title: Optimized thiol derivatizing reagent for the mass spectral analysis of disubstituted epoxy fatty acids.
abstract: A novel procedure is described for the derivatization of fatty acid epoxides in the presence of their corresponding diols. The acidic character of 2,3,5,6-tetrafluorobenzenethiol promotes favorable mass fragmentation of linoleate and arachidonate derived epoxide derivatives and reduces alkene isomerization to a manageable side reaction, eliminated through the addition of a thiol scavenger. After silylation, regioisomeric mixtures of epoxy- and dihydroxylipids are simultaneously detected and discriminated using gas chromatography with electron impact mass spectral detection. Silylated hydroxysulfanyloctadecanoids yielded instrumental detection limits of 5 pg/microl, sufficient sensitivity for the quantification of endogenous epoxylipids.
authors.affiliation: Department of Entomology and the University of California Davis Cancer Research Center, University of California, 95616, USA.
authors.forename: J W
authors.initials: JW
authors.lastname: Newman
authors.forename: B D
authors.initials: BD
authors.lastname: Hammock
mesh_terms: D004852:Epoxy Compounds / Q000737:chemistry*; D005227:Fatty Acids / Q000032:analysis* / Q000737:chemistry; D008401:Gas Chromatography-Mass Spectrometry / Q000379:methods*; D013438:Sulfhydryl Compounds / Q000737:chemistry*
chemical_list: D004852:Epoxy Compounds; D005227:Fatty Acids; D013438:Sulfhydryl Compounds