Skip to main content
Log in

A ToF-MS with a Highly Efficient Electrostatic Ion Guide for Characterization of Ionic Liquid Electrospray Sources

  • Research Article
  • Published:
Journal of The American Society for Mass Spectrometry

Abstract

We report on the development of a time-of-flight (ToF) mass spectrometer with a highly efficient electrostatic ion guide for enhancing detectability in ToF mass spectrometry. This 65-cm long ion guide consists of 13 cascaded stages of Einzel lens to collect a large fraction of emitted charges over a wide emission angle and energy spread for time-of-flight measurements. Simulations show that the ion guide can collect 100% of the charges with up to 23° emission half-angle or 30% energy spread irrespective of their specific charge. We demonstrate this ion guide as applied to electrospray ion sources. Experiments performed with tungsten needle electrospraying the ionic liquid EMI-BF4 showed that up to 80% of the emitted charges could be collected at the end of the flight tube. Flight times of monomers and dimers emitted from the needles were measured in both positive and negative emission polarities. The setup was also used to characterize the electrospray from microfabricated silicon capillary emitters and nearly 30% charges could be collected even from a 40° emission half-angle. This setup can thus increase the fraction of charge collection for ToF measurement and spray characteristics can be obtained from a very large fraction of the emission in real time.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Figure 1
Figure 2
Figure 3
Figure 4
Figure 5
Figure 6

Similar content being viewed by others

References

  1. Cotter, R.J.: Time-of-flight Mass Spectrometry: Instrumentation and Applications in Biological Research, 1st ed., ACS Professional Reference Books: Washington DC (1997)

  2. Cameron, A.E., Eggers Jr., D.F.: An ion elocitron. Rev. Sci. Instrum. 19, 605–607 (1948)

    Article  CAS  Google Scholar 

  3. Wiley, W.C., McLaren, I.H.: Time of flight mass spectrometer with improved resolution. Rev. Sci. Instrum. 26, 1150–1157 (1955)

    Article  CAS  Google Scholar 

  4. Karas, M., Hillencamp, F.: Laser desorption ionization of proteins with molecular masses exceeding 10 000 Daltons. Analytical Chemistry 60, 2291–2301 (1988)

    Article  Google Scholar 

  5. Tanaka, K., Waki, H., Ido, Y., Akita, S., Yoshida, Y., Yoshida, T., Mastuo, T.: Protein and polymer analyses up to m/z 100,000 by laser ionization time-of-flight mass spectrometry. Rapid Commun. Mass Spectrom. 2, 151–153 (1988)

    Article  CAS  Google Scholar 

  6. Cornish, T.J., Cotter, R.J.: Tandem time-of-flight mass spectrometer. Anal. Chem. 65, 1043–1047 (1993)

    Article  CAS  Google Scholar 

  7. Fenn, J.B., Mann, M., Meng, C.K., Wong, S.F., Whitehouse, C.M.: Electrospray ionization for mass spectrometry of large biomolecules. Science 246, 64–71 (1989)

    Article  CAS  Google Scholar 

  8. Fenn, J.B.: Electrospray ionization mass spectrometry: how it all began. J. Biomed. Tech. 13, 101–118 (2002)

    Google Scholar 

  9. Ho, C.S., Lam, C.W.K., Chan, M.H.M., Cheung, R.C.K., Law, L.K., Lit, L.C.W., Ng, K.F., Suen, M.W.M., Tai, H.L.: Electrospray ionization mass spectrometry: principles and clinical applications. Clin. Biochem. Rev. 24, 3–12 (2003)

    CAS  Google Scholar 

  10. Vestal, M.L.: The future of biological mass spectrometry. J. Am. Soc. Mass Spectrom. 22, 953–959 (2011)

    Article  CAS  Google Scholar 

  11. Lozano, P.C.: Energy properties of an EMI-Im ionic liquid ion source. J. Phys. D Appl. Phys. 39, 126–134 (2006)

    Article  CAS  Google Scholar 

  12. Lozano, P.: Studies on the ion-droplet mixed regime in colloid thrusters. PhD Dissertation, Department of Aeronautics and Astronautics, MIT, USA (2003)

