Suitable in-situ derivatization of alcohols by reaction with basic amines in Direct Analysis in Real Time mass spectrometry

Roman S Borisov; Cesar Esparza; Sergei V Goriainov; Vladimir G Zaikin

doi:10.1016/j.talanta.2019.03.037

Suitable in-situ derivatization of alcohols by reaction with basic amines in Direct Analysis in Real Time mass spectrometry

Talanta. 2019 Aug 1:200:31-40. doi: 10.1016/j.talanta.2019.03.037. Epub 2019 Mar 7.

Authors

Roman S Borisov¹, Cesar Esparza², Sergei V Goriainov³, Vladimir G Zaikin⁴

Affiliations

¹ A.V.Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 29 Leninsky pr.,119991 Moscow, Russia; Рeoples Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya St, Moscow 117198, Russia. Electronic address: borisov@ips.ac.ru.
² Рeoples Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya St, Moscow 117198, Russia.
³ A.V.Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 29 Leninsky pr.,119991 Moscow, Russia; Рeoples Friendship University of Russia (RUDN University), 6 Miklukho-Maklaya St, Moscow 117198, Russia.
⁴ A.V.Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, 29 Leninsky pr.,119991 Moscow, Russia.

PMID: 31036190
DOI: 10.1016/j.talanta.2019.03.037

Abstract

This work highlights the discovered in-situ analytical reaction between primary/secondary alcohols and nitrogenous bases (pyridine, quinoline) that involves the substitution of hydroxyl groups for nitrogen-containing charged species and proceeds in an ionization region of Direct Analysis in Real Time mass spectrometry (DART-MS) instrument at gas stream temperature of 150-450 °C. Resulted cations provide strong signals in mass spectra and this ensures high sensitivity of the analysis. Collision induced dissociation of such precursor ions gives rise to characteristic and simple fragmentation mass spectra revealing mainly protonated nitrogenous bases and carbonium cations resulting from the elimination of neutral nitrogen-containing bases. The dependence of signal response on gas stream temperature was elucidated. It was also found that, independently of gas stream temperature, high volatility low-molecular weight alcohols did not demonstrate characteristic DART spectra owing to a high rate of desorption/evaporation which does not provide sufficient probability of the reaction. To the best of our knowledge, this type of specific reactions in a plasma-based source of DART mass spectrometer is reported for the first time. It represents a new and interesting derivatization approach providing a rapid and sensitive complement method for the detection and identification of individual monools of various origin, profiling plant sterols and other steroid alcohols in different matrices.

Keywords: Alcohols analysis; DART mass spectrometry; DART plasma reaction; Derivatization; Nitrogeneous reagents.