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Fernandes-Whaley, M.* ; Mühlberger, F. ; Whaley, A.* ; Adam, T. ; Zimmermann, R. ; Rohwer, E.* ; Walte, A.*

On-line derivatization for resonance-enhanced multiphoton ionization time-of-flight mass spectrometry:Detection of aliphatic aldehydes and amines via reactive coupling of aromatic photo ionization labels.

Anal. Chem. 77, 1-10 (2005)
DOI
Open Access Green as soon as Postprint is submitted to ZB.
Resonance-enhanced multiphoton ionization time-of-flight mass spectrometry (REMPI-TOFMS) is a powerful technique for the on-line analysis of aromatic compounds with unique features regarding selectivity and sensitivity. Aliphatic compounds, however, are difficult to address by REMPI due to their unfavorable photo ionization properties. This paper describes the proof of concept for an on-line derivatization approach for converting nonaromatic target analytes into specific, photoionizable aromatic derivatives that are readily detectable by REMPI-TOFMS. A multichannel silicone trap or poly(dimethylsiloxane) (PDMS) open tubular capillary was used as a reaction medium for the derivatization of volatile alkyl aldehydes and alkylamines with aromatic "photoionization labels"and to concentrate the resulting aromatic derivatives. The aldehydes formaldehyde, acetaldehyde, acrolein, and crotonal, which when underivatized are poorly detectable by REMPI, were converted into their easily photoionizable phenylhydrazone derivatives by the on-line reaction with phenylhydrazine as reagent. Similarly, the methyl-, ethyl-, propyl-, and butylamines were converted into their REMPI-ionizable benzaldehyde alkylimine derivatives by the on-line reaction with benzaldehyde as reagent. The derivatives were thermally desorbed from the PDMS matrix and transferred into the REMPI-TOFMS for detection. The REMPI-TOFMS detection limits obtained for acetaldehyde; acrolein; crotonal; and methyl-, ethyl-, propyl-, and butylamine using this photo ionization labeling method were in the sub-parts-per-million range and, thus, readily below the permissible exposure limits set by OSHA.
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Publication type Article: Journal article
Document type Scientific Article
Corresponding Author
Keywords on-line derivatization; time-of-flight mass spectrometry; amines; aldehydes; photo ionization labels; REMPI; REMPI-TOFMS
ISSN (print) / ISBN 0003-2700
e-ISSN 1520-6882
Journal Analytical Chemistry
Quellenangaben Volume: 77, Issue: 1, Pages: 1-10 Article Number: , Supplement: ,
Publisher American Chemical Society (ACS)
Non-patent literature Publications
Reviewing status Peer reviewed
Institute(s) Institute of Ecological Chemistry (IOEC)