  13. Bamberger, C., Renz, U., Bamberger, A.: Digital imaging mass spectrometry. J. Am. Soc. Mass Spectrom. 22, 1079–1087 (2011)

    Article  CAS  Google Scholar 

  14. Ebata, S., Ishihara, M., Kumondai, K., Mibuka, R., Uchino, K., Yurimoto, H.: Development of an ultra-high performance multi-turn TOF-SIMS/SNMS system MULTUM-SIMS/SNMS. J. Am. Soc. Mass Spectrom. 24, 222–229 (2013)

    Article  CAS  Google Scholar 

  15. May, J.C., Russell, D.H.: A mass-selective variable-temperature drift tube ion mobility-mass spectrometer for temperature dependent ion mobility studies. J. Am. Soc. Mass Spectrom. 22, 1134–1145 (2011)

    Article  CAS  Google Scholar 

  16. Contino, N.C., Pierson, E.E., Keifer, D.Z., Jarrold, M.F.: Charge detection mass spectrometry with resolved charge states. J. Am. Soc. Mass Spectrom. 24, 101–108 (2013)

    Article  CAS  Google Scholar 

  17. Guilhaus, M.: Principles and Instrumentation in time-of-flight mass spectrometry. J. Mass Spectrom. 30, 1519–1532 (1995)

    Article  CAS  Google Scholar 

  18. Mühlberger, F., Saraji-Bozorgzad, M., Gonin, M., Fuhrer, K., Zimmermann, R.: Compact ultrafast orthogonal acceleration time-of-flight mass spectrometer for on-line gas analysis by electron impact ionization and soft single photon ionization using an electron beam pumped rare gas excimer lamp as VUV-light source. Anal. Chem. 79, 8118–8124 (2007)

    Article  Google Scholar 

  19. Kitahara, Y., Takahashi, S., Kuramoto, N., Sala, M., Tsugoshi, T., Sablier, M., Fujii, T.: Ion attachment mass spectrometry combined with infrared image furnace for thermal analysis: evolved gas analysis studies. Anal. Chem. 81, 3155–3158 (2009)

    Article  CAS  Google Scholar 

  20. Basile, F., Zhang, S., Kandar, S.K., Lu, L.: Mass spectrometry characterization of the thermal decomposition/digestion (TDD) at cysteine in peptides and proteins in the condensed phase. J. Am. Society Mass Spectrom. 22, 1926–1940 (2011)

    Article  CAS  Google Scholar 

  21. van Wuijckhuijse, A. L, van Baar, B. L. M.: Recent advances in real-time mass spectrometry detection of bacteria. In: Zourob, M., Elwary S., Turner, A. (eds.) Principles of Bacterial Detection: Biosensors, Recognition Receptors and Microsystems, pp. 929–954. Springer, New York (2008)

  22. Arnold, R.J., Karty, J.A., Ellington, A.D., Reilly, J.P.: Monitoring the growth of a bacteria culture by MALDI-MS of whole cells. Anal. Chem. 71, 1990–1996 (1999)

    Article  CAS  Google Scholar 

  23. Wilkes, J.G., Rafli, F., Sutherland, J.B., Rushing, L.G., Buzatu, D.A.: Pyrolysis mass spectrometry for distinguishing potential hoax materials from bioterror agents. Rapid Commun. Mass Spectrom. 20, 2383–2386 (2006)

    Article  CAS  Google Scholar 

  24. Spraggins, J.M., Caprioli, R.M.: High-speed MALDI-TOF imaging mass spectrometry: rapid ion image acquisition and considerations for next generation instrumentation. J. Am. Soc. Mass Spectrom. 22, 1022–1031 (2011)

    Article  CAS  Google Scholar 

  25. Romero-Sanz, I., Bocanegra, R., de la Moraa, J.F., Gamero-Castano, M.: Source of heavy molecular ions based on Taylor cones of ionic liquids operating in the pure ion evaporation regime. J. Appl. Phys. 94, 3599–3605 (2003)

    Article  CAS  Google Scholar 

  26. Marcuccio, S., Genovese, A., Andrenucci, M.: Experimental performance of field emission microthrusters. J. Propulsion Power 14, 774–781 (1998)

