کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
1205136 1493657 2012 10 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
Quantification of achiral and chiral methylsulfonyl polychlorinated biphenyl metabolites by column-switching liquid chromatography–atmospheric pressure photoionization–tandem mass spectrometry
موضوعات مرتبط
مهندسی و علوم پایه شیمی شیمی آنالیزی یا شیمی تجزیه
پیش نمایش صفحه اول مقاله
Quantification of achiral and chiral methylsulfonyl polychlorinated biphenyl metabolites by column-switching liquid chromatography–atmospheric pressure photoionization–tandem mass spectrometry
چکیده انگلیسی

An enantioselective heart-cut column-switching liquid chromatography–atmospheric pressure photoionization–tandem mass spectrometry method was developed for the analysis of 25 methylsulfonyl polychlorinated biphenyl metabolites in tissue extracts. Use of a pyrenyl-ethyl silica column in the first dimension enabled separation of all but two pairs of isobaric analytes. Enantioseparation was achieved for 9 out of the 10 atropisomeric analytes using a Chiralpak AD-H amylose-based column within 93 min, resulting in greater chromatographic resolution of enantioseparation over shorter analysis time by up to a factor of three, compared to previous one-dimensional and multi-dimensional gas chromatography-based methods. Precision for concentration and enantiomer fraction measurements was within 11% and 3% relative standard deviation, respectively. Limits of detection ranged from 0.01 to 1.73 ng on-column. Meta-congeners had poorer sensitivity (i.e., ng on-column), consistent with existing gas chromatography-based methods. Despite this limitation, the method was successfully applied to the analysis of Greenland sledge dog adipose tissue extracts, which had highly non-racemic residues of 4-methylsulfonyl-2,2′,3,5′,6-pentachlorobiphenyl and 4′-methylsulfonyl-2,2′,3,3′,4,6′-hexachlorobiphenyl, consistent with past reports in Arctic mammals.


► A novel method was created to quantify methylsulfonyl PCBs and their atropisomers.
► First time PYE column used to fractionate methylsulfonyl PCBs.
► First use of APPI and column-switching LC for quantifying achiral and chiral congeners.
► Analysis time was up to three times less than existing gas chromatography methods.
► Highly non-racemic methylsulfonyl PCBs were found in sledge dogs fed whale blubber.

ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Journal of Chromatography A - Volume 1268, 14 December 2012, Pages 64–73
نویسندگان
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