Regulated In Situ Generation of Molecular Ions or Protonated Molecules under Atmospheric-Pressure Helium-Plasma-Ionization Mass Spectrometric Conditions

American Chemical Society (ACS) - Tập 26 - Trang 1252-1255 - 2015
Rekha Gangam1, Julius Pavlov1, Athula B. Attygalle1
1Center for Mass Spectrometry, Department of Chemistry, Chemical Biology, and Biomedical Engineering, Stevens Institute of Technology, Hoboken, USA

Tóm tắt

In an enclosed atmospheric-pressure helium-plasma ionization (HePI) source engulfed with dehumidified ambient gases, molecular cations are generated from compounds such as toluene, bromobenzene, and iodobenzene. Evidently, the ionization is effected by a direct Penning mechanism attributable to interactions of the gas-phase analyte with metastable helium atoms. It is widely known that secondary ions generated from ambient gases also play an important role in the overall ionization process. For example, when the ambient gases bear even traces of moisture, the analytes are ionized by proton transfer reactions with gaseous H3O+. In this study, we demonstrate how a controlled variation of experimental conditions can manipulate the abundance of molecular ions and protonated molecules in a HePI source.

Tài liệu tham khảo

Takáts, Z., Wiseman, J.M., Gologan, B., Cooks, R.G.: Mass spectrometry sampling under ambient conditions with desorption electrospray ionization. Science 306, 471–473 (2004) Takáts, Z., Wiseman, J.M., Cooks, R.G.: Ambient mass spectrometry using desorption electrospray ionization (DESI): instrumentation, mechanisms and applications in forensics, chemistry, and biology. J. Mass Spectrom. 40, 1261–1275 (2005) Cody, R.B., Laramée, J.A., Durst, H.D.: Versatile new ion source for the analysis of materials in open air under ambient conditions. Anal. Chem. 77, 2297–2302 (2005) Harris, G.A., Galhena, A.S., Fernández, F.M.: Ambient sampling/ionization mass spectrometry: applications and current trends. Anal. Chem. 83, 4508–4538 (2011) Nyadong, L., Galhena, A.S., Fernández, F.M.: Desorption electrospray/metastable-induced ionization: a flexible multimode ambient ion generation technique. Anal. Chem. 81, 7788–7794 (2009) Song, L., Gibson, S.C., Deepak, B., Cook, K.D., Bartmess, J.E.: Ionization mechanism of positive-ion direct analysis in real time: a transient microenvironment concept. Anal. Chem. 81, 10080–10088 (2009) Symonds, J.M., Galhena, A.S., Fernández, F.M., Orlando, T.M.: Microplasma discharge ionization source for ambient mass spectrometry. Anal. Chem. 82, 621–627 (2010) Venter, A.R., Douglass, K.A., Shelley, J.T., Hasman, G., Honarvar, E.: Mechanisms of real-time, proximal sample processing during ambient ionization mass spectrometry. Anal. Chem. 86, 233–249 (2013) Chen, H., Gamez, G., Zenobi, R.: What can we learn from ambient ionization techniques? J. Am. Soc. Mass Spectrom. 20, 1947–1963 (2009) Chernetsova, E.S., Morlock, G.E., Revelsky, I.A.: DART mass spectrometry and its applications in chemical analysis. Russ. Chem. Rev. 80, 235–255 (2011) Ding, X., Duan, Y.: Plasma-based ambient mass spectrometry techniques: the current status and future perspective. Mass Spectrom. Rev. doi:10.1002/mas.21415 Monge, M.E., Harris, G.A., Dwivedi, P., Fernández, F.M.: Mass spectrometry: recent advances in direct open air surface sampling/ionization. Chem. Rev. 113, 2269–2308 (2013) Alberici, R.M., Simas, R.C., Sanvido, G.B., Romão, W., Lalli, P.M., Benassi, M., Cunha, I.B.S., Eberlin, M.N.: Ambient mass spectrometry: bringing MS into the “real world.”. Anal. Bioanal. Chem. 398, 265–294 (2010) Klee, A., Derpmann, V., Wißdorf, W., Klopotowski, S., Kersten, H., Brockmann, K.J., Benter, T., Albrecht, S., Bruins, A.P., Dousty, F., Kauppila, T.J., Kostiainen, R., O’Brien, R., Robb, D.B., Syage, J.A.: Are clusters important in understanding the mechanisms in atmospheric pressure ionization? Part 1: Reagent ion generation and chemical control of ion populations. J. Am. Soc. Mass Spectrom. 25, 1310–1321 (2014) Albert, A., Shelley, J.T., Engelhard, C.: Plasma-based ambient desorption/ionization mass spectrometry: state-of-the-art in qualitative and quantitative analysis. Anal. Bioanal. Chem. 406, 6111–6127 (2014) Gross, J.H.: Direct analysis in real time—a critical review on DART-MS. Anal. Bioanal. Chem. 406, 63–80 (2014) Penning, F.M.: Über Ionisation durch metastabile Atome. Naturwissenschaften 15, 818 (1927) Yang, H., Wan, D., Song, F., Liu, Z., Liu, S.: Argon direct analysis in real time mass spectrometry in conjunction with makeup solvents: a method for analysis of labile compounds. Anal. Chem. 85, 1305–1309 (2013) Cody, R.B.: Observation of molecular ions and analysis of nonpolar compounds with the direct analysis in real time ion source. Anal. Chem. 81, 1101–1107 (2009) Chan, C.-C., Bolgar, M.S., Scott, A., Miller, S.A., Attygalle, A.B...: Desorption ionization by charge exchange (DICE) for sample analysis under ambient conditions by mass spectrometry. J. Am. Soc. Mass Spectrom. 21, 1554–1560 (2010) Ray, A.D., Hammond, J., Major, H.: Molecular ions and protonated molecules observed in the atmospheric solids analysis probe analysis of steroids. Eur. J. Mass Spectrom. 16, 169–174 (2010) Rummel, J.L., McKenna, A.M., Marshall, A.G., Eyler, J.R., Powell, D.H.: The coupling of direct analysis in real time ionization to Fourier transform ion cyclotron resonance mass spectrometry for ultrahigh-resolution mass analysis. Rapid Commun. Mass Spectrom. 24, 784–790 (2010) Yang, Z., Attygalle, A.B...: Aliphatic hydrocarbon spectra by helium ionization mass spectrometry (HIMS) on a modified atmospheric-pressure source designed for electrospray ionization. J. Am. Soc. Mass Spectrom. 22, 1395–1402 (2011) Cody, R.B., Dane, A.J.: Soft ionization of saturated hydrocarbons, alcohols, and nonpolar compounds by negative-ion direct analysis in real-time mass spectrometry. J. Am. Soc. Mass Spectrom. 24, 329–334 (2013) Attygalle, A.B..., Gangam, R., Pavlov, J.: Real-time monitoring of in situ gas-phase H/D exchange reactions of organic cations by atmospheric pressure helium plasma ionization mass spectrometry (HePI-MS). Anal. Chem. 86, 928–935 (2014) Li, Y.: Applications of a confined DART (direct analysis in real time) ion source for online in vivo analysis of human breath. Anal. Methods 5, 6933–6940 (2013)