    Article  CAS  Google Scholar 

  27. Zorzos, A.N., Lozano, P.C.: The use of ionic liquid ion sources in focused ion beam applications. J. Vacuum Sci. Technol. B 26, 2097–2102 (2008)

    Article  CAS  Google Scholar 

  28. Fedkiw, T.P., Lozano, P.C.: Development and characterization of an iodine field emission ion source for focused ion beam applications. J. Vacuum Sci. Technol. B 27, 2648–2653 (2009)

    Article  CAS  Google Scholar 

  29. Lozano, P., Martínez-Sánchez, M.: Ionic liquid ion sources: suppression of electrochemical reactions using voltage alternation. J. Colloid Interface Sci. 280, 149–154 (2004)

    Article  CAS  Google Scholar 

  30. Courtney, D.G.: Ionic liquid ion source emitter arrays fabricated on bulk porous substrates for spacecraft propulsion. PhD Dissertation, Department of Aeronautics and Astronautics, MIT, USA (2011)

  31. Terhune, K.J., King, L.B., He, K., Cumings, J.: In situ visualization of ionic liquid electrospray emission using transmission electron microscopy. Proceedings of the 49th AIAA/ASME/SAE/ASEE Joint Propulsion Conference. San Jose, CA, July 14–17, p. 146 (2013)

  32. Chakraborty, S., Ataman, C., Dandavino, S., Shea, H.: Microfabrication of an electrospray thruster for small spacecraft. Proceedings of POWERMEMS 2012. Atlanta, GA, December 2–5, p. 073 (2012)

  33. Miller, S. W., Prince, B. D.: Capillary extraction of the ionic liquid [Bmim][DCA] for variable flow rate operations. Proceedings of the 48th AIAA/ASME/SAE/ASEE Joint Propulsion Conference and Exhibit Atlanta, GA, July 30–August 1 (2012)

  34. Gamero, C.M.: The structure of electrospray beams in vacuum. J Fluid Mech 604, 339–368 (2008)

    Google Scholar 

  35. Krpoun, R.: Micromachined electrospray thrusters for spacecraft propulsion. PhD Dissertation, EPFL, Switzerland (2009)

  36. Krpoun, R., Shea, H.R.: Integrated out-of-plane nano-electrospray thruster arrays for spacecraft propulsion. J. Micromech. Microeng. 19, 045019 (2009)

    Article  Google Scholar 

  37. Andersson, G.: Angle-resolved ion scattering spectroscopy at surfaces of pure liquids: topography and orientation of molecules. Phys. Chem. Chem. Phys. 7, 2942–2947 (2005)

    Article  CAS  Google Scholar 

  38. Romero-Sanz, I., de la Mora, J.F.: Energy distribution and spatial structure of electrosprays of ionic liquids in vacuo. J. Appl. Phys. 4, 2123–2129 (2004)

    Article  Google Scholar 

  39. Ryan, C., Daykin-Iliopoulos, A., Stark, J.A., Salaverri A., Vargas, E., Rangsten, P., Dandavino, S., Ataman, C., Chakraborty, S., Courtney, D., Shea, H.: Experimental progress towards the MicroThrust MEMS electrospray electric propulsion system. Proceedings of the 33rd International Electric Propulsion Conference, Washington DC, Oct. 6–10, p. 146 (2013)

  40. Sise, O., Ulu, M., Dogan, M.: Multi-element cylindrical electrostatic lens systems for focusing and controlling charged particles. Nuclear Instrum. Methods Phys. Res. A: Accelerators, Spectrometers, Detectors, and Associated Equipment. 554, 114–131 (2005)

  41. Riddle, G.H.N.: Electrostatic Einzel lenses with reduced spherical aberration for use in field emission guns. J. Vacuum Sci. Technol. 15, 857–860 (1978)

    Article  Google Scholar 

  42. Imhof, R.E., Read, F.H.: A three-aperture electron optical lens for producing an image of variable energy but fixed position. J. Sci. Instrum. 1, 859–860 (1968)

    Article  Google Scholar 

  43. Rohrbacher, A., Continett, R.E.: Multiple-ion-beam time-of-flight mass spectrometer. Rev. Sci. Instrum. 72, 3386–3389 (2001)

