Abstract
Differential mobility spectrometry or field asymmetric waveform ion mobility spectrometry (FAIMS) is a new tool for separation and identification of gas-phase ions, particularly in conjunction with mass spectrometry. In FAIMS, ions are filtered by the difference between mobilities in gases (K) at high and low electric field intensity (E) using asymmetric waveforms. An infinite number of possible waveform profiles make maximizing the performance within engineering constraints a major issue for FAIMS technology refinement. Earlier optimizations assumed the non-constant component of mobility to scale as E 2, producing the same result for all ions. Here we show that the optimum profiles are defined by the full series expansion of K(E) that includes terms beyond the first that is proportional to E 2. For many ion/gas pairs, the first two terms have different signs, and the optimum profiles at sufficiently high E in FAIMS may differ substantially from those previously reported, improving the resolving power by up to 2.2 times. This situation arises for some ions in all FAIMS systems, but becomes more common in recent miniaturized devices that employ higher E. With realistic K(E) dependences, the maximum waveform amplitude is not necessarily optimum, and reducing it by up to ∼20% to 30% is beneficial in some cases. The present findings are particularly relevant to targeted analyses where separation depends on the difference between K(E) functions for specific ions.
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Buryakov, I. A.; Krylov, E. V.; Nazarov, E. G.; Rasulev, U. K. A New Method of Separation of Multi-Atomic Ions by Mobility at Atmospheric Pressure Using a High-Frequency Amplitude-Asymmetric Strong Electric Field. Int. J. Mass Spectrom. Ion Processes. 1993, 128, 143–148.
Purves, R. W.; Guevremont, R. Electrospray Ionization High-Field Asymmetric Waveform Ion Mobility Spectrometry-Mass Spectrometry. Anal. Chem. 1999, 71, 2346–2357.
Miller, R. A.; Eiceman, G. A.; Nazarov, E. G.; King, A. T. A Novel Micromachined High-Field Asymmetric Waveform-Ion Mobility Spectrometer. Sens. Actuators B. 2000, 67, 300–306.
Shvartsburg, A. A.; Li, F.; Tang, K.; Smith, R. D. High-Resolution Field Asymmetric Waveform Ion Mobility Spectrometry Using New Planar Geometry Analyzers. Anal. Chem. 2006, 78, 3706–3714.
Guevremont, R. High-Field Asymmetric Waveform Ion Mobility Spectrometry: A New Tool for Mass Spectrometry. J. Chromatogr. A. 2004, 1058, 3–19.
Gabryelski, W.; Froese, K. L. Characterization of Naphthenic Acids by Electrospray Ionization High-Field Asymmetric Waveform Ion Mobility Spectrometry Mass Spectrometry. Anal. Chem. 2003, 75, 4612–4623.
Eiceman, G. A.; Krylov, E. V.; Tadjikov, B.; Ewing, R. G.; Nazarov, E. G.; Miller, R. A. Differential Mobility Spectrometry of Chlorocarbons with a Micro-Fabricated Drift Tube. Analyst. 2004, 129, 297–304.
Gabryelski, W.; Wu, F.; Froese, K. L. Comparison of High-Field Asymmetric Waveform Ion Mobility Spectrometry with GC Methods in Analysis of Haloacetic Acids in Drinking Water. Anal. Chem. 2003, 75, 2478–2486.
Sander, L. C.; Sharpless, K. E.; Satterfield, M. B.; Ihara, T.; Phinney, K. W.; Yen, J. H.; Wise, S. A.; Gay, M. L.; Lam, J. W.; McCooeye, M.; Gardner, G.; Fraser, C.; Sturgeon, R.; Roman, M. Determination of Ephedrine Alkaloids in Dietary Supplement Standard Reference Materials. Anal. Chem. 2005, 77, 3101–3112.
Liu, X.; Zhao, Y. Y.; Chan, K.; Hrudey, S. E.; Li, X. F.; Li, J. J. Analysis of Nitrosamines by Capillary Electrospray-High-Field Asymmetric Waveform Ion Mobility Spectrometry-MS with Programmed Compensation Voltage. Electrophoresis. 2007, 28, 1327–1334.
Schmidt, H.; Tadjimukhamedov, F.; Mohrenz, I. V.; Smith, G. B.; Eiceman, G. A. Microfabricated Differential Mobility Spectrometry with Pyrolysis Gas Chromatography for Chemical Characterization of Bacteria. Anal. Chem. 2004, 76, 5208–5217.
