Abstract
An experimental investigation and theoretical analysis are reported on charge competition in electrospray ionization (ESI) and its effects on the linear dynamic range of ESI mass spectrometric (MS) measurements. The experiments confirmed the expected increase of MS sensitivities as the ESI flow rate decreases. However, different compounds show somewhat different mass spectral peak intensities even at the lowest flow rates, at the same concentration and electrospray operating conditions. MS response for each compound solution shows good linearity at lower concentrations and levels off at high concentration, consistent with analyte “saturation” in the ESI process. The extent of charge competition leading to saturation in the ESI process is consistent with the relative magnitude of excess charge in the electrospray compared to the total number of analyte molecules in the solution. This ESI capacity model allows one to predict the sample concentration limits for charge competition and the on-set of ionization suppression effects, as well as the linear dynamic range for ESI-MS. The implications for quantitative MS analysis and possibilities for effectively extending the dynamic range of ESI measurements are discussed.
Article PDF
Similar content being viewed by others
Avoid common mistakes on your manuscript.
References
Yamashita M.; Fenn J. B. Electrospray Ion Source. Another Variation on the Free-Jet Theme. J. Phys. Chem. 1984, 88, 4451–4459.
Fenn J. B.; Mann M.; Meng C. K.; Wong S. F.; Whitehouse C. M. Electrospray Ionization-Principles and Practice. Mass Spectrom. Rev. 1990, 9, 37–70.
Smith R. D.; Loo J. A.; Loo R. R. O.; Busman M.; Udseth H. R. Principles and Practice of Electrospray Ionization Mass-Spectrometry for Large Polypeptides and Proteins. Mass Spectrom. Rev. 1991, 10, 359–451.
Cech N. B.; Enke C. G. Practical Implications of Some Recent Studies in Electrospray Ionization Fundamentals. Mass Spectrom. Rev. 2001, 20, 362–387.
Wilm M.; Mann M. Analytical Properties of the Nanoelectrospray Ion Source. Anal. Chem. 1996, 68, 1–8.
Schmit A.; Karas M.; Dulcks T. Effect of Different Solution Flow Rates on Analyte Ion Signals in Nano-ESI MS, or: When Does ESI Turn Into Nano-ESI? J. Am. Soc. Mass Spectrom. 2003, 14, 492–500.
Wilm M.; Mann M. Electrospray and Taylor-Cone Theory, Dole’s Beam of Macromolecules at Last? Int. J. Mass Spectrom. Ion Processes. 1994, 136, 167–180.
Fernandez de la Mora J.; Loscertales I. G. The Current Emitted by Highly Conducting Taylor Cones. J. Fluid Mech. 1994, 260, 155–184.
Juraschek R.; Dulcks T.; Karas M. Nanoelectrospray—More Than Just a Minimized-Flow Electrospray Ionization Source. J. Am. Soc. Mass Spectrom. 1999, 10, 300–308.
Gabelica V.; Vreuls C.; Filee P.; Duval V.; Joris B.; De Pauw E. Advantages and Drawbacks of Nanospray for Studying Noncovalent Protein-DNA Complexes by Mass Spectrometry. Rapid Commun. Mass Spectrom. 2002, 16, 1723–1728.
Tang L.; Kebarle P. Dependence of Ion Intensity in Electrospray Mass Spectrometry on the Concentration of the Analytes in the Electrosprayed Solution. Anal. Chem. 1993, 65, 3654–3668.
Kebarle P.; Tang L. From Ions in Solution to Ions in the Gas-Phase—The Mechanism of Electrospray Mass-Spectrometry. Anal. Chem. 1993, 65, 972A-986A.
Enke C. G. A Predictive Model for Matrix and Analyte Effects in Electrospray Ionization of Singly-Charged Ionic Analytes. Anal. Chem. 1997, 69, 4885–4893.
Kostiainen R.; Bruins A. P. Effect of Solvent on Dynamic Range and Sensitivity in Pneumatically-Assisted Electrospray (Ion Spray) Mass Spectrometry. Rapid Commun. Mass Spectrom. 1996, 10, 1393–1399.
Zook D. R.; Bruins A. P. On Cluster Ions, Ion Transmission, and Linear Dynamic Range Limitations in Electrospray (Ionspray) Mass Spectrometry. Int. J. Mass Spectrom. Ion Processes. 1997, 162, 129–147.
