Effect of Sample Plates and Sample Matrix on the Quantification Capabilities of Surface-Assisted Flowing Atmospheric-Pressure Afterglow Mass Spectrometry (SA-FAPA-MS)

Abstract

Ambient desorption/ionization mass spectrometry (ADI-MS) has been broadly applied to accomplish direct analysis without sample preparation or separation. However, quantification capabilities and analytical performance are sometimes limited. Here, we report signal enhancement effects and improved quantification capabilities in plasma-based ADI-MS, when a flowing atmospheric-pressure afterglow (FAPA) source is used to probe analytes on tailored thin-layer chromatography (TLC) plates. It was found that quantitative results could be achieved when the TLC plate merely served as a sampling plate without a preceding separation step. Specifically, the dynamic response of caffeine, nicotine, acetaminophen, and progesterone was investigated with FAPA-MS on a variety of different TLC surfaces (normal-phase silica, reversed-phase-modified silica, cyano [CN]-modified silica, and dimethyl [RP2]-modified silica). All analytes were studied as single-analyte standards and in a multianalyte mixture to evaluate the effect of sample plates and sample matrix on analytical performance and competitive ionization processes. Overall, dimethyl (RP2)- and CN-modified silica resulted in superior performance compared to other TLC materials. After careful optimization and without the use of internal standards, linear ranges of five orders of magnitude were accessible for caffeine and nicotine. Limits of detection down to femtomole amounts of analyte were achieved. Quantitation limits using RP2-TLC and FAPA-MS were 0.062, 0.062l, 0.31, and 14 pmol for caffeine, nicotine, progesterone, and acetaminophen, respectively. Interestingly, the presence of nicotine at relatively high amounts reduced the signal of the other analytes, an observation that was found to correlate with the differences in the enthalpy of vaporization (ΔH_vap) and proton affinity. To prove the quantitative capabilities, nicotine quantification in a real matrix-heavy e-liquid sample was demonstrated using an isotopically labeled standard. The use of TLC-based surfaces with FAPA-MS can aid in the direct and quantitative mass spectrometric investigation of complex mixtures.

Graphical Abstract

This is a visual representation of the abstract.

Keywords

Ambient desorption/ionization mass spectrometry flowing atmospheric-pressure afterglow surface-assisted electronic cigarette e-liquid

Get full access to this article

View all access options for this article.

References

Takats

Wiseman

J.M.

Gologan

Cooks

R.G.

. “Mass Spectrometry Sampling Under Ambient Conditions with Desorption Electrospray Ionization”. Science. 2004. 306(5695): 471–473. 10.1126/science.110440

Cody

R.B.

Laramee

J.A.

Durst

H.D.

. “Versatile New Ion Source for the Analysis of Materials in Open Air Under Ambient Conditions”. Anal. Chem. 2005. 77(8): 2297–2302. doi:10.1021/ac050162j

Feider

C.L.

Krieger

DeHoog

R.J.

Eberlin

L.S.

. “Ambient Ionization Mass Spectrometry: Recent Developments and Applications”. Anal. Chem. 2019. 91(7): 4266–4290. 10.1021/acs.analchem.9b00807

Albert

Shelley

J.T.

Engelhard

. “Plasma-Based Ambient Desorption/Ionization Mass Spectrometry: State-of-the-Art in Qualitative and Quantitative Analysis”. Anal. Bioanal. Chem. 2014. 406(25): 6111–6127. 10.1007/s00216-014-7989-z

Ding

X.L.

Duan

Y.X.

. “Plasma-Based Ambient Mass Spectrometry Techniques: The Current Status and Future Prospective”. Mass Spectrom. Rev. 2015. 34(4): 449–473. 10.1002/mas.21415

Smoluch

Mielczarek

Silberring

. “Plasma-Based Ambient Ionization Mass Spectrometry in Bioanalytical Sciences”. Mass Spectrom. Rev. 2016. 35(1): 22–34. 10.1002/mas.21460

Ouyang

. “Ambient Ionization and Miniature Mass Spectrometry System for Chemical and Biological Analysis”. TrAC, Trends Anal. Chem. 2016. 85(Pt. A): 10–19. 10.1016/j.trac.2016.04.009

Chen

R.H.