    Article  CAS  Google Scholar 

  44. Gillig, K.J., Ruotolo, B.T., Stone, E.G., Russell, D.H.: An electrostatic focusing ion guide for ion mobility-mass spectrometry. Int. J. Mass Spectrom. 239, 43–49 (2004)

    Article  CAS  Google Scholar 

  45. Blasé, R.C., Silveira, J.A., Gillig, K.J., Gamage, C.M., Russell, D.H.: Increased ion transmission in IMS: a high resolution, periodic-focusing DC ion guide ion mobility spectrometer. Int. J. Mass Spectrom. 301, 166–173 (2011)

    Article  Google Scholar 

  46. Dandavino, S., Ataman, C., Chakraborty, S., Shea, H., Ryan, C., Stark J.: Design and fabrication of the thruster heads for the MicroThrust MEMS electrospray propulsion system. Proceedings of the 33rd International Electric Propulsion Conference. Washington DC, Oct. 6–10, p. 127 (2013)

  47. Lozano, P., Martínez-Sánchez, M.: Ionic liquid ion sources: characterization of externally wetted emitters. J. Colloid Interface Sci. 282, 415–421 (2005)

    Article  CAS  Google Scholar 

  48. Variable gain High Speed Current Amplifier DHPCA-100. Available at: http://www.femto.de/en/products/current-amplifiers/variable-gain-up-to-200-mhz-dhpca.html. Accessed 28 Nov 2013

  49. Part Types Gallery. Available at: http://www.kimballphysics.com/ev-parts/technology/product-overview. Accessed 28 Nov 2013

  50. Castro, S., de la Mora, J.F.: Effect of tip curvature on ionic liquid emission from Taylor cones of ionic liquids from externally wetted tungsten tips. J. Appl. Phys. 105, 034903 (2009)

    Article  Google Scholar 

  51. Regulated products. Available at: http://www.emcohighvoltage.com/regulated-power-supply.php. Accessed 28 Nov 2013

  52. Precision, Wide Bandwidth 3-Port Isolation Amplifier: AD210. Available at: http://www.analog.com/static/imported-files/data_sheets/AD210.pdf. Accessed 28 Nov 2013

  53. PVX-4140 Datasheet. Available at: http://www.ixyscolorado.com/index2.php?page=shop.product_details&flypage=flypage.tpl&product_id=26&category_id=25&option=com_virtuemart&Itemid=29. Accessed 28 Nov 2013

  54. Larriba, C., Castro, S., de la Mora, J.F., Lozano, P.: Mono-energetic source of kilodalton ions from Taylor cones of ionic liquids. J. Appl. Phys. 101, 084303 (2007)

    Article  Google Scholar 

  55. Ataman, C., Dandavino, S., Shea H.: Wafer-level integrated electrospray emitters for a pumpless microthruster system operating on high efficiency ion-mode. Proceedings of MEMS 2012, Paris, France, 1293−1296 (2012)

Download references

Acknowledgments

The authors acknowledge Dr. C. N. Ryan from Queen Mary University, London, for important discussions. This work was partially supported by the Swiss National Science Foundation under grant 200021_146365, the ESA NPI programme, and the FP7 MicroThrust project, grant agreement number 263035, funded by the EC Seventh Framework Programme theme FP7-SPACE-2010.

Author information

Authors and Affiliations

Authors

Corresponding author

Correspondence to Subha Chakraborty.

Electronic supplementary material

Below is the link to the electronic supplementary material.

Supplementary Figure S1

(DOC 106 kb)

Supplementary Figure S2

(DOC 106 kb)

Supplementary Figure S3

(DOC 334 kb)

Supplementary Figure S4

(DOC 96 kb)

Rights and permissions

Reprints and permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Chakraborty, S., Ataman, C., Courtney, D.G. et al. A ToF-MS with a Highly Efficient Electrostatic Ion Guide for Characterization of Ionic Liquid Electrospray Sources. J. Am. Soc. Mass Spectrom. 25, 1364–1373 (2014). https://doi.org/10.1007/s13361-014-0914-z

Download citation

  • Received:

  • Revised:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s13361-014-0914-z

Key words

Navigation