Analytical and Bioanalytical Chemistry

, Volume 410, Issue 16, pp 3639–3648 | Cite as

Ion concentration in micro and nanoscale electrospray emitters

Paper in Forefront

Abstract

Solution-phase ion transport during electrospray has been characterized for nanopipettes, or glass capillaries pulled to nanoscale tip dimensions, and micron-sized electrospray ionization emitters. Direct visualization of charged fluorophores during the electrospray process is used to evaluate impacts of emitter size, ionic strength, analyte size, and pressure-driven flow on heterogeneous ion transport during electrospray. Mass spectrometric measurements of positively- and negatively-charged proteins were taken for micron-sized and nanopipette emitters under low ionic strength conditions to further illustrate a discrepancy in solution-driven transport of charged analytes. A fundamental understanding of analyte electromigration during electrospray, which is not always considered, is expected to provide control over selective analyte depletion and enrichment, and can be harnessed for sample cleanup.

Graphical abstract

Fluorescence micrographs of ion migration in nanoscale pipettes while solution is electrosprayed

Keywords

Microfluidics / Microfabrication Nanoparticles / Nanotechnology Electroanalytical methods 

Notes

Acknowledgements

The authors thank Prof. Gary Hieftje for valuable discussions related to this work. The Indiana University Nanoscale Characterization is acknowledged for use of the scanning electron microscope. Electronic Instrument Services and Mechanical Instrument Services at Indiana University are acknowledged for assistance with instrumental setup. E.M.Y. thanks the Bill Carroll Family fellowship for financial support. Additional financial support was provided by Indiana University.

Compliance with ethical standards

This study required no human or animal samples and research conducted complied with ethical standards set forward by Indiana University.

Conflict of interest

The authors declare that they have no competing interests.

Supplementary material

216_2018_1043_MOESM1_ESM.pdf (3.4 mb)
ESM 1 (PDF 3531 kb)

