Analysis of molecular isotopic structures at high precision and accuracy by Orbitrap 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...
| Main Authors: | , , , , , , , , , , , |
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| Format: | Journal Article |
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Wiley InterScience
2017
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| Online Access: | http://hdl.handle.net/20.500.11937/57781 |
| _version_ | 1848760096463519744 |
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| author | Eiler, J. Cesar, J. Chimiak, L. Dallas, B. Grice, Kliti Griep-Raming, J. Juchelka, D. Kitchen, N. Lloyd, M. Makarov, A. Robins, R. Schwieters, J. |
| author_facet | Eiler, J. Cesar, J. Chimiak, L. Dallas, B. Grice, Kliti Griep-Raming, J. Juchelka, D. Kitchen, N. Lloyd, M. Makarov, A. Robins, R. Schwieters, J. |
| author_sort | Eiler, J. |
| building | Curtin Institutional Repository |
| collection | Online Access |
| description | © 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. |
| first_indexed | 2025-11-14T10:10:21Z |
| format | Journal Article |
| id | curtin-20.500.11937-57781 |
| institution | Curtin University Malaysia |
| institution_category | Local University |
| last_indexed | 2025-11-14T10:10:21Z |
| publishDate | 2017 |
| publisher | Wiley InterScience |
| recordtype | eprints |
| repository_type | Digital Repository |
| spelling | curtin-20.500.11937-577812017-11-20T08:58:09Z Analysis of molecular isotopic structures at high precision and accuracy by Orbitrap mass spectrometry Eiler, J. Cesar, J. Chimiak, L. Dallas, B. Grice, Kliti Griep-Raming, J. Juchelka, D. Kitchen, N. Lloyd, M. Makarov, A. Robins, R. Schwieters, J. © 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. 2017 Journal Article http://hdl.handle.net/20.500.11937/57781 10.1016/j.ijms.2017.10.002 Wiley InterScience restricted |
| spellingShingle | Eiler, J. Cesar, J. Chimiak, L. Dallas, B. Grice, Kliti Griep-Raming, J. Juchelka, D. Kitchen, N. Lloyd, M. Makarov, A. Robins, R. Schwieters, J. Analysis of molecular isotopic structures at high precision and accuracy by Orbitrap mass spectrometry |
| title | Analysis of molecular isotopic structures at high precision and accuracy by Orbitrap mass spectrometry |
| title_full | Analysis of molecular isotopic structures at high precision and accuracy by Orbitrap mass spectrometry |
| title_fullStr | Analysis of molecular isotopic structures at high precision and accuracy by Orbitrap mass spectrometry |
| title_full_unstemmed | Analysis of molecular isotopic structures at high precision and accuracy by Orbitrap mass spectrometry |
| title_short | Analysis of molecular isotopic structures at high precision and accuracy by Orbitrap mass spectrometry |
| title_sort | analysis of molecular isotopic structures at high precision and accuracy by orbitrap mass spectrometry |
| url | http://hdl.handle.net/20.500.11937/57781 |