Abstract
Twenty-three different dications were investigated for their effectiveness in pairing with singly charged anions, thereby allowing the electrospray ionization mass spectrometry (ESI-MS) detection of anions as positively charged complexes. Nitrate, iodide, cyanate, monochloroacetate, benzenesulfonate, and perfluoro-octanoate were chosen as representative test anions as they differ in mass, size-to-charge ratio, chaotropic nature, and overall complexity. Detection limits were found using direct injection of the anion into a carrier liquid containing the dication. Detection limits are given for all six anions with each of the 23 dications. Each anion was easily detected at the ppb (µg/L) and often the ppt (ng/L) levels using certain dicationic reagents. The ability of dicationic reagents to pair with anions and produce ESI-MS signals varied tremendously. Indeed, only a few dications can be considered broadly useful and able to produce sensitive results. Liquid chromatography (LC)-ESI-MS also was investigated and used to show how varying the dicationic reagent produced significantly different peak intensities. Also, the use of tandem mass spectrometry can lead to even greater sensitivity when using imidazolium based dications.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
Pretsch, E. The New Wave of Ion — Selective Electrodes. Trends Anal. Chem. 2007, 26(1), 46–51.
Buck, R. P.; Lindner, E. Tracing the History of Selective Ion Sensors. Anal. Chem. 2001, 73(3), 88A-97A.
Haddad, P. R. Ion Chromatography. Anal. Bioanal. Chem. 2004, 379(3), 341–343.
Kuban, P.; Dasgupta, P. K. Capillary Ion Chromatography. J. Sep. Sci. 2004, 27(17/18), 1441–1457.
Hansen, E. H.; Wang, J.-H. The Three Generations of Flow Injection Analysis. Anal. Lett. 2004, 37(3), 345–359.
Miro, M.; Frenzel, W. What Flow Injection has to Offer in the Environmental Analytical Field. Microchim. Acta. 2004, 148(1/2), 1–20.
Whitehouse, C. M.; Dreyer, R. N.; Yamashita, M.; Fenn, J. B. Electrospray Interface for Liquid Chromatographs and Mass Spectrometers. Anal. Chem. 1985, 57(3), 675–679.
Cech, N. B.; Enke, C. G. Practical Implications of Some Recent Studies in Electrospray Ionization Fundamentals. Mass Spectrom. Rev. 2001, 20(6), 362–387.
Voyksner, R. D. Combining Liquid Chromatography with Electrospray Mass Spectrometry. Cole, R. B., Ed.; In Electrospray Ionization Mass Spectrometry; pp 323–341. Wiley: New York, 323–341.
Henriksen, T.; Juhler, R. K.; Svensmark, B.; Cech, N. B. The Relative Influences of Acidity and Polarity on Responsiveness of Small Organic Molecules to Analysis with Negative Ion Electrospray Ionization Mass Spectrometry (ESI-MS). J. Am. Soc. Mass Spectrom. 2005, 16(4), 446–455.
Kebarle, P.; Yeunghaw, H. On the Mechanism of Electrospray Mass Spectrometry. Cole, R. B., Ed.; In Electrospray Ionization Mass Spectrometry, p 14 Wiley: New York,
Cole, R. B.; Zhu, J.-H. Chloride Anion Attachment in Negative Ion Electrospray Ionization Mass Spectrometry. Rapid Commun. Mass Spectrom. 1999, 13(7), 607–611.
Apffel, A.; Chakel, J. A.; Fischer, S.; Lichtenwalter, K.; Hancock, W. S. Analysis of Oligonucleotides by HPLC-Electrospray Ionization Mass Spectrometry. Anal. Chem. 1997, 69(7), 1320–1325.
Straub, R. F.; Voyksner, R. D. Negative Ion Formation in Electrospray Mass Spectrometry. J. Am. Soc. Mass Spectrom. 1993, 4(7), 578–587.
