Identification of cis/trans isomers of methyl ester and oxazoline derivatives of unsaturated fatty acids using GC–FTIR–MS

Abstract

AbstractIdentification of cis/trans isomers of unsaturated fatty acids cannot usually be achieved by GC‐MS (gas chromatography‐mass spectrometry) without reference substances. In this study a GC‐FTIR‐MS system (gas chromatography‐Fourier transform‐mass spectrometry) was used to identify fatty acid methyl esters (FAMEs) and differentiate between the cis/trans isomers. Besides methyl esters, 2‐alkenyl‐4,4‐dimethyloxazoline derivatives (DMOX), which have been used to locate double bond positions of unsaturated fatty acids, were examined with respect to their suitability for cis/trans differentiation.A combined GC‐FTIR‐MS system with a wide band (4000–550 cm−1) mercury cadmium telluride (MCT) detector was used in series and parallel to identify 31 reference unsaturated fatty acids, including 7 pairs of cis/trans isomers. Serum samples of healthy persons and commercially available fish oil were analyzed as examples of complex mixtures. Using splitless injection the detection limit for the less sensitive IR detector was 25 ng/μl in case of the weak cis and trans bands.In the FTIR spectra cis/trans isomers were identified by analysis of bands arising from CH out‐of‐plane (oop) bending: for both the FAME and DMOX derivatives cis‐1,2‐disubstituted double bonds give a strong band near 720 cm−1 and the corresponding trans isomers near 967 cm−1. cis Isomers could be identified further by a band at 3012 cm−1. With the combined data of the GC‐FTIR‐MS system it is now possible to identify polyunsaturated fatty acids with regard to the discrimination of cis/trans isomers.