Determination of the enantiomer fraction of PBB 149 by gas chromatography/electron capture negative ionization tandem mass spectrometry in the selected reaction monitoring mode.
Enantioselective determination of the atropisomers of 2,2',3,4',5',6-hexabromobiphenyl (PBB 149) in a purified sample from a bird egg was attempted in this work. By application of the classic method for PBB determination, i.e. gas chromatography coupled to electron capture negative ionization mass spectrometry (GC/ECNI-MS) using the bromide ions, the enantiomers interfered with another brominated compound. Subsequent measurements clarified that this interference did not occur in the mass chromatogram of the molecular ion of PBB 149. Therefore, a GC/ECNI tandem mass spectrometry (MS/MS) method was developed, based on the fragmentation of [M]-. A suitable precursor-product ion transition was found for m/z 627.5 --> 80 +/- 1.5, representing the most abundant ion trace of the molecular ion and the bromide ions. Optimization of the ion source temperature, the methane gas pressure, and the collision voltages resulted in a robust method that could solve the problem. Subsequent injections of a technical PBB product (Firemaster BP-6) resulted in the anticipated racemic proportion (enantiomer fraction (EF) = 0.50 +/- 0.02 (n = 8)). By contrast, the EF in the purified extract of a bird egg was found to be 0.42 +/- 0.02 (n = 10), indicative of a significant enantioenrichment of the second eluting atropisomer. Additional measurements were performed on a non-chiral column. These measurements allowed for the detection of 16 hexabromobiphenyls (hexa-BBs) in Firemaster BP-6. These comparisons verified that PBB 149 enantiomers did not interfere with an isomer that could falsify the enantiomer fraction in the sample. The novel method using GC/ECNI-MS/MS in the selected reaction monitoring (SRM) mode was eight times more sensitive than application of conventional GC/ECNI-MS selected ion monitoring (SIM) analysis of the molecular ion.
von der Recke
Roland
R
Institute of Food Chemistry, University of Hohenheim, Stuttgart, Germany.
Mariussen
Espen
E
Berger
Urs
U
Götsch
Arntraut
A
Herzke
Dorte
D
Vetter
Walter
W
D000818:Animals; D001717:Birds; D008401:Gas Chromatography-Mass Spectrometry / Q000379:methods*; D010063:Ovum / Q000737:chemistry; D011075:Polybrominated Biphenyls / Q000032:analysis* / Q000737:chemistry*; D013237:Stereoisomerism
D011075:Polybrominated Biphenyls; C508634:2,2',3,4',5',6-hexabromobiphenyl