PuSH - Publikationsserver des Helmholtz Zentrums München

Export: TXT Text RIS Endnote (RIS) BIB BibTeX
Reinnicke, S. ; Bernstein, A. ; Elsner, M.

Small and reproducible isotope effects during methylation with trimethylsulfonium hydroxide (TMSH): A convenient derivatization method for isotope analysis of negatively charged molecules.

Anal. Chem. 82, 2013-2019 (2010)
DOI PMC
Open Access Green möglich sobald Postprint bei der ZB eingereicht worden ist.
Negatively charged analytes must be derivatized prior to gas chromatography-isotope ratio mass spectrometry (GC-IRMS), with stringent control of isotope fractionation. Current methods require offline sample preparation. This study tests for the first time trimethylsulfonium hydroxide (TMSH) as online methylation agent prior to isotope analysis, addressing the herbicides bentazone and MCPA. Fully automated derivatization was achieved in a temperature-programmable GC injector, where reactants were injected into a packed liner, solvents were removed by split flow, and subsequent flash heating triggered the derivatization, thereby transferring derivatives onto the chromatographic column. Stoichiometric addition of TMSH resulted in complete conversion giving accurate and reproducible nitrogen isotope values of bentazone. In contrast, reproducible carbon isotope analysis required TMSH in > or = 250-fold excess. Contrary to expectations, delta(13)C values became more negative at smaller TMSH excess. This indicates that elevated methyl group concentrations in the pore space of the injection liner facilitated close-to-equilibrium rather than kinetic isotope fractionation resulting in reproducible derivatization conditions. delta(13)C results under these conditions compared favorably with liquid chromatography-IRMS: low standard deviations (0.3 per thousand for GC-IRMS, 0.1 per thousand for LC-IRMS) and a comparable offset of 1 per thousand compared to elemental analyzer-IRMS demonstrate that both methods represent expedient ways for online isotope analysis of anionic target compounds.
Impact Factor
Scopus SNIP
Web of Science
Times Cited
Scopus
Cited By
Altmetric
5.214
2.320
18
28
Tags
Anmerkungen
Besondere Publikation
Auf Hompepage verbergern

Zusatzinfos bearbeiten
Eigene Tags bearbeiten
Privat
Eigene Anmerkung bearbeiten
Privat
Auf Publikationslisten für
Homepage nicht anzeigen
Als besondere Publikation
markieren
Publikationstyp Artikel: Journalartikel
Dokumenttyp Wissenschaftlicher Artikel
Schlagwörter Ratio mass-spectrometry; Gas-chromatography; Amino-acids; Biodegradation pathways; Delta-C-13 analysis; Enhance volatility; Fatty-acids; Carbon; Fractionation; Transformation
Sprache englisch
Veröffentlichungsjahr 2010
HGF-Berichtsjahr 2010
ISSN (print) / ISBN 0003-2700
e-ISSN 1520-6882
Zeitschrift Analytical Chemistry
Quellenangaben Band: 82, Heft: 5, Seiten: 2013-2019 Artikelnummer: , Supplement: ,
Verlag American Chemical Society (ACS)
Begutachtungsstatus Peer reviewed
Institut(e) Institute of Groundwater Ecology (IGOE)
PSP-Element(e) G-550700-001
PubMed ID 20143836
DOI 10.1021/ac902750s
Scopus ID 77749322383
Erfassungsdatum 2010-12-06
[➜Korrektur melden]