Deng

J.W.

Fang

Yao

, et al. “Recent Applications of Ambient Ionization Mass Spectrometry in Environmental Analysis”. Trends Environ. Anal. Chem. 2017. 15: 1–11. 10.1016/j.teac.2017.07.001

Chen

Tang

Guo

C.A.

Zhang

S.C.

, et al. “Plasma-Based Ambient Mass Spectrometry: A Step Forward to Practical Applications”. Anal. Methods. 2017. 9(34): 4908–4923. 10.1039/C7AY00965H

10.

Forbes

T.P.

Sisco

. “Recent Advances in Ambient Mass Spectrometry of Trace Explosives”. Analyst. 2018. 143(9): 1948–1969. 10.1039/C7AN02066J

11.

Shelley

J.T.

Badal

S.P.

Engelhard

Hayen

. “Ambient Desorption/Ionization Mass Spectrometry: Evolution from Rapid Qualitative Screening to Accurate Quantification Tool”. Anal. Bioanal. Chem. 2018. 410(17): 4061–4076. 10.1007/s00216-018-1023-9

12.

Nie

H.G.

Jiang

L.P.

Ruan

G.H.

, et al. “Recent Advances of Ambient Ionization Mass Spectrometry Imaging in Clinical Research”. J. Sep. Sci. 2020. 43(15): 3146–3163. 10.1002/jssc.202000273

13.

Yue

H.L.

F.Y.

Zhao

Z.J.

Duan

Y.X.

. “Plasma-Based Ambient Mass Spectrometry: Recent Progress and Applications”. Mass Spectrom. Rev. 2021. 42(1): 95–130. 10.1002/mas.21712

14.

Cody

R.B.

. “Observation of Molecular Ions and Analysis of Nonpolar Compounds with the Direct Analysis in Real Time Ion Source”. Anal. Chem. 2009. 81(3): 1101–1107. 10.1021/ac8022108

15.

Gross

J.H.

. “Direct Analysis in Real Time: A Critical Review on DART-MS”. Anal. Bioanal. Chem. 2014. 406(1): 63–80. 10.1007/s00216-013-7316-0

16.

Andrade

F.J.

Shelley

J.T.

Wetzel

W.C.

Webb

, et al. “Atmospheric Pressure Chemical Ionization Source. 1. Ionization of Compounds in the Gas Phase”. Anal. Chem. 2008. 80(8): 2646–2653. 10.1021/ac800156y

17.

Andrade

F.J.

Shelley

J.T.

Wetzel

W.C.

Webb

, et al. “Atmospheric Pressure Chemical Ionization Source. 2. Desorption-Ionization for the Direct Analysis of Solid Compounds”. Anal. Chem. 2008. 80(8): 2654–2663. 10.1021/ac800210s

18.

Andrade

F.J.

Wetzel

W.C.

Chan

G.C.-Y.

Webb

, et al. “A New, Versatile, Direct-Current Helium Atmospheric-Pressure Glow Discharge”. J. Anal. At. Spectrom. 2006. 21(11): 1175–1184. 10.1039/B607544D

19.

Shelley

J.T.

Wiley

J.S.

Hieftje

G.M.

. “Ultrasensitive Ambient Mass Spectrometric Analysis with a Pin-to-Capillary Flowing Atmospheric-Pressure Afterglow Source”. Anal. Chem. 2011. 83(14): 5741–5748. 10.1021/ac201053q

20.

Pfeuffer

K.P.

Schaper

J.N.

Shelley

J.T.

