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Effects of molecular entanglements during electrospray of high molecular weight polymers

  • Focus: Synthetic Polymers
  • Published:
Journal of the American Society for Mass Spectrometry

Abstract

Concentration-dependent bimodal size distributions (comprised of single-molecule particles and multimolecule clusters) observed by microscopic examination of particles collected during electrospray (ES) of dilute solutions of high molecular weight polymers suggest that chain entanglement can interfere with the droplet subdivisions believed to be intrinsic to the electrospray process. The feasibility of such interference is discussed in the context of the spray model of Kebarle, along with its potential impact on the ES mass spectrometry of macromolecules.

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References

  1. Festag, R.; Alexandratos, S. D.; Cook, K. D.; Joy, D. C.; Annis, B.; Wunderlich, B. Single- and Few-Chain Polystyrene Particles by Electrospray. Macromolecules 1997, 30, 6238–6242.

    Article  CAS  Google Scholar 

  2. DeGennes, P. G. Scaling Concepts in Polymer Physics Cornell University Press: Ithaca, 1979;219–241.

    Google Scholar 

  3. Nohmi, T.; Fenn, J. B. Electrospray Mass Spectrometry of Poly(ethylene glycols) with Molecular Weights up to Five Million. J. Am. Chem. Soc. 1992, 114, 3241–3246.

    Article  CAS  Google Scholar 

  4. 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.

    Article  CAS  Google Scholar 

  5. Bugarski, B.; Li, Q.; Goosen, M. F.; Poncelet, D.; Neufeld, R. J.; Vunjak, G. Electrostatic Droplet Generation: Mechanism of Polymer Droplet Formation. AIChE J. 1994, 40, 1026–1031.

    Article  Google Scholar 

  6. Tang, K.; Gomez, A. On the Structure of an Electrostatic Spray of Monodisperse Droplets. Phys. Fluids 1994, 6, 2317–2332.

    Article  Google Scholar 

  7. Gomez, A.; Tang, K. Charge and Fission of Droplets in Electrostatic Sprays. Phys. Fluids 1994, 6, 404–414.

    Article  CAS  Google Scholar 

  8. Grigoŕev, A. I.; Shiryawva, S. O.; Verbitsky, S. S. Theory of Production of Monodisperse Particles by Electrostatic Spraying of Liquids. J. Colloid Interface Sci. 1991, 146, 137–151.

    Article  Google Scholar 

  9. Chen, R.; Cheng, X.; Mitchell, D. W.; Hofstadler, S. A.; Wu, Q.; Rockwood, A. L.; Sherman, M. G.; Smith, R. D. Trapping, Detection, and Mass Determination of Coliphage T4 DNA Ions of 108 Da by Electrospray Ionization Fourier Transform Ion Cyclotron Resonance Mass Spectrometry. Anal. Chem. 1995, 67, 1159–1163.

    Article  CAS  Google Scholar 

  10. Buchanan, M. V.; Hettich, R. L. Fourier Transform Mass Spectrometry of High-Mass Biomolecules. Anal. Chem. 1993, 65, 245A-259A.

    Article  CAS  Google Scholar 

  11. Dole, M.; Mack, L. L.; Hines, R. L.; Mobley, R. C.; Ferguson, L. D.; Alice, M. B. Molecular Beams of Macroions. J. Chem. Phys. 1968, 49, 2240–2249.

    Article  CAS  Google Scholar 

  12. Gieniec, J.; Mack, L. L.; Nakamae, K.; Gupta, C.; Kumar, V.; Dole, M. Electrospray Mass Spectroscopy of Macromolecules: Applications of an Ion-Drift Spectrometer. Biomed. Mass Spectrom. 1984, 11, 259–268.

    Article  CAS  Google Scholar 

  13. Jasieczek, C. B.; Buzy, A.; Haddleton, D. M.; Jennings, K. R. Electrospray Ionization Mass Spectrometry of Poly(styrene). Rapid Commun. Mass Spectrom. 1996, 10, 509–514;

    Article  CAS  Google Scholar 

  14. Deery, M. J.; Jennings, K. R.; Jasieczek, C. B.; Haddleton, D. M.; Jackson, A. T.; Yates, H. T.; Scrivens, J. H. A. Study of Cation Attachment to Polystyrene by Means of Matrix-assisted Laser Desorption/Ionization and Electrospray Ionization-Mass Spectrometry. Rapid Commun. Mass Spectrom. 1997, 11, 57–62.

    Article  CAS  Google Scholar 

  15. Nielen, M. W. F. Characterization of Synthetic Polymers by Size-exclusion Chromatography/Electrospray Ionization Mass Spectrometry. Rapid Commun. Mass Spectrom. 1996, 10, 1652–1660.

    Article  CAS  Google Scholar 

  16. Ikonomou, M. G.; Blades, A. T.; Kebarle, P. Investigations of the Electrospray Interface for Liquid Chromatography/Mass Spectrometry. Anal. Chem. 1990, 62, 957–967.

    Article  CAS  Google Scholar 

  17. Davies, C. N. Evaporation of Airborne Droplets, in Fundamentals of Aerosol Science, D. T. Shaw, Ed.; Wiley: New York, 1978; pp 135–164.

    Google Scholar 

  18. Daoud, M.; Jannink, G. Temperature-Concentration Diagram of Polymer Solutions. J. Phys. (Paris) 1976, 37, 973–979.

    Article  CAS  Google Scholar 

  19. Koszterszitz, G.; Barnikol, W. K.; Schulz, G. V. Die Bestimmung der Molekulargewichtsverteilung von nichtkristallisierenden Polymeren mit dem Elektronenmikroskop, 4. Makromol. Chem. 1977, 178, 1133–1148.

    Article  CAS  Google Scholar 

  20. Bu, H.; Pang, Y.; Song, D.; Yu, T.; Voll, T. M.; Czornyj, G.; Wunderlich, B. Single-Molecule Single Crystals J. Poly. Sci., Part B: Poly. Phys. 1991, 29, 139–152.

    Article  CAS  Google Scholar 

  21. 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.

    Article  CAS  Google Scholar 

  22. Taflin, D. C.; Ward, T. L.; Davis, E. J. Electrified Droplet Fission and the Rayleigh Limit. Langmuir 1989, 5, 376–384.

    Article  CAS  Google Scholar 

  23. Kumaki, J. Polystyrene Monomolecular Particles Attained by Spreading Dilute Solutions on the Water Surface. Macromolecules 1986, 19, 2258–2263.

    Article  CAS  Google Scholar 

  24. Mark, J. Handbook of Physical Properties of Polymers 1996 AIP Press: Woodbury, 337.

    Google Scholar 

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Correspondence to Kelsey D. Cook.

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Festag, R., Alexandratos, S.D., Joy, D.C. et al. Effects of molecular entanglements during electrospray of high molecular weight polymers. J Am Soc Mass Spectrom 9, 299–304 (1998). https://doi.org/10.1016/S1044-0305(98)00004-X

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  • DOI: https://doi.org/10.1016/S1044-0305(98)00004-X

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