H<inf>3</inf>O⁺, NO⁺ and O<inf>2</inf>⁺^. reactions with saturated and unsaturated monoketones and diones, focus on hydration of product ions

Kód výsledku v IS VaVaI

RIV/61388955:_____/19:00497665 - isvavai.cz

Výsledek na webu

http://hdl.handle.net/11104/0290191

DOI - Digital Object Identifier

10.1016/j.ijms.2018.10.027

Jazyk výsledku

angličtina

Název v původním jazyce

H3O⁺, NO⁺ and O2^+. reactions with saturated and unsaturated monoketones and diones, focus on hydration of product ions

Popis výsledku v původním jazyce

A selected ion flow tube, SIFT, study has been carried out for the reactions of the SIFT-MS reagent ions H3O+, NO+ and O2+[rad] with 21 ketones, M, comprising 13 saturated monoketones of which 10 are linear and 3 are branched, 5 unsaturated monoketones and 3 diones. The collisional rate coefficients, kc, were calculated for the H3O+ reactions that all proceed via rapid proton transfer and the relative rate coefficients for the NO+ and O2+[rad] reactions were obtained experimentally. The product ion distributions for all 63 reactions were obtained at two sample gas absolute humidity (0.5% and 5.5%), the higher humidity intended to simulate that of exhaled breath. A major objective was to understand how the product ions of the reactions formed hydrates, which is important for accurate quantification of metabolites in humid air samples by SIFT-MS and by secondary electrospray ionisation, SESI. The MH+ product ions of the H3O+ reactions readily hydrate at the higher humidity, the monohydrate being dominant for both the saturated and unsaturated ketones, whereas the dihydrate was dominant for the dione reactions. In the NO+ reactions, formation of the NO+M adduct ions was dominant for the saturated and unsaturated ketones, but charge transfer producing the M+[rad] parent cation was very dominant in the dione reactions. The O2+[rad] reactions all proceeded via dissociative charge transfer producing the parent cation M+[rad] and closed shell and open shell cation fragments. Except for the dione parent cations, the M+[rad] ions hydrated, as did the open shell fragment ions of the O2+[rad] reactions, but the closed shell fragment ions did not hydrate.

Název v anglickém jazyce

H3O⁺, NO⁺ and O2^+. reactions with saturated and unsaturated monoketones and diones, focus on hydration of product ions

Popis výsledku anglicky

A selected ion flow tube, SIFT, study has been carried out for the reactions of the SIFT-MS reagent ions H3O+, NO+ and O2+[rad] with 21 ketones, M, comprising 13 saturated monoketones of which 10 are linear and 3 are branched, 5 unsaturated monoketones and 3 diones. The collisional rate coefficients, kc, were calculated for the H3O+ reactions that all proceed via rapid proton transfer and the relative rate coefficients for the NO+ and O2+[rad] reactions were obtained experimentally. The product ion distributions for all 63 reactions were obtained at two sample gas absolute humidity (0.5% and 5.5%), the higher humidity intended to simulate that of exhaled breath. A major objective was to understand how the product ions of the reactions formed hydrates, which is important for accurate quantification of metabolites in humid air samples by SIFT-MS and by secondary electrospray ionisation, SESI. The MH+ product ions of the H3O+ reactions readily hydrate at the higher humidity, the monohydrate being dominant for both the saturated and unsaturated ketones, whereas the dihydrate was dominant for the dione reactions. In the NO+ reactions, formation of the NO+M adduct ions was dominant for the saturated and unsaturated ketones, but charge transfer producing the M+[rad] parent cation was very dominant in the dione reactions. The O2+[rad] reactions all proceeded via dissociative charge transfer producing the parent cation M+[rad] and closed shell and open shell cation fragments. Except for the dione parent cations, the M+[rad] ions hydrated, as did the open shell fragment ions of the O2+[rad] reactions, but the closed shell fragment ions did not hydrate.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

GA18-12902S: Hmotnostní spektrometrie se sekundární elektrosprejovou ionizací (SESI-MS) pro kvantifikaci plynných analytů v ovzduší, prostoru nad vzorky a v dechu

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2019

Kód důvěrnosti údajů

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

Název periodika

International Journal of Mass Spectrometry

ISSN

1387-3806

e-ISSN

—

Svazek periodika

435

Číslo periodika v rámci svazku

JAN 2019

Stát vydavatele periodika

NL - Nizozemsko

Počet stran výsledku

8

Strana od-do

173-180

Kód UT WoS článku

000453773300023

EID výsledku v databázi Scopus

2-s2.0-85056246467