title: Analysis of carbonyl compounds via headspace solid-phase microextraction with on-fiber derivatization and gas chromatographic-ion trap tandem mass spectrometric determination of their O-(2,3,4,5,6-pentafluorobenzyl)oxime derivatives.
abstract: An improved method for the analysis of carbonyls is described utilizing a headspace solid-phase microextraction (HS-SPME) step and on-fiber derivatization with O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) hydrochloride. Thermal desorption of the oxime derivatives formed on the fiber is followed by gas chromatographic separation coupled to an ion trap tandem mass spectrometer (GC-ITMS). Selecting specific fragment ions within the electron ionization (EI(+)) mass spectra of these oxime derivatives as precursor ions for MS-MS fragmentation provides a suitable method for the target analysis of individual carbonyl classes, such as alkanals, (E)-2-alkenals, (E,E)-2,4-alkadienals, and others. Retention indices on polar as well as on apolar stationary phases along with EI(+) mass spectra patterns are presented for a large set of oxime derivatives, giving valuable information needed for unambiguous assignment of substances in complex sample matrices. The fast sample preparation and derivatization step via HS-SPME can be automated and is applicable to a variety of biological samples and foodstuffs, allowing rapid and sensitive screening analyses of important aldehydic biomarkers and aroma active compounds.
authors.affiliation: Dienstleistungszentrum Ländlicher Raum Rheinpfalz, Breitenweg 71, D-67435 Neustadt an der Weinstrasse, Germany. hans-georg.schmarr@dlr.rlp.de
authors.forename: Hans-Georg
authors.initials: HG
authors.lastname: Schmarr
authors.forename: Theodoros
authors.initials: T
authors.lastname: Potouridis
authors.forename: Sebastian
authors.initials: S
authors.lastname: Ganss
authors.forename: Wei
authors.initials: W
authors.lastname: Sang
authors.forename: Benedikt
authors.initials: B
authors.lastname: Köpp
authors.forename: Ursula
authors.initials: U
authors.lastname: Bokuz
authors.forename: Ulrich
authors.initials: U
authors.lastname: Fischer
mesh_terms: D002255:Carbonic Acid / Q000032:analysis* / Q000737:chemistry; D005464:Fluorobenzenes / Q000737:chemistry*; D008401:Gas Chromatography-Mass Spectrometry / Q000379:methods*; D015394:Molecular Structure; D010091:Oximes / Q000032:analysis* / Q000737:chemistry*; D052617:Solid Phase Microextraction / Q000379:methods*; D053719:Tandem Mass Spectrometry / Q000379:methods*
chemical_list: D005464:Fluorobenzenes; D010091:Oximes; D002255:Carbonic Acid