The mechanism of oleic acid nitration by •NO2

Kavita Jain, Anjaiah Siddam, Archana Marathi, Uzzal Roy, J R Falck, Michael Balazy

Research output: Contribution to journalArticle

39 Citations (Scopus)

Abstract

Fatty acid nitration is a recently discovered process that generates biologically active nitro lipids; however, its mechanism has not been fully characterized. For example, some structural details such as vinyl and allyl isomers of the nitro fatty acids have not been established. To characterize lipids that originated from a biomimetic reaction of •NO2 with oleic acid, we synthesized several isomers of nitro oleic acids and studied their chromatography and mass spectra by various techniques of mass spectrometry. LC/MS analysis performed on a high resolution micro column detected molecular carboxylic anions of various oleic acid nitro isomers (NO2OA). Esterification of NO2OA with pentafluorobenzyl bromide and diisopropylethylamine as a catalyst produced a unique isoxazole ester derivative exclusively from allyl NO2OA isomers via dehydration of the nitro group at ambient temperatures. This new analytical procedure revealed that •NO2 generated two vinyl and two allyl isomers of NO2OA. The vinyl isomers showed high regioselectivity with the 1.8:1 preference for the 10-NO2OA isomer that was absent among allylic isomers. The nitration also generated elaidic acid via cis-trans isomerization and diatereoisomers of vicinal nitro hydroxy, nitro keto and α-nitro epoxy stearic acids with high stereo and regioselectivity. Nitration of small unilamelar phospholipid vesicles resulted in several phospholipids containing nitro lipids and elaidic acid amenable to hydrolysis by phospholipase A2.

Original languageEnglish (US)
Pages (from-to)269-283
Number of pages15
JournalFree Radical Biology and Medicine
Volume45
Issue number3
DOIs
StatePublished - Aug 1 2008

Fingerprint

Nitration
Oleic Acid
Isomers
Lipids
Phospholipids
Fatty Acids
Stearic Acids
Oleic Acids
Isoxazoles
Biomimetics
Esterification
Phospholipases A2
Dehydration
Regioselectivity
Anions
Chromatography
Mass Spectrometry
Esters
Hydrolysis
Temperature

Keywords

  • Elaidic acid
  • Isoxazoles
  • Mass spectrometry
  • Nitro lipids
  • Nitro phospholipids
  • Nitrogen dioxide

ASJC Scopus subject areas

  • Medicine(all)
  • Toxicology
  • Clinical Biochemistry

Cite this

The mechanism of oleic acid nitration by •NO2 . / Jain, Kavita; Siddam, Anjaiah; Marathi, Archana; Roy, Uzzal; Falck, J R; Balazy, Michael.

In: Free Radical Biology and Medicine, Vol. 45, No. 3, 01.08.2008, p. 269-283.

Research output: Contribution to journalArticle

Jain, Kavita ; Siddam, Anjaiah ; Marathi, Archana ; Roy, Uzzal ; Falck, J R ; Balazy, Michael. / The mechanism of oleic acid nitration by •NO2 In: Free Radical Biology and Medicine. 2008 ; Vol. 45, No. 3. pp. 269-283.
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