Document Detail


Superoxide radical anion adduct of 5,5-dimethyl-1-pyrroline N-oxide (DMPO). 2. The thermodynamics of decay and EPR spectral properties.
MedLine Citation:
PMID:  16833946     Owner:  NLM     Status:  MEDLINE    
Abstract/OtherAbstract:
The formation of the superoxide radical anion (O2*-) adduct of the nitrone 5,5-dimethyl-1-pyrroline N-oxide (DMPO) as detected by electron paramagnetic resonance (EPR) spectroscopy is one of the most common techniques for O2*- detection in chemical and biological systems. However, the nature of DMPO-O2H has confounded spin-trapping investigators over the years, since there has been no independently synthesized DMPO-O2H to date. A density functional theory (DFT) approach was used to predict the isotropic hyperfine coupling constants arising from the N, beta-H, and gamma-H nuclei of DMPO-O2H using explicit interactions with water molecules as well as via a bulk dielectric effect employing the polarizable continuum model (PCM). Theoretical calculation on the thermodynamics of DMPO-O2H decay shows favorable intramolecular rearrangement to form a nitrosoaldehyde and a hydroxyl radical as products, consistent with experimental observations. Some pathways for the bimolecular decomposition of DMPO-O2H and DMPO-OH have also been computed.
Authors:
Frederick A Villamena; John K Merle; Christopher M Hadad; Jay L Zweier
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Publication Detail:
Type:  Journal Article; Research Support, N.I.H., Extramural; Research Support, Non-U.S. Gov't; Research Support, U.S. Gov't, Non-P.H.S.    
Journal Detail:
Title:  The journal of physical chemistry. A     Volume:  109     ISSN:  1089-5639     ISO Abbreviation:  J Phys Chem A     Publication Date:  2005 Jul 
Date Detail:
Created Date:  2006-07-12     Completed Date:  2007-07-12     Revised Date:  2007-12-03    
Medline Journal Info:
Nlm Unique ID:  9890903     Medline TA:  J Phys Chem A     Country:  United States    
Other Details:
Languages:  eng     Pagination:  6089-98     Citation Subset:  IM    
Affiliation:
Center for Biomedical EPR Spectroscopy and Imaging, The Davis Heart and Lung Research Institute, College of Medicine, The Ohio State University, Columbus, Ohio 43210, USA. villamena-1@medctr.osu-edu
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MeSH Terms
Descriptor/Qualifier:
Anions / chemistry
Cyclic N-Oxides / chemistry*
Electron Spin Resonance Spectroscopy*
Electrons
Hydroxyl Radical / chemistry
Kinetics
Models, Chemical
Models, Molecular
Molecular Structure
Oxidation-Reduction
Spin Labels*
Spin Trapping*
Superoxides / chemistry*
Thermodynamics
Grant Support
ID/Acronym/Agency:
HL38324/HL/NHLBI NIH HHS; HL63744/HL/NHLBI NIH HHS; HL65608/HL/NHLBI NIH HHS
Chemical
Reg. No./Substance:
0/Anions; 0/Cyclic N-Oxides; 0/Spin Labels; 11062-77-4/Superoxides; 3317-61-1/5,5-dimethyl-1-pyrroline-1-oxide; 3352-57-6/Hydroxyl Radical

From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine


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