Xu X.; Nolan S. P.; Cole R. B. Electrochemical Oxidation and Nucleophilic-Addition Reactions of Metallocenes in Electrospray Mass-Spectrometry. Anal. Chem. 1994, 66, 119–125.
Cech N. B.; Enke C. G. Relating Electrospray Ionization Response to Nonpolar Character of Small Peptides. Anal. Chem. 2000, 72, 2717–2723.
Cloupeau M.; Prunet-Foch B. Electrostatic Spraying of Liquids in Cone-Jet Mode. J. Electr. 1989, 22, 135–159.
Chen D. R.; Pui D. Y. H.; Kaufman S. L. Electrospraying of Conducting Liquids for Monodisperse Aerosol Generation in the 4 nM to 1.8 mU-M Diameter Range. J. Aerosol Sci. 1995, 26, 963–977.
Hartman R. P. A.; Brunner D. J.; Camelot M. A.; Marijnissen J. C. M.; Scarlett B. Electrohydrodynamic Atomization in the Cone-Jet Mode Physical Modeling of the Liquid Cone and Jet. J. Aerosol Sci. 1999, 30, 823–849.
Tang K.; Smith R. D. Physical/Chemical Separations in the Breakup of Highly Charged Droplets from Electrosprays. J. Am. Soc. Mass Spectrom. 2001, 12, 343–347.
Tolmachev A. V.; Kim T.; Udseth H. R.; Smith R. D.; Bailey T. H.; Futrell J. H. Simulation-Based Optimization of the Electrodynamic Ion Funnel for High Sensitivity Electrospray Ionization Mass Spectrometry. Int. J. Mass Spectrom. 2001, 203, 31–47.
Kim T.; Tang K.; Udseth H. R.; Smith R. D. A Multicapillary Inlet Jet Disruption Electrodynamic Ion Funnel Interface for Improved Sensitivity Using Atmospheric Pressure Ion Sources. Anal. Chem. 2001, 73, 4162–4170.
Tang K.; Tolmachev A. V.; Nikolaev E.; Zhang R.; Belov M. E.; Udseth H. R.; Smith R. D. Independent Control of Ion Transmission in a Jet Disrupter Dual-Channel Ion Funnel Electrospray Ionization MS Interface. Anal. Chem. 2002, 74, 5431–5437.
Smith R. D.; Shen Y.; Tang K. Ultrasensitive and Quantitative Analyses from Combined Separations-Mass Spectrometry for the Characterization of Proteomes. Acc. Chem. Res. 2004, 37, 269–278.
Znamenskiy V.; Marginean I.; Vertes A. Solvated Ion Evaporation from Charged Water Nanodroplets. J. Phy. Chem. 2003, 107, 7406–7412.
Tang K.; Lin Y.; Matson D. W.; Kim T.; Smith R. D. Generation of Multiple Electrosprays Using Microfabricated Emitter Arrays for Improved Mass Spectrometric Sensitivity. Anal. Chem. 2001, 73, 1658–1663.
Shen Y.; Moore R. J.; Zhao R.; Blonder J.; Auberry D. L.; Masselon C.; Pasa-Tolic L.; Hixson K. K.; Auberry K. J.; Smith R. D. High-Efficiency On-Line Solid-Phase Extraction Coupling to 15-150-Microm-i.d. Column Liquid Chromatography for Proteomic Analysis. Anal. Chem. 2003, 75, 3264–3273.
Shen Y.; Tolic N.; Masselon C.; Pasa-Tolic L.; Camp, D. G. II.; Hixson K. K.; Zhao R.; Anderson G. A.; Smith R. D. Ultrasensitive Proteomics Using High-Efficiency On-Line Micro-SPE-NanoLC-NanoESI MS and MS/MS. Anal. Chem. 2004, 76, 144–154.
Author information
Authors and Affiliations
Corresponding author
Additional information
Published online August 27, 2004
Rights and permissions
About this article
Cite this article
Tang, K., Page, J.S. & Smith, R.D. Charge competition and the linear dynamic range of detection in electrospray ionization mass spectrometry. J Am Soc Mass Spectrom 15, 1416–1423 (2004). https://doi.org/10.1016/j.jasms.2004.04.034
Received:
Revised:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1016/j.jasms.2004.04.034