Analysis of the ion mobility spectra of chloroacetophenone, tris(2-chloroethyl)amine, and methanethiol

Objectives. To determine the ion mobilities of chloroacetophenone, tris(2-chloroethyl)amine, and methanethiol; the structure of ions corresponding to characteristic signals; the detection limits of chloroacetophenone, tris(2-chloroethyl)amine, and methanethiol with the Kerber-T ion drift detector and the Segment automatic stationary gas detector.
Methods. Ion mobility spectrometry was used in order to determine the ion mobilities and detect analytes. The enthalpies of reactions of ion formation were calculated using the ORCA 4.1.1 software by means of the B3LYP density functional method with the 6-31G(d,p) basis set.
Results. The ion mobilities of chloroacetophenone, tris(2-chloroethyl)amine, and methanethiol were determined. A method for recording ion mobility spectra and their mathematical processing was developed. The dependencies of the change in ion mobility spectra on the analyte concentration were also studied. Possible mechanisms were proposed for the formation of the ion mobility spectra observed, in accordance with the ionization features of chloroacetophenone, tris(2-chloroethyl)amine, and methanethiol. The enthalpies of ion formation were calculated. The ionization schemes of the compounds were shown. The generalized results of experimental studies were presented, as were the features of compound identification taking into account the structure of the spectra, the concentrations of substances, and the detection conditions.
Conclusions. Characteristic signals of chloroacetophenone, tris(2-chloroethyl)amine, and methanethiol were identified. All studied hazardous substances can be detected with an ion mobility spectrometer at concentrations at the ppm level. The following detection limits of the substances were determined with the Segment gas detector: chloroacetophenone, 245 mg/m³; tris(2-chloroethyl)amine, 0.01 mg/m³; and methanethiol, 0.8 mg/m³.

1. Mäkinen M.A., Anttalainen O.A., Sillanpää M.E. Ion mobility spectrometry and its applications in detection of chemical warfare agents. Anal. Chem. 2010;82(23):9594–9600. https://doi.org/10.1021/ac100931n

2. Yamaguchi S., Asada R., Kishi Sh., Sekioka R., Kitagawa N., Tokita K., Yamamoto S., Seto Y. Detection performance of a portable ion mobility spectrometer with 63Ni radioactive ionization for chemical warfare agents. Forensic Toxicol. 2010;28(2):84–95. https://doi.org/10.1007/s11419-010-0092-z

3. Hernandez-Mesa M., Ropartz D., Garcia-Campana A.M., Rogniaux H., Dervilly-Pinel G., Le Bizec B. Ion mobility spectrometry in food analysis: Principles, current applications and future trends. Molecules. 2019;24(15):2706. https://doi.org/10.3390/molecules24152706

4. Jafari M.T., Khayamian T., Shaer V., Zarei N. Determination of veterinary drug residues in chicken meat using corona discharge ion mobility spectrometry. Anal. Chim. Acta. 2007;581(1): 147–153. https://doi.org/10.1016/j.aca.2006.08.005

5. Hashemian Z., Mardihallaj A., Khayamian T. Analysis of biogenic amines using corona discharge ion mobility spectrometry. Talanta. 2010;81(3):1081–1087. https://doi.org/10.1016/j.talanta.2010.02.001

6. Allers M., Schaefer Ch., Ahrens A., Schlottmann F., Hitzemann M., Kobelt T., Zimmermann S., Hetzer R. Detection of volatile toxic industrial chemicals with classical ion mobility spectrometry and high-kinetic energy ion mobility spectrometry. Anal. Chem. 2022;94(2):1211−1220. https://doi.org/10.1021/acs.analchem.1c04397

7. Смолин Ю.М., Кобцев Б.Н., Новоселов Н.П. Метод спектрометрии ионной подвижности для обнаружения химических загрязнений окружающей среды. Вестник ТГТУ. 2009;15(3):620–628.

8. Krylova N., Krylov E., Eiceman G.A., Stone J.A. Effect of moisture on the field dependency of mobility for gas-phase ions of organophosphorus compounds at atmospheric pressure with field asymmetric ion mobility spectrometry. J. Phys. Chem. A. 2003;107(19):3648–3654. https://doi.org/10.1021/jp0221136

9. Eiceman G.A., Kapras Z., Hill H.H. Ion Mobility Spectrometry. 3rd ed. Boca Raton: CRC Press; 2014. 444 p.

10. Borsdorf H., Eiceman G.A. Ion mobility spectrometry: Principles and applications. Appl. Spectroscopy Rev. 2006;41(4): 323–375. https://doi.org/10.1080/05704920600663469

11. Marquez-Sillero I., Aguilera-Herrador E., Cardenas S., Valcarcel M. Ion-mobility spectrometry for environmental analysis. TrAC Trends in Analytical Chemistry. 2011;30(5): 677–690. https://doi.org/10.1016/j.trac.2010.12.007

12. Александрова Д.А., Меламед Т.Б., Баберкина Е.П., Коваленко А.Е., Кузнецов Вл. Вит., Кузнецов Вит. Вл., Фенин А.А., Шалтаева Ю.Р., Беляков В.В. Спектрометрия ионной подвижности имидазола и возможности его определения. Журн. аналит. химии. 2021;76(11):989–996. https://doi.org/10.31857/S0044450221110025

13. Александрова Д.А., Меламед Т.Б., Баберкина Е.П., Фенин А.А., Осинова Е.С., Коваленко А.Е., Якушин Р.В., Шалтаева Ю.Р., Беляков В.В., Зыкова Д.И. Спектрометрия ионной подвижности N-метилимидазола и возможности его определения. Тонкие Химические Технологии. 2021;16(6):512–525. https://doi.org/10.32362/2410-6593-2021-16-6-512-525