Assigning atropisomer elution orders using atropisomerically enriched polychlorinated biphenyl fractions generated by microsomal metabolism

Abstract

Changes in the enantiomeric fraction of chiral polychlorinated biphenyls (PCBs) are a powerful tool to investigate the movement of PCBs in the environment, for example as part of source apportionment and ecological studies. Environmental studies typically employ a series of cyclodextrin-based gas chromatography columns to separate all environmentally relevant PCB congeners. The elution order of most PCB atropisomers has not been established on different enantioselective columns due to the unavailability of analytical standards. To overcome this limitation, the current study generated atropisomerically enriched fractions of chiral PCBs with rat liver microsomes. Subsequently, the enrichment profile of the enriched PCB fractions was used to determine the elution order of PCB atropisomers on selected enantioselective gas chromatography columns. While the elution order of PCB 95, 131, 132, 136, 149 and 176 atropisomers was identical on all enantioselective columns investigated, an inversion of the elution order was observed for PCB 45, 84, 91 and 174 atropisomers on a few columns. These results demonstrate that atropisomerically enriched fractions obtained from microsomal metabolism can be used to unambiguously establish the relative elution order of the atropisomers of PCBs and potentially other environmental pollutant, especially if pure enantiomers are not available.