Selected ion flow tube study of the reactions of H3O+ and NO+ with a series of primary alcohols in the presence of water vapour in support of selected ion flow tube mass spectrometry

0484029 - ÚFCH JH 2018 RIV GB eng J - Článek v odborném periodiku
Španěl, Patrik - Žabka, Ján - Zymak, Illia - Smith, D.
Selected ion flow tube study of the reactions of H3O+ and NO+ with a series of primary alcohols in the presence of water vapour in support of selected ion flow tube mass spectrometry.
Rapid Communications in Mass Spectrometry. Roč. 31, č. 5 (2017), s. 437-446. ISSN 0951-4198. E-ISSN 1097-0231
Grant CEP: GA ČR GA13-28882S; GA ČR(CZ) GA14-19693S
Institucionální podpora: RVO:61388955
Klíčová slova: trace gas-analysis * sift-ms * breath analysis * fa-sift * ptr-ms
Obor OECD: Physical chemistry
Impakt faktor: 1.970, rok: 2017

RATIONALE: Alcohols are often present in foods and other biological media, including exhaled breath, urine and cell culture headspace. For their analysis by selected ion flow tube mass spectrometry (SIFT-MS), the ion chemistry initiated by the reactions of the reagent ions H3O+ and NO+ with alcohol molecules in the presence of water molecules needs to be understood and quantitatively described.
METHODS: The reactions of H3O+ and NO+ ions have been studied with the primary alcohols, methanol, ethanol,
1-propanol, 1-butanol, 1-pentanol and 1-hexanol, under the conditions used for SIFT-MS analyses (1 Torr Hen 0.1 Torr
air sample, 300 K) and over a range of sample gas humidity from 1% to 5.5%.
RESULTS: The H3O+ reactions led to the formation of protonated alcohol molecules MH+ and their hydrates
MH+(H2O)1,2,3 and (MH+-H2O) fragment ions. The NO+ reactions were observed to proceed mainly via hydride ion
transfer, resulting in the formation of [M–H]+ product ions. Formation of the NO+M adduct ions was also observed
due to ligand switching between the NO+(H2O)1,2 hydrated reagent ions and M, and via direct NO+/M association in
the case of ethanol. The variation in the percentages of the hydrated product ions with the air sample humidity is reported.
CONCLUSIONS: This detailed study has provided the kinetics data, including the secondary hydrated ion product
distributions, for the reactions of a number of volatile primary alcohols with the SIFT-MS reagent ions H3O+ and NO+,
which allows their analyses by SIFT-MS in humid air and also helps in the interpretation of proton transfer reaction
(PTR)-MS data.
Trvalý link: http://hdl.handle.net/11104/0279186