Cole, R. B.; Harrata, A. K. Charge-State Distribution and Electric-Discharge Suppression in Negative-Ion Electrospray Mass Spectrometry Using Chlorinated Solvents. Rapid Commun. Mass Spectrom. 1992, 6(8), 536–539.
Martinelango, P. K.; Anderson, J. L.; Dasgupta, P. K.; Armstrong, D. W.; Al-Horr, R. S.; Slingsby, R. W. Gas-Phase Ion Association Provides Increased Selectivity and Sensitivity for Measuring Perchlorate by Mass Spectrometry. Anal. Chem. 2005, 77(15), 4829–4835.
Martinelango, P. K.; Guemues, G.; Dasgupta, P. K. Matrix Interference Free Determination of Perchlorate in Urine by Ion Association-Ion Chromatography-Mass Spectrometry. Anal. Chim. Acta. 2006, 567(1), 79–86.
Dyke, J. V.; Kirk, A. B.; Kalyani, M. P.; Dasgupta, P. K. Sample Processing Method for the Determination of Perchlorate in Milk. Anal. Chim. Acta. 2006, 567(1), 73–78.
Martinelango, P. K.; Tian, K.; Dasgupta, P. K. Perchlorate in Seawater. Anal. Chim. Acta. 2006, 567(1), 100–107.
Soukup-Hein, R. J.; Remsburg, J. W.; Dasgupta, P. K.; Amstrong, D. W. A General, Sensitive, Positive Ion Mode ESI-MS Approach for the Analysis of Singly Charged Inorganic and Organic Anions Using a Dicationic Reagent. Anal. Chem. 2007, 79(19), 7346–7352.
Anderson, J. L.; Ding, R.; Ellern, A.; Armstrong, D. W. Structure and Properties of High Stability Geminal Dicationic Ionic Liquids. J. Am. Chem. Soc. 2005, 127(2), 593–604.
Huang, K.; Han, X.; Zhang, X.; Armstrong, D. W. PEG-linked Geminal Dicationic Ionic Liquids as Selective, High Stability Gas Chromatographic Stationary Phases. Anal. Bioanal. Chem. 2007, in press.
Payagala, T.; Huang, J.; Breitbach, Z. S.; Sharma, P. S.; Armstrong, D. W. Unsymmetrical Dicationic Ionic Liquids: Manipulation of Physicochemical Properties Using Specific Structural Architectures. Chem. Mater. J. 2007, 19(24), 5848–5850.
Giller, S.; Le Curieux, F.; Erb, F.; Marzin, D. Comparative Genotoxicity of Halogenated Acetic Acids Found in Drinking Water. Mutagenesis. 1997, 12(5), 321–328.
Kennedy, G. L., Jr.; Butenhoff, J. L.; Olsen, G. W.; O’Connor, J. C.; Seacat, A. M.; Perkins, R. G.; Biegel, L. B.; Murphy, S. R.; Farrar, D. G. The Toxicology of Perfluoro-octanoate. Crit. Rev. Toxicol. 2004, 34(4), 351–384.
Kumar, K. S. Fluorinated Organic Chemicals: A Review. Res. J. Chem. Environ. 2005, 9(3), 50–79.
Borsdorf, H.; Eiceman, G. A. Ion Mobility Spectrometry: Principles and Applications. Appl. Spectrosc. Rev. 2006, 41(4), 323–375.
Wyttenbach, T.; Bowers, M. T. Gas-Phase Conformations: The Ion Mobility/Ion Chromatography Method. Topics Curr. Chem. 2003, 225(Mod. Mass Spectrom.), 207–232.
Author information
Authors and Affiliations
Corresponding author
Additional information
Published online November 7, 2007
Rights and permissions
About this article
Cite this article
Remsburg, J.W., Soukup-Hein, R.J., Crank, J.A. et al. Evaluation of dicationic reagents for their use in detection of anions using positive ion mode ESI-MS via gas phase ion association. J. Am. Soc. Spectrom. 19, 261–269 (2008). https://doi.org/10.1016/j.jasms.2007.11.002
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1016/j.jasms.2007.11.002