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dc.contributor.authorEiler, J.
dc.contributor.authorCesar, J.
dc.contributor.authorChimiak, L.
dc.contributor.authorDallas, B.
dc.contributor.authorGrice, Kliti
dc.contributor.authorGriep-Raming, J.
dc.contributor.authorJuchelka, D.
dc.contributor.authorKitchen, N.
dc.contributor.authorLloyd, M.
dc.contributor.authorMakarov, A.
dc.contributor.authorRobins, R.
dc.contributor.authorSchwieters, J.
dc.identifier.citationEiler, J. and Cesar, J. and Chimiak, L. and Dallas, B. and Grice, K. and Griep-Raming, J. and Juchelka, D. et al. 2017. Analysis of molecular isotopic structures at high precision and accuracy by Orbitrap mass spectrometry. Journal of Mass Spectrometry.

© 2017 Elsevier B.V. Several technologies are being developed to examine the intramolecular isotopic structures of molecules (i.e., site-specific and multiple substitution), but limitations in sample size and type or (for mass spectrometry) resolution have so far prevented the creation of a general technique. We have now demonstrated the capacity for precise and accurate study of molecular isotopic contents and structures by Fourier transform mass spectrometry, using instruments containing a Thermo Scientific™ Orbitrap™ mass analyzer, here the Thermo Scientific Q Exactive GC™ and Q Exactive HF™ instruments. Orbitrap mass analyzers achieve mass resolutions in the range ~250,000-1. M (FWHM) in the mass range of greatest interest to studies of molecular isotopic structure, 50-200. amu. This allows for resolution of many nearly isobaric interferences for compounds containing H, C, N, O and/or S. In this paper we show that internal and external experimental reproducibilities of isotope ratio analyses using the Orbitrap analysis can conform to shot-noise lim its down to levels of tenths of per mil (1SE), with similar accuracy when standardized to reference materials. Precision reaches ±0.015‰ for exceptionally long integrations. Such measurements do not call for modifications to the ion optics of the Q Exactive instruments, but do require specially designed sample introduction devices to permit sample/standard comparison and long integration times. The sensitivity of the Q Exactive instruments permit analysis of sub-nanomolar samples and quantification of multiply-substituted species. Site-specific capabilities arise from the fact that mass spectra of molecular analytes commonly contain diverse fragment ion species, each of which samples a specific sub-set of molecular sites.

dc.publisherWiley InterScience
dc.titleAnalysis of molecular isotopic structures at high precision and accuracy by Orbitrap mass spectrometry
dc.typeJournal Article
dcterms.source.titleJournal of Mass Spectrometry
curtin.departmentDepartment of Chemistry
curtin.accessStatusFulltext not available

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