theory without taking into account the explicit water interaction.

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