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

Result code in IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F21%3A00547340" target="_blank" >RIV/61388955:_____/21:00547340 - isvavai.cz</a>

Result on the web

<a href="http://hdl.handle.net/11104/0323587" target="_blank" >http://hdl.handle.net/11104/0323587</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/rcm.9187" target="_blank" >10.1002/rcm.9187</a>

Result language

angličtina

Original language name

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

Original language description

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.

Czech name

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Czech description

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Type

J_imp - Article in a specialist periodical, which is included in the Web of Science database

CEP classification

—

OECD FORD branch

10403 - Physical chemistry

Project

<a href="/en/project/GA18-12902S" target="_blank" >GA18-12902S: Secondary electrospray ionization mass spectrometry (SESI-MS) for quantification of gaseous analytes in air, headspace and breath</a><br>

Continuities

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year

2021

Confidentiality

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Name of the periodical

Rapid Communications in Mass Spectrometry

ISSN

0951-4198

e-ISSN

1097-0231

Volume of the periodical

35

Issue of the periodical within the volume

22

Country of publishing house

GB - UNITED KINGDOM

Number of pages

15

Pages from-to

e9187

UT code for WoS article

000706436700006

EID of the result in the Scopus database

2-s2.0-85116945318