An examination of pentafluorobenzoyl derivatization strategies for the analysis of fatty alcohols using gas chromatography/electron capture negative ion chemical ionization–mass spectrometry

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.