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Sensitivity of secondary electrospray ionization mass spectrometry to a range of volatile organic compounds: Ligand switching ion chemistry and the influence of Zspray (TM) guiding electric fields
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SYSNO ASEP 0547340 Druh ASEP J - Článek v odborném periodiku Zařazení RIV J - Článek v odborném periodiku Poddruh J Článek ve WOS Název Sensitivity of secondary electrospray ionization mass spectrometry to a range of volatile organic compounds: Ligand switching ion chemistry and the influence of Zspray (TM) guiding electric fields Tvůrce(i) Dryahina, Kseniya (UFCH-W) RID, ORCID
Polášek, Miroslav (UFCH-W) RID, ORCID
Smith, D. (GB)
Španěl, Patrik (UFCH-W) RID, ORCIDČíslo článku e9187 Zdroj.dok. Rapid Communications in Mass Spectrometry. - : Wiley - ISSN 0951-4198
Roč. 35, č. 22 (2021)Poč.str. 15 s. Jazyk dok. eng - angličtina Země vyd. GB - Velká Británie Klíč. slova trace gas-analysis ; flow tube ; sift-ms ; exhaled breath ; water-vapor ; h3o+ ; no+ ; o-2(+) ; series ; aldehydes Vědní obor RIV CF - Fyzikální chemie a teoretická chemie Obor OECD Physical chemistry CEP GA18-12902S GA ČR - Grantová agentura ČR Způsob publikování Omezený přístup Institucionální podpora UFCH-W - RVO:61388955 UT WOS 000706436700006 EID SCOPUS 85116945318 DOI 10.1002/rcm.9187 Anotace Rationale Secondary electrospray ionization (SESI) is currently only semi-quantitative. In the Zspray (TM) arrangement of SESI-MS, the transfer of ions from near atmospheric pressure to a triple quadrupole is achieved by guiding electric fields that partially desolvate both reagent and analyte ions which must be understood. Also, to make SESI-MS more quantitative, the mechanisms and the kinetics of the reaction processes, especially ligand switching reactions of hydrated hydronium reagent ions, H3O+(H2O)(n), with volatile organic compound (VOC) molecules, need to be understood. Methods A modified Zspray (TM) ESI ion source operating at sub-atmospheric pressure with analyte sample gas introduced via an inlet coaxial with the spray was used. Variation of the ion-guiding electric fields was used to reveal the degree of desolvation of both reagent and analyte ions. The instrument sensitivity was determined for several classes of VOCs by introducing bag samples of suitably varying concentrations as quantified on-line using selected ion flow tube MS. Results Electric field desolvation resulted in largely protonated VOCs, MH+, and their monohydrates, MH+H2O, and for some VOCs proton-bound dimer ions, MH+M, were formed. There was a highly linear response of the ion signal to the measured VOC sample concentration, which provided the instrument sensitivities, S, for 25 VOCs. The startling results show very wide variations in S from near 0 to 1 for hydrocarbons, and up to 100, on a relative scale, for polar compounds such as monoketones and unsaturated aldehydes. Conclusions The complex ion chemistry occurring in the SESI ion source, largely involving gas-phase ligand switching, results in widely variable sensitivities for different classes of VOCs. The sensitivity is observed to depend on the dipole moment and proton affinity of the analyte VOC molecule, M, and to decrease with the observed fraction of MH+H2O, but other yet unrecognized factors must play a significant role. Pracoviště Ústav fyzikální chemie J.Heyrovského Kontakt Michaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196 Rok sběru 2022 Elektronická adresa http://hdl.handle.net/11104/0323587
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