Ray

S. J.

et al. “Halo-Shaped Flowing Atmospheric Pressure Afterglow: A Heavenly Design for Simplified Sample Introduction and Improved Ionization in Ambient Mass Spectrometry”. Anal. Chem. 2013. 85(15): 7512–7518. 10.1021/ac401524x

21.

Shelley

J.T.

Wiley

J.S.

Chan

G.C.-Y.

Schilling

, et al. “Characterization of Direct-Current Atmospheric-Pressure Discharges Useful for Ambient Desorption/Ionization Mass Spectrometry”. J. Am. Soc. Mass Spectrom. 2009. 20(5): 837–844. 10.1016/j.jasms.2008.12.020

22.

Paglia

Ifa

D.R.

C.P.

Corso

, et al. “Desorption Electrospray Ionization Mass Spectrometry Analysis of Lipids After Two-Dimensional High-Performance Thin-Layer Chromatography Partial Separation”. Anal. Chem. 2010. 82(5): 1744–1750. 10.1021/ac902325j

23.

Pasilis

S.P.

Kertesz

Van Berkel

G.J.

Schulz

, et al. “HPTLC/DESI-MS Imaging of Tryptic Protein Digests Separated in Two Dimensions”. J. Mass Spectrom. 2008. 43(12): 1627–1635. 10.1002/jms.1431

24.

Van Berkel

G.J.

Ford

M.J.

Deibel

M.A.

. “Thin-Layer Chromatography and Mass Spectrometry Coupled Using Desorption Electrospray Ionization”. Anal. Chem. 2005. 77(5): 1207–1215. 10.1021/ac048217p

25.

Morlock

Chernetsova

E.S.

. “Coupling of Planar Chromatography with Direct Analysis in Real Time Mass Spectrometry”. Cent. Eur. J. Chem. 2012. 10(3): 703–710. 10.2478/s11532-012-0025-2

26.

Kiguchi

Oka

Tamada

Kobayashi

, et al. “Thin-Layer Chromatography/Direct Analysis in Real Time Time-of-Flight Mass Spectrometry and Isotope Dilution to Analyze Organophosphorus Insecticides in Fatty Foods”. J. Chromatogr. A. 2014. 1370: 246–254. 10.1016/j.chroma.2014.10.037

27.

Eichner

Spangenberg

. “Optimized Determination of Caffeine, Equol, and Artemisinin by High-Performance Thin-Layer Chromatography-Direct Analysis in Real Time-Time of Flight-Mass Spectrometry”. J. Planar. Chromatogr.–Mod. TLC. 2019. 32(3): 197–203. 10.1556/1006.2019.32.3.4

28.

Gong

Zhang

Embile

I.B.

She

, et al. “Low-Temperature Plasma Probe Mass Spectrometry for Analytes Separated on Thin-Layer Chromatography Plates: Direct vs Laser Assisted Desorption”. J. Am. Soc. Mass Spectrom. 2020. 31(9): 1981–1993. 10.1021/jasms.0c00246

29.

Ceglowski

Smoluch

Reszke

Silberring

, et al. “Flowing Atmospheric-Pressure Afterglow Combined with Laser Ablation for Direct Analysis of Compounds Separated by Thin-Layer Chromatography”. Anal. Bioanal. Chem. 2016. 408(3): 815–823. 10.1007/s00216-015-9165-5

30.

Kuhlmann

Heide

Engelhard

. “Fast Screening and Quantitative Mass Spectral Imaging of Thin-Layer Chromatography Plates with Flowing Atmospheric-Pressure Afterglow High-Resolution Mass Spectrometry”. Anal. Bioanal. Chem. 2019. 411(23): 6213–6225. 10.1007/s00216-019-02013-8

31.

Heide

Escobar-Carranza

C.C.

