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PredicateObject
rdf:type
lifeskim:mentions
pubmed:issue
22
pubmed:dateCreated
2006-6-14
pubmed:abstractText
Spin trapping by 5,5-dimethylpyrroline-N-oxide (DMPO) was used for the detection of radicals in Fenton media in the presence and absence of Nafion perfluorinated ionomers. For ethanol as solvent, the same types of spin adducts were detected in the presence or absence of Nafion. Solvent-derived adducts, DMPO/*OC2H5 and DMPO/*CH(OH)CH3, were identified, and their presence was rationalized by Fe(III)-catalyzed nucleophilic addition of ethanol to the spin trap and hydrogen abstraction by *OH radicals; oxygen radical adducts, DMPO/*O2(-) and DMPO/*OOH, were also detected. In Fenton media with methanol as solvent (and no Nafion), the DMPO/*O2(-) adduct dominated immediately after sample preparation, and a mixture consisting of DMPO/*OCH3, DMPO/*CH3, DMPO/*O2(-), and DMPO/*OOH adducts was detected after 30 min. In the presence of Nafion, only the adduct DMPO/*OH was detected. For water as solvent, only the DMPO/*OH adduct was detected, in both the absence and the presence of Nafion. The full hyperfine tensor components of this adduct were determined in Fenton media in the presence of Nafion with water and methanol as solvents. In Nafion/water exposed to the Fenton reagent at 358 K for 3 h, a DMPO adduct of a carbon-centered radical was also identified and assigned to a Nafion-derived fragment; its exact nature is under investigation. Variations of the 14N and Hbeta hyperfine splittings of a given adduct with the local polarity were key to the identification of some DMPO adducts, in particular DMPO/*O2(-). Both *OOH and O2*- adducts, with different 14N and Hbeta splittings, were detected simultaneously in some samples, for the first time in the spin trapping literature. Comparison with the results of a direct electron spin resonance study of Nafion exposed to the Fenton reagent indicated that spin trapping by DMPO can provide complementary information on the type of radicals present during Nafion degradation. The spin trapping approach described in this paper is limited, however, to systems that do not contain organic solvents.
pubmed:language
eng
pubmed:journal
pubmed:citationSubset
IM
pubmed:chemical
pubmed:status
MEDLINE
pubmed:month
Jun
pubmed:issn
1520-6106
pubmed:author
pubmed:issnType
Print
pubmed:day
8
pubmed:volume
110
pubmed:owner
NLM
pubmed:authorsComplete
Y
pubmed:pagination
10720-8
pubmed:meshHeading
pubmed:year
2006
pubmed:articleTitle
Spin trapping by 5,5-dimethylpyrroline-N-oxide in Fenton media in the presence of Nafion perfluorinated membranes: limitations and potential.
pubmed:affiliation
Department of Chemistry, University of Detroit Mercy, Detroit, Michigan 48219, USA.
pubmed:publicationType
Journal Article, Research Support, U.S. Gov't, Non-P.H.S., Research Support, Non-U.S. Gov't