Shnayderman, M.; Mansfield, B.; Yip, P.; Clark, H. A.; Krebs, M. D.; Cohen, S. J.; Zeskind, J. E.; Ryan, E. T.; Dorkin, H. L.; Callahan, M. V.; Stair, T. O.; Gelfand, J. A.; Gill, C. J.; Hitt, B.; Davis, C. E. Species-Specific Bacterial Identification Using Differential Mobility Spectrometry and Bioinformatics Pattern Recognition. Anal. Chem. 2005, 77, 5930–5937.
Lu, Y.; Harrington, P. B. Forensic Applications of Gas Chromatography-Differential Mobility Spectrometry with Two-Way Classification of Ignitable Liquids from Fire Debris. Anal. Chem. 2007, 79, 6752–6759.
Guevremont, R.; Barnett, D. A.; Purves, R. W.; Vandermey, J. Analysis of a Tryptic Digest of Pig Hemoglobin Using ESI-FAIMS-MS. Anal. Chem. 2000, 72, 4577–4584.
Venne, K.; Bonneil, E.; Eng, K.; Thibault, P. Improvement in Peptide Detection for Proteomics Analyses Using NanoLC-MS and High-Field Asymmetry Waveform Ion Mobility Mass Spectrometry. Anal. Chem. 2005, 77, 2176–2186.
Tang, K.; Li, F.; Shvartsburg, A. A.; Strittmatter, E. F.; Smith, R. D. Two-Dimensional Gas-Phase Separations Coupled to Mass Spectrometry for Analysis of Complex Mixtures. Anal. Chem. 2005, 77, 6381–6388.
Li, J.; Purves, R. W.; Richards, J. C. Coupling Capillary Electrophoresis and High-Field Asymmetric Waveform Ion Mobility Spectrometry-Mass Spectrometry for the Analysis of Complex Lipopolysaccharides. Anal. Chem. 2004, 76, 4676–4683.
Kapron, J.; Wu, J.; Mauriala, T.; Clark, P.; Purves, R. W.; Bateman, K. P. Simultaneous Analysis of Prostanoids Using Liquid Chromatography/High-Field Asymmetric Waveform Ion Mobility Spectrometry/Tandem Mass Spectrometry. Rapid Commun. Mass Spectrom. 2006, 20, 1504–1510.
Hatsis, P.; Brockman, A. H.; Wu, J. T. Evaluation of High-Field Asymmetric Waveform Ion Mobility Spectrometry Coupled to Nanoelectrospray Ionization for Bioanalysis in Drug Discovery. Rapid Commun. Mass Spectrom. 2007, 21, 2295–2300.
Mie, A.; Jornten-Karlsson, M.; Axelsson, B. O.; Ray, A.; Reimann, C. T. Enantiomer Separation of Amino Acids by Complexation with Chiral Reference Compounds and High-Field Asymmetric Waveform Ion Mobility Spectrometry: Preliminary Results and Possible Limitations. Anal. Chem. 2007, 79, 2850–2858.
Purves, R. W.; Barnett, D. A.; Ells, B.; Guevremont, R. Elongated Conformers of Charge States +11 to +15 of Bovine Ubiquitin Studied Using ESI-FAIMS-MS. J. Am. Soc. Mass Spectrom. 2001, 12, 894–901.
Borysik, A. J. H.; Read, P.; Little, D. R.; Bateman, R. H.; Radford, S. E.; Ashcroft, A. E. Separation of β2-microglobulin Conformers by High-Field Asymmetric Waveform Ion Mobility Spectrometry (FAIMS) Coupled to Electrospray Ionization Mass Spectrometry. Rapid Commun. Mass Spectrom. 2004, 18, 2229–2234.
Robinson, E. W.; Leib, R. D.; Willams, E. R. The Role of Conformation on Electron Capture Dissociation of Ubiquitin. J. Am. Soc. Mass Spectrom. 2006, 17, 1470–1480.
Shvartsburg, A. A.; Bryskiewicz, T.; Purves, R. W.; Tang, K.; Guevremont, R.; Smith, R. D. Field Asymmetric Waveform Ion Mobility Spectrometry Studies of Proteins: Dipole Alignment in Ion Mobility Spectrometry?. J. Phys. Chem. B. 2006, 110, 21966–21980.
