title: An examination of pentafluorobenzoyl derivatization strategies for the analysis of fatty alcohols using gas chromatography/electron capture negative ion chemical ionization-mass spectrometry.
abstract: Gas chromatography/electron capture negative ion chemical ionization-mass spectrometry (GC/ECNICI-MS) combined with pentafluorobenzoyl derivatization (PFBoyl) is frequently used for the sensitive detection of fatty alcohols (FOH). However, this derivatization technique suffers from a lack of established reaction protocols, time-consuming reactions, and the presence of reagent artifacts or unwanted derivatization by-products which can hinder analyte detection. Here, strategies are presented to reduce the problems associated with PFBoyl-derivatization, including (1) the optimization of reaction conditions (derivatization time and temperature) for a variety of PFBoyl-derivatized FOH, (2) an investigation of microwave-accelerated derivatization (MAD) as a rapid alternative heating mechanism for the PFBoyl-derivatization of FOH, and (3) an analysis of an alternative strategy employing a solvent extraction procedure post-derivatization to reduce the detrimental effects commonly associated with PFBoyl derivatization reagents. The optimal reaction conditions for the PFBoyl-derivatization of FOH were determined to be 60°C for 45 min. The investigation in MAD demonstrated the potential of obtaining comparable PFBoyl-derivatizations to those obtained using traditional heating methods, albeit in a reaction time of 3 min. An examination of several solvents for post-derivatization extraction revealed improved relative response factors in comparison to those obtained without solvent extraction. The best solvents for the PFBoyl-FOH extraction, dichloromethane and tert-butyl methyl ether, were also compared to the no solvent extraction samples with standard response curves and PFBoyl-derivatized FOH in Bligh-Dyer extracted rat plasma.
authors.affiliation: Department of Biochemistry and Molecular Biology, School of Medicine, and Center for Cardiovascular Research, Saint Louis University, 1100 Grand Ave., Saint Louis, MO 63104, USA.
authors.forename: John A
authors.initials: JA
authors.lastname: Bowden
authors.forename: David A
authors.initials: DA
authors.lastname: Ford
mesh_terms: D000818:Animals; D001565:Benzoates / Q000737:chemistry*; D005233:Fatty Alcohols / Q000032:analysis* / Q000097:blood* / Q000302:isolation & purification; D008401:Gas Chromatography-Mass Spectrometry / Q000191:economics / Q000379:methods*; D008872:Microwaves; D010949:Plasma / Q000737:chemistry*; D051381:Rats; D012997:Solvents / Q000737:chemistry; D013997:Time Factors; D005464:Fluorobenzenes; D005466:Fluorocarbons
chemical_list: D001565:Benzoates; D005233:Fatty Alcohols; D012997:Solvents; C014737:pentafluorobenzoyl chloride; D005464:Fluorobenzenes; D005466:Fluorocarbons