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Determination of Enantiomer Ratios of Bornane Congeners in Biological Samples Using Heart-Cut Multidimensional Gas Chromatography
Authors:Henk-Jan de Geus  Ruth Baycan-Keller  Michael Oehme  Jacob de Boer  Udo A Th Brinkman
Abstract:The enantiomeric ratios of the chlorinated bornanes, 2-exo, 5,5,9,9,10, 10-heptachlorobornane (B20030]-(022)), 2-endo,3-exo,5-endo,6-exo,8, 8,10,10-octachlorobornane (B12012]-(202), Parlar No. 26), 2-exo,3-endo,6-endo,8,9,10,10-heptachlorobornane (B21001]-(112)), 2,2,5,5,9,9, 10,10-octachlorobornane (B30030]-(022), Parlar No. 38), 2-endo,3-exo,5-endo6-exo,8,8,9,10,10-nonachlorobornane (B12012]-(212), Parlar No. 50), and 2,2,5,5,8,9,9,10,10-nonachlorobornane (B30030]-(122), Parlar No. 62) were determined in a hake liver (Merluccius merluccius) and in two whitebeaked dolphin blubber (Lagenorynchus albirostris) samples. The analysis was performed by heart-cut multidimensional gas chromatography using an electron capture detector (ECD). Ultra 2 (5%-phenyl-95%-methylsilicone) was used as stationary phase in the first column and enantioselectivity was obtained in the second column with a phase consisting of a mixture of OV-1701 and heptakis(2,3,6-O-tert- butyldimethylsilyl)-β-cyclodextrin (10 : 1). All reference standards were also tested on the enantioselective column alone. The comparison of the two systems showed that deviations of ±0.12 from the racemic enantiomer ratio can be observed for the single column due to co-eluting impurities which are present in the reference standards. In most of the heart-cut chromatograms of the biota samples about 15 peaks could be found, showing the importance of a multidimensional separation system for an interference-free quantification by ECD. In all biological samples a significant deviation from the racemic enantiomer ratio was found for B30030]-(022) (Parlar No. 38) and for B30030]-(122) (Parlar No. 62). This indicates that an enantioselective disposition of the congeners occurs. In addition, considerations are presented concerning the relationship between congener structure and enantiomeric disposition.
Keywords:Bornane congeners  toxaphene compounds  heart-cut multidimensional gas chromatography  enantioselectivity  chiral GC separation  biological samples
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