Shvartsburg, A. A.; Li, F.; Tang, K.; Smith, R. D. Characterizing the Structures and Folding of Free Proteins Using 2-D Gas-Phase Separations: Observation of Multiple Unfolded Conformers. Anal. Chem. 2006, 78, 3304–3315; Ibid. 8575.
Buryakov, I. A.; Kolomiets, Y. N.; Luppu, B. V. Detection of Explosive Vapors in the Air Using an Ion Drift Nonlinearity Spectrometer. J. Anal. Chem. 2001, 56, 336–340.
Buryakov, I. A.; Kolomiets, Y. N. Rapid Determination of Explosives and Narcotics Using a Multicapillary-Column Gas Chromatograph and an Ion-Mobility Spectrometer. J. Anal. Chem. 2003, 58, 944–950.
Buryakov, I. A. Qualitative Analysis of Trace Constituents by Ion Mobility Increment Spectrometer. Talanta. 2003, 61, 369–375.
Buryakov, I. A. Express Analysis of Explosives, Chemical Warfare Agents and Drugs with Multicapillary Column Gas Chromatography and Ion Mobility Increment Spectrometry. J. Chromatogr. B. 2004, 800, 75–82.
Eiceman, G. A.; Krylov, E.; Krylova, N.; Nazarov, E. G.; Miller, R. A. Separation of Ions from Explosives in Differential Mobility Spectrometry by Vapor-Modified Drift Gas. Anal. Chem. 2004, 76, 4937–4944.
Buryakov, I. A.; Kolomietz, Y. N.; Bolotov, A. V.; Vasin, A. I.; Vlasov, Y. N. Registration of Lewisite Vapors in Air Using an Ion Mobility Spectrometer. J. Anal. Chem. 2002, 57, 606–610.
McDaniel, E. W.; Mason, E. A. Transport Properties of Ions in Gases; Wiley: NY. 1988.
Krylov, E. V.; Nazarov, E. G.; Miller, R. A. Differential Mobility Spectrometer: Model of Operation. Int. J. Mass Spectrom. 2007, 266, 76–85.
Eiceman, G. A.; Karpas, Z. Ion Mobility Spectrometry; CRC: Boca Raton, FL, 2005.
Akridge, G. R.; Ellis, H. W.; Pai, R. Y.; McDaniel, E. W. Mobilities of Li+ Ions in He, Ne, and Ar and of Na+ Ions in He, Ne, Ar, and CO2. J. Chem. Phys. 1975, 62, 4578–4579.
Iinuma, K.; Imai, M.; Satoh, Y.; Takebe, M. Mobilities of Li+ Ions in HCl, HBr, and HI at Room Temperature. J. Chem. Phys. 1988, 89, 7035–7036.
Barnett, D. A.; Ells, B.; Guevremont, R.; Purves, R. W.; Viehland, L. A. Evaluation of Carrier Gases for Use in High-Field Asymmetric Waveform Ion Mobility Spectrometry. J. Am. Soc. Mass Spectrom. 2000, 11, 1125–1133.
Ruotolo, B. T.; McLean, J. A.; Gillig, K. J.; Russell, D. H. The Influence and Utility of Varying Field Strength for the Separation of Tryptic Peptides by Ion Mobility-Mass Spectrometry. J. Am. Soc. Mass Spectrom. 2005, 16, 158–165.
Gorshkov, M. P. Method for Analysis of Additives to Gases. USSR Inventor’s Certificate No. 966583; 1982.
Buryakov, I. A.; Krylov, E. V.; Soldatov, V. P. Method for Analysis of Additives to Gases. USSR Inventor’s Certificate No. 1337934; 1987.
Buryakov, I. A.; Krylov, E. V.; Makas, A. L.; Nazarov, E. G.; Pervukhin, V. V.; Rasulev, U. K. Ion Division by their Mobility in High-Tension Alternating Electric Field. Tech. Phys. Lett. 1991, 17, 412.
Krylov, E. V. Comparison of the Planar and Coaxial Field Asymmetrical Waveform Ion Mobility Spectrometer. Int. J. Mass Spectrom. 2003, 225, 39–51.
Elistratov, A. A.; Shibkov, S. V. A Model of Nonlinear Ion Drift Spectrometry for Gas Detectors with Separating Chamber of Cylindrical Geometry. Tech. Phys. Lett. 2004, 30, 183–185.