References

  1. 1.
    Aebersold R, Mann M. Mass spectrometry-based proteomics. Nature. 2003;422:198–207.CrossRefGoogle Scholar
  2. 2.
    Yates JR, Ruse CI, Nakorchevsky A. Proteomics by mass spectrometry: approaches, advances, and applications. Annu Rev Biomed Eng. 2009;11:49–79.CrossRefGoogle Scholar
  3. 3.
    Dettmer K, Aronov PA, Hammock BD. Mass spectrometry-based metabolomics. Mass Spectrom Rev. 2007;26:51–78.CrossRefGoogle Scholar
  4. 4.
    Bantscheff M, Schirle M, Sweetman G, Rick J, Kuster B. Quantitative mass spectrometry in proteomics: a critical review. Anal Bioanal Chem. 2007;389:1017–31.CrossRefGoogle Scholar
  5. 5.
    Marginean I, Parvin L, Heffernan L, Vertes A. Flexing the electrified meniscus: the birth of a jet in electrosprays. Anal Chem. 2004;76:4202–7.CrossRefGoogle Scholar
  6. 6.
    Gomez A, Tang K. Charge and fission of droplets in electrostatic sprays. Phys Fluids. 1994;6:404–14.CrossRefGoogle Scholar
  7. 7.
    Dole M, Mack LL, Hines RL, Mobley RC, Ferguson LD, Alice MB. Molecular beams of macroions. J Chem Phys. 1968;49:2240–9.CrossRefGoogle Scholar
  8. 8.
    Iribarne JV, Thomson BA. On the evaporation of small ions from charged droplets. J Chem Phys. 1976;64:2287–94.CrossRefGoogle Scholar
  9. 9.
    Ahadi E, Konermann L. Modeling the behavior of coarse-grained polymer chains in charged water droplets: implications for the mechanism of electrospray ionization. J Phys Chem B. 2012;116:104–12.CrossRefGoogle Scholar
  10. 10.
    Konermann L, Rodriguez AD, Liu J. On the formation of highly charged gaseous ions from unfolded proteins by electrospray ionization. Anal Chem. 2012;84:6798–804.CrossRefGoogle Scholar
  11. 11.
    Blades AT, Ikonomou MG, Kebarle P. Mechanism of electrospray mass spectrometry. electrospray as an electrolysis cell. Anal Chem. 1991;63:2109–14.CrossRefGoogle Scholar
  12. 12.
    Van Berkel GJ, Zhou F. Electrospray as a controlled-current electrolytic cell: electrochemical ionization of neutral analytes for detection by electrospray mass spectrometry. Anal Chem. 1995;67:3958–64.CrossRefGoogle Scholar
  13. 13.
    Hop CECA, Saulys DA, Gaines DF. Electrospray mass spectrometry of borane salts: the electrospray needle as an electrochemical cell. J Am Soc Mass Spectrom. 1995;6:860–5.CrossRefGoogle Scholar
  14. 14.
    Jackson GS, Enke CG. Electrical equivalence of electrospray ionization with conducting and nonconducting needles. Anal Chem. 1999;71:3777–84.CrossRefGoogle Scholar
  15. 15.
    Li Y, Pozniak BP, Cole RB. Mapping of potential gradients within the electrospray emitter. Anal Chem. 2003;75:6987–94.CrossRefGoogle Scholar
  16. 16.
    Pozniak BP, Cole RB. Ambient gas influence on electrospray potential as revealed by potential mapping within the electrospray capillary. Anal Chem. 2007;79:3383–91.CrossRefGoogle Scholar
  17. 17.
    Pozniak BP, Cole RB. Negative ion mode evolution of potential buildup and mapping of potential gradients within the electrospray emitter. J Am Soc Mass Spectrom. 2004;15:1737–47.CrossRefGoogle Scholar
  18. 18.
    Van Berkel GJ, Zhou FM, Aronson JT. Changes in bulk solution ph caused by the inherent controlled-current electrolytic process of an electrospray ion source. Int J Mass Spectrom Ion Processes. 1997;162:55–67.CrossRefGoogle Scholar
  19. 19.
    Van Berkel GJ, Asano KG, Schnier PD. Electrochemical processes in a wire-in-a-capillary bulk-loaded, nano-electrospray emitter. J Am Soc Mass Spectrom. 2001;12:853–62.CrossRefGoogle Scholar
  20. 20.
    Hu J, Jiang X-X, Wang J, Guan Q-Y, Zhang P-K, Xu J-J, et al. Synchronized polarization induced electrospray: comprehensively profiling biomolecules in single cells by combining both positive-ion and negative-ion mass spectra. Anal Chem. 2016;88:7245–51.CrossRefGoogle Scholar
  21. 21.
    Gong X, Xiong X, Zhao Y, Ye S, Fang X. Boosting the signal intensity of nanoelectrospray ionization by using a polarity-reversing high-voltage strategy. Anal Chem. 2017;89:7009–16.CrossRefGoogle Scholar
