On-line hydrogenation in GC-MS analysis of cyclic fatty acid monomers isolated from heated linseed oil
A simple on-line hydrogenation method in GC-MS analysis of unsaturated fatty acid esters is described. Using hydrogen as carrier gas, hydrogenation takes place in a capillary reactor connected to the outlet of the analytical column in the oven of the gas chromatograph. The reactor is a fused silica tube (60 cm×0.32 mm i.d.) coated with palladium acetylacetonate. Selective hydrogenation of olefinic bonds is achieved after a normal chromatographic run. Structural information (carbon-skeleton, double bond equivalents) can thus be deduced, and structural correlations between the saturated and unsaturated components can be obtained. Structures of cyclic fatty acid esters isolated from heated linseed oil were elucidated using this simple method which was found very useful for structural investigations on unsaturated compounds by GC-MS.
Evaluation of poly(90% biscyanopropyl/10% cyanopropylphenyl siloxane) capillary columns for the gas chromatographic quantification of trans fatty acids in non-hydrogenated vegetable oils.
Current gas chromatographic (GC) methods for the analysis of fatty acids (FA) were optimized primarily for the quantification of the trans 18:1 FAs (18:1 tFAs) produced during the partial hydrogenation of fats and oils. Recent regulatory action regarding the application of partial hydrogenation in the processing of edible fats and oils may reshape the FA composition of these products. The higher content in 18:3 tFAs compared to 18:1 tFAs of most refined non-hydrogenated vegetable oils (RNHVO), and the challenge in their quantification applying current methods, suggest the need for new methodologies. This manuscript describes a simple GC method for the analysis of FAs in RNHVOs utilizing a 100m (0.25mm I.D.) capillary column coated with poly(90% biscyanopropyl/10% cyanopropylphenyl siloxane) (90% BCS). The optimization of the chromatographic conditions and the detection of co-eluting compounds were carried out by applying comprehensive two dimensional gas chromatography with online reduction (GC-OR×GC). Results showed that 90% BCS capillary columns operated at the elution temperature of 162°C provide the separation of the 18:1, 18:2 and 18:3 tFAs, contained in RNHVOs, from other components. A minor constituent of Canola oil, 16:3n-3, partially co-eluted with trans-18:1 FAMEs. This simple GC method showed the ability to measure trans-fat in RNHVOs at the level of 0.5g/100g, providing comparable quantitative results to the more complex GC×GC methodology.
Intentional poisoning cases of animals with anticholinesterase pesticide-carbofuran in Sri Lanka.
Carbofuran is a broad spectrum insecticide and nematicide which inhibits acetyl cholinesterase. Several intentional poisoning cases of animals and birds including crows, dogs, cow, and elephant, using carbofuran were reported in Sri Lanka. Qualitative analysis of carbofuran in biological specimens was carried out using T.L.C and GC-MS. The quantitative analysis was carried out by HPLC using Zorbax Eclips XDB-C18 (150 x 4.6 mm I.D x 5 microm particle size) column with acetonitrile: water 25:75 v/v mobile phase and UV detection at 210 nm. The liquid-liquid extraction with chloroform was reproducible and sensitive. The procedure was validated in terms of linearity (0.996<r<0.999) for concentrations ranging from 1 to 200 microg/ml, repeatability (RSD 4.4% at 100 microg/ml, n=10) extraction recovery (91.7% at 100 microg/g, 77.3% at 20 microg/g), limit of detection (S/N ratio=3, 0.7 microg/ml) and limit of quantification (S/N ratio=10, 2.4 microg/ml). The method was found satisfactory and successfully applied in fatal cases of animals and birds due to carbofuran poisoning. The fatal carbofuran levels detected were in the range of 42-910 microg/g in crow's gizzard and contents, 50-800 microg/g in dog's stomach contents, 13-20 microg/g in dog's liver, 0.9 microg/g in cow's stomach and contents, 35 microg/g in elephant's stomach and contents.