Engelhard

. “Quantitative Detection of Caffeine in Beverages Using Flowing Atmospheric-Pressure Afterglow (FAPA) Ionization High-Resolution Mass Spectrometry Imaging and Performance Evaluation of Different Thin-Layer Chromatography Plates as Sample Substrates”. Anal. Bioanal. Chem. 2022. 414(15): 4481–4495. 10.1007/s00216-022-04045-z

32.

Pluskal

Castillo

Villar-Briones

Oresic

. “MZmine 2: Modular Framework for Processing, Visualizing, and Analyzing Mass Spectrometry-Based Molecular Profile Data”. BMC Bioinformatics. 2010. 11(395): 1–11. 10.1186/1471-2105-11-395

33.

Lipkind

Hanshaw

Chickos

J.S.

. “Hypothetical Thermodynamic Properties. Subcooled Vaporization Enthalpies and Vapor Pressures of Polyaromatic Heterocycles and Related Compounds”. J. Chem. Eng. Data. 2009. 54(10): 2930–2943. 10.1021/je900034d

34.

Boller

Wiedemann

H.G.

. “Vapor Pressure Determination by Pressure DSC”. J. Therm. Anal. Calorim. 1998. 53(2): 431–439. 10.1023/A:1010133106907

35.

Vecchio

Tomassetti

. “Vapor Pressures and Standard Molar Enthalpies, Entropies and Gibbs Energies of Sublimation of Three 4-Substituted Acetanilide Derivatives”. Fluid Phase Equilib. 2009. 279(1): 64–72. 10.1016/j.fluid.2009.02.001

36.

Muller

. “Glossary of Terms Used in Physical Organic Chemistry”. Pure Appl. Chem. 1994. 66(5): 1077–1184. 10.1351/pac199466051077

37.

Angelelli

Aschi

Cacace

Pepi

, et al. “Gas-Phase Reactivity of Hydroxylamine Toward Charged Electrophiles: A Mass Spectrometric and Computational Study of the Protonation and Methylation of H₂NOH”. J. Phys. Chem. 1995. 99(17): 6551–6556. 10.1021/j100017a041

38.

Bohme

D.K.

Mackay

G.I.

Schiff

H.I.

. “Determination of Proton Affinities from the Kinetics of Proton-Transfer Reactions. VII. The Proton Affinities of O₂, H₂, Kr, O, N₂, Xe, CO₂, CH₄, N₂O, and CO”. J. Chem. Phys. 1980. 73(10): 4976–4986. 10.1063/1.439975

39.

Haynes

W.M.

. CRC Handbook of Chemistry and Physics. Boca Raton, Florida: CRC Press, 2016.

40.

Bahrami

Tabrizchi

Farrokhpour

. “Protonation of Caffeine: A Theoretical and Experimental Study”. Chem. Phys. 2013. 415: 222–227. 10.1016/j.chemphys.2013.01.022

41.

Bahrami

Farrokhpour

. “Corona Discharge Ionization of Paracetamol Molecule: Peak Assignment”. Spectrochim. Acta, Part A. 2015. 135: 646–651. 10.1016/j.saa.2014.07.064

42.

Kauppila

T.J.

Talaty

Jackson

A.U.

Kotiaho

, et al. “Carbohydrate and Steroid Analysis by Desorption Electrospray Ionization Mass Spectrometry”. Chem. Commun. 2008. 23: 2674–2676. 10.1039/B804413A.

43.

Farsalinos

K.E.

Gillman

. “Carbonyl Emissions in E-Cigarette Aerosol: A Systematic Review and Methodological Considerations”. Front. Physiol. 2018. 8(1119): 1–14. 10.3389/fphys.2017.01119

Supplementary Material

Please find the following supplemental material available below.

For Open Access articles published under a Creative Commons License, all supplemental material carries the same license as the article it is associated with.

For non-Open Access articles published, all supplemental material carries a non-exclusive license, and permission requests for re-use of supplemental material or any part of supplemental material shall be sent directly to the copyright owner as specified in the copyright notice associated with the article.

0.00 MB

2.93 MB

8.24 MB