  22. 22.
    Wei Z, Han S, Gong X, Zhao Y, Yang C, Zhang S, et al. Rapid removal of matrices from small-volume samples by step-voltage nanoelectrospray. Angew Chem Int Ed. 2013;52:11025–8.CrossRefGoogle Scholar
  23. 23.
    Wang Q, Zhong H, Zheng Y, Zhang S, Liu X, Zhang X, et al. Analyte migration electrospray ionization for rapid analysis of complex samples with small volume using mass spectrometry. Analyst. 2014;139:5678–81.CrossRefGoogle Scholar
  24. 24.
    Yuill EM, Sa N, Ray SJ, Hieftje GM, Baker LA. Electrospray ionization from nanopipette emitters with tip diameters of less than 100 nm. Anal Chem. 2013;85:8498–502.CrossRefGoogle Scholar
  25. 25.
    Juraschek R, Dülcks T, Karas M. Nanoelectrospray — more than just a minimized-flow electrospray ionization source. J Am Soc Mass Spectrom. 1999;10:300–8.CrossRefGoogle Scholar
  26. 26.
    Wei C, Bard AJ, Feldberg SW. Current rectification at quartz nanopipet electrodes. Anal Chem. 1997;69:4627–33.CrossRefGoogle Scholar
  27. 27.
    Ai Y, Zhang M, Joo SW, Cheney MA, Qian S. Effects of electroosmotic flow on ionic current rectification in conical nanopores. J Phys Chem C. 2010;114:3883–90.CrossRefGoogle Scholar
  28. 28.
    Sa N, Baker LA. Experiment and simulation of ion transport through nanopipettes of well-defined conical geometry. J Electrochem Soc. 2013;160:H376–H81.CrossRefGoogle Scholar
  29. 29.
    Shi W, Sa N, Thakar R, Baker LA. Nanopipette delivery: influence of surface charge. Analyst. 2015;140:4835–42.CrossRefGoogle Scholar
  30. 30.
    van Duijn E, Bakkes PJ, Heeren RMA, van den Heuvel RHH, van Heerikhuizen H, van der Vies SM, et al. Monitoring macromolecular complexes involved in the chaperonin-assisted protein folding cycle by mass spectrometry. Nat Methods. 2005;2:371–6.CrossRefGoogle Scholar
  31. 31.
    Verkerk UH, Kebarle P. Ion-ion and ion-molecule reactions at the surface of proteins produced by nanospray. Information on the number of acidic residues and control of the number of ionized acidic and basic residues. J Am Soc Mass Spectrom. 2005;16:1325–41.CrossRefGoogle Scholar
  32. 32.
    Hu J, Guan Q-Y, Wang J, Jiang X-X, Wu Z-Q, Xia X-H, et al. Effect of nanoemitters on suppressing the formation of metal adduct ions in electrospray ionization mass spectrometry. Anal Chem. 2017;89:1838–45.CrossRefGoogle Scholar
  33. 33.
    Mchedlov-Petrossyan NO, Shapovalov SA, Egorova SI, Kleshchevnikova VN, Arias Cordova E. A new application of rhodamine 200 b (sulfo rhodamine b). Dyes Pigm. 1995;28:7–18.CrossRefGoogle Scholar
  34. 34.
    Milanova D, Chambers RD, Bahga SS, Santiago JG. Electrophoretic mobility measurements of fluorescent dyes using on-chip capillary electrophoresis. Electrophoresis. 2011;32:3286–94.CrossRefGoogle Scholar
  35. 35.
    Martin MM, Lindqvist L. The ph dependence of fluorescein fluorescence. J Lumin. 1975;10:381–90.CrossRefGoogle Scholar
  36. 36.
    Eyring CF, MacKeown SS, Millikan RA. Fields currents from points. Phys Rev. 1928;31:900–9.CrossRefGoogle Scholar
  37. 37.
    Jones AR, Thong KC. The production of charged monodisperse fuel droplets by electrical dispersion. J Phys D: Appl Phys. 1971;4:1159–66.CrossRefGoogle Scholar
  38. 38.
    Smith DPH. The electrohydrodynamic atomization of liquids. IEEE Trans Ind Appl. 1986;IA-22:527–35.CrossRefGoogle Scholar
  39. 39.
    Hemdan ES, Zhao Y-J, Sulkowski E, Porath J. Surface topography of histidine residues: a facile probe by immobilized metal ion affinity chromatography. Proc Natl Acad Sci U S A. 1989;86:1811–5.CrossRefGoogle Scholar
  40. 40.
    Saha-Shah A, Green CM, Abraham DH, Baker LA. Segmented flow sampling with push-pull theta pipettes. Analyst. 2016;141:1958–65.CrossRefGoogle Scholar

Copyright information

© Springer-Verlag GmbH Germany, part of Springer Nature 2018

Authors and Affiliations

  1. 1.Department of ChemistryIndiana UniversityBloomingtonUSA

Personalised recommendations