Shvartsburg, A. A.; Mashkevich, S. V.; Smith, R. D. Feasibility of Higher-Order Differential Ion Mobility Separations Using New Asymmetric Waveforms. J. Phys. Chem. A. 2006, 110, 2663–2673.
Krylov, E. V. Pulses of Special Shapes Formed on a Capacitive Load. Inst. Exp. Tech. 1997, 40, 628–631.
Shvartsburg, A. A.; Tang, K.; Smith, R. D. Optimization of the Design and Operation of FAIMS Analyzers. J. Am. Soc. Mass Spectrom. 2005, 16, 2–12.
Shvartsburg, A. A.; Tang, K.; Smith, R. D. Modeling the Resolution and Sensitivity of FAIMS Analyses. J. Am. Soc. Mass Spectrom. 2004, 15, 1487–1498.
Boyle, B.; Koehl, A.; Parris, R.; Ruiz-Alonso, D.; Rush, M.; Wilks, A. A MEMS Fabricated Device for Field Asymmetric Ion Mobility Spectrometry. Proceedings of the 59th Pittcon Conference, New Orleans, LA (03/2008).
Nazarov, E. G.; Coy, S. L.; Krylov, E. V.; Miller, R. A.; Eiceman, G. A. Pressure Effects in Differential Mobility Spectrometry. Anal. Chem. 2006, 78, 7697–7706.
Papanastasiou, D.; Wollnik, H.; Rico, G.; Tadjimukhamedov, F.; Mueller, W.; Eiceman, G. A. Differential Mobility Separation of Ions Using a Rectangular Asymmetric Waveform. J. Phys. Chem. A. 2008, 112, 3638–3645.
Buryakov, I. A.; Krylov, E. V.; Soldatov, V. P. Drift Spectrometer for Trace Detection of Substances in Gases. USSR Inventor’s Certificate No. 1412447; 1989.
Viehland, L. A.; Guevremont, R.; Purves, R. W.; Barnett, D. A. Comparison of High-Field Ion Mobility Obtained from Drift Tubes and a FAIMS Apparatus. Int. J. Mass Spectrom. 2000, 197, 123–130.
Meek, J. M.; Craggs, J. D. Electrical Breakdown of Gases; Wiley: New York, 1978.
Guevremont, R.; Barnett, D. A.; Purves, R. W.; Viehland, L. A. Calculation of Ion Mobilities from Electrospray Ionization High-Field Asymmetric Waveform Ion Mobility Spectrometry Mass Spectrometry. J. Chem. Phys. 2001, 114, 10270–10277.
Buryakov, I. A. Determination of Kinetic Transport Coefficients for Ions in Air as Functions of Electric Field and Temperature. Tech. Phys. 2004, 49, 967–972.
Krylov, E.; Nazarov, E. G.; Miller, R. A.; Tadjikov, B.; Eiceman, G. A. Field Dependence of Mobilities for Gas-Phase-Protonated Monomers and Proton-Bound Dimers of Ketones by Planar Field Asymmetric Waveform Ion Mobility Spectrometer (PFAIMS). J. Phys. Chem. A. 2002, 106, 5437–5444.
Krylova, N.; Krylov, E.; Eiceman, G. A.; Stone, J. A. Effect of Moisture on the Field Dependence of Mobility for Gas-Phase Ions of Organophosphorus Compounds at Atmospheric Pressure with Field Asymmetric Ion Mobility Spectrometry. J. Phys. Chem. A. 2003, 107, 3648–3654.
Buryakov, I. A. Effect of the Water Vapor Density on the Field Dependence of the Ion Mobility Increment for Nitro Compounds in Air. Tech. Phys. Lett. 2007, 33, 861–864.
Barnett, D. A.; Ells, B.; Guevremont, R.; Purves, R. W. Separation of Leucine and Isoleucine by Electrospray Ionization High-Field Asymmetric Waveform Ion Mobility Spectrometry-Mass Spectrometry. J. Am. Soc. Mass Spectrom. 1999, 10, 1279–1284.
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Published online May 16, 2008
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Shvartsburg, A.A., Smith, R.D. Optimum waveforms for differential ion mobility spectrometry (FAIMS). J Am Soc Mass Spectrom 19, 1286–1295 (2008). https://doi.org/10.1016/j.jasms.2008.05.008
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DOI: https://doi.org/10.1016/j.jasms.2008.05.008