NDLI: Variations in GC–MS Response Between Analytes and Deuterated Analogs

Content Provider	Springer Nature Link
Author	Alzweiri, Muhammed Khanfar, Mohammad Al Hiari, Yusuf
Copyright Year	2015
Abstract	Isotopic analogs are commonly used as appropriate internal standards. It was observed that analytes usually have higher mass responses than their equimolar deuterated analogs leading to quantification discrepancy. The standard addition method was adopted on dimethyl azelate (DMA) and d 6-dimethyl azelate (d 6-DMA) to investigate possible reasons for this behavior. Cross contribution of mass responses, intermolecular deuterium–hydrogen exchange during chromatographic separation, and deviation in mass ionization response of C–H against C–D bonds were studied. GC–MS analysis revealed that neither cross contribution of ions nor H2/H exchange was responsible for the difference in responses between DMA and d 6-DMA. On the other hand, a study of carbon nucleus relaxation conducted by 13C-NMR showed that relaxation rate of carbonyl carbon in d 6-DMA is faster than DMA (9 and 3 s−1, respectively). This indicates rapid interaction between spin of deuterium nucleus with spin of unpaired electrons in the structure. Accordingly, DMA has more electrons in triplet/singlet state (i.e., unpaired electrons) in each time moment promoting propagation of radicalization reactions inside the electron impact chamber. In conclusion, this should increase the response of total ion current (TIC) and generate overestimated results for equimolar ratios of analytes such as dimethyl azelate, dimethyl adipate and dimethyl phthalate against their deuterated counterparts.
Starting Page	251
Ending Page	258
Page Count	8
File Format	PDF
ISSN	00095893
Journal	Chromatographia
Volume Number	78
Issue Number	3-4
e-ISSN	16121112
Language	English
Publisher	Springer Berlin Heidelberg
Publisher Date	2015-01-20
Publisher Place	Berlin, Heidelberg
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	Gas chromatography Deuterated analog Mass response Carbon relaxation Chromatography Proteomics Pharmacy Laboratory Medicine
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Analytical Chemistry Biochemistry Clinical Biochemistry

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