title: Product ion distributions for the reactions of NO+with some physiologically significant aldehydes obtained using a SRI-TOF-MS instrument.
abstract: Product ion distributions for the reactions of NO+with 22 aldehydes involved in human physiology have been determined under the prevailing conditions of a selective reagent ionization time of flight mass spectrometry (SRI-TOF-MS) at an E/N in the flow/drift tube reactor of 130 Td. The chosen aldehydes were fourteen alkanals (the C2-C11 n-alkanals, 2-methyl propanal, 2-methyl butanal, 3-methyl butanal, and 2-ethyl hexanal), six alkenals (2-propenal, 2-methyl 2-propenal, 2-butenal, 3-methyl 2-butenal, 2-methyl 2-butenal, and 2-undecenal), benzaldehyde, and furfural. The product ion fragmentations patterns were determined for both dry air and humid air (3.5% absolute humidity) used as the matrix buffer/carrier gas in the drift tube of the SRI-TOF-MS instrument. Hydride ion transfer was seen to be a common ionization mechanism in all these aldehydes, thus generating (M-H)+ions. Small fractions of the adduct ion, NO+M, were also seen for some of the unsaturated alkenals, in particular 2-undecenal, and heterocyclic furfural for which the major reactive channel was non-dissociative charge transfer generating the M+parent ion. Almost all of the reactions resulted in partial fragmentation of the aldehyde molecules generating hydrocarbon ions; specifically, the alkanal reactions resulted in multiple product ions, whereas, the alkenals reactions produced only two or three product ions, dissociation of the nascent excited product ion occurring preferentially at the 2-position. The findings of this study are of particular importance for data interpretation in studies of aldehydes reactions employing SRI-TOF-MS in the NO+mode.
authors.affiliation: Breath Research Institute of the University of Innsbruck, Rathausplatz 4, A-6850 Dornbirn, Austria.
authors.forename: Paweł
authors.initials: P
authors.lastname: Mochalski
authors.affiliation: Breath Research Institute of the University of Innsbruck, Rathausplatz 4, A-6850 Dornbirn, Austria ; Vorarlberg University of Applied Sciences, Hochschulstr. 1, A-6850 Dornbirn, Austria.
authors.forename: Karl
authors.initials: K
authors.lastname: Unterkofler
authors.affiliation: J. Heyrovský Institut of Physical Chemistry, Academy of Sciences of the Czech Republic, Dolejškova 3, 18223 Prague 8, Czech Republic.
authors.forename: Patrik
authors.initials: P
authors.lastname: Španěl
authors.affiliation: Institute for Science and Technology in Medicine, Medical School, Keele University, Thornburrow Drive, Hartshill, Stoke-on-Trent ST4 7QB, UK.
authors.forename: David
authors.initials: D
authors.lastname: Smith
authors.affiliation: Breath Research Institute of the University of Innsbruck, Rathausplatz 4, A-6850 Dornbirn, Austria ; Univ.-Clinic for Anesthesia and Intensive Care, Innsbruck Medical University, Anichstr 35, A-6020 Innsbruck, Austria.
authors.forename: Anton
authors.initials: A
authors.lastname: Amann
keywords: Aldehydes; Fragmentation patterns; NO+ reactions; PTR-MS; SRI-TOF-MS; VOCs
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