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Comparison of mass spectrometric techniques for generating molecular weight information on a class of ethoxylated oligomers

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

An Erratum to this article was published on 01 June 1998

Abstract

The results of fast atom bombardment (FAB), time-of-flight secondary ion mass spectrometry (ToF-SIMS), matrix-assisted laser desorption/ionization (MALD/I), electrospray ionization (ESI), and field desorption (FD) analyses of ethoxylated oligomers of 2,4,7,9-tetramethyl-5-decyne-4,7-diol (Surfynol® 104) were compared.Each of these desorption mass spectrometry (MS) techniques can produce spectra of unfragmented cationized oligomers. From the observed ion series we calculate average molecular weight information. We have compared the results of mass spectrometric analyses of a series of ethoxylated Surfynol surfactants. Our data indicate that FAB, ToF-SIMS, MALDI/I, and ESI produce similar results for the lower molecular weight species, but that as the average molecular weight increases FAB and SIMS produce slightly lower results than MALD/I and FD. This could be due to increased fragmentation. ESI produced a result similar to FAB and SIMS for the highest average molecular weight material. Further experiments compare the mass spectral results with gas chromatographic quantitative data. Although gas chromatography is not expected to accurately analyze the higher mass oligomers, we observe significant differences in intensities of the short-chain oligomers (especially the 0- and 1-mers) when compared to the desorption mass spectrometer results. These differences may reflect poor cationization efficiency for very short oligomer chains in the mass spectrometric analyses.

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References

  1. Sperling, L. H. Introduction to Physical Polymer Science; Wiley: New York, 1986.

    Google Scholar 

  2. Smith, R. D.; Fjeldsted, J.; Lee, M. L. Int. J. Mass Spectrom. Ion Phys. 1983, 46, 217.

    Article  CAS  Google Scholar 

  3. Vincenti, M.; Pelizzetti, E.; Guarini, A.; Costanzi, S. Anal. Chem. 1992, 64, 1879.

    Article  CAS  Google Scholar 

  4. Prokai, L. Field Desorption Mass Spectrometry; Dekker: New York, 1990; pp 254–262.

    Google Scholar 

  5. Lattimer, R. P.; Harmon, D. J.; Welch, K. R. Anal. Chem. 1979, 51, 1293.

    Article  CAS  Google Scholar 

  6. Scrivens, J. H.; Jennings, R. C. K. J.; Yates, H.; Taylor, M. J.; Jackson, A. Proceedings of the 42nd ASMS Conference on Mass Spectrometry and Allied Topics, Chicago, IL, 1994; 313.

  7. Saito, J.; Toda, S.; Tanaka, S. Bunseki Kagaku, 1980, 29, 462.

    CAS  Google Scholar 

  8. Oshiro, H.; Sato, J.; Shimada, M. Kanzei Chuo Bunsekishoho 1986, 26, 23.

    CAS  Google Scholar 

  9. Barber, M.; Bordoli, R.; Sedgwick, R. D.; Tyler, A. N. J. J. Chem. Soc. Chem. Commun. 1981, 325.

  10. Facino, R. M.; Carini, M.; Minghetti, P.; Moneti, G.; Arlandini, E.; Melis, S. Biomed. Environ. Mass Spectrom. 1989, 18, 673.

    Article  CAS  Google Scholar 

  11. Seraglia, R.; Traldi, P.; Mendichi, R.; Sartore, L.; Schiavon, O.; Veronese, R. M. Anal. Chim. Acta 1992, 262, 277.

    Article  CAS  Google Scholar 

  12. Fenn, J. B. J. Am. Soc. Mass Spectrom. 1993, 4, 524.

    Article  CAS  Google Scholar 

  13. Yamashita, M.; Fenn, J. B. J. Phys. Chem. 1984, 88, 4451.

    Article  CAS  Google Scholar 

  14. Yamashita, M.; Fenn, J. B. J. Phys. Chem. 1984, 88, 4471.

    Google Scholar 

  15. Fenn, J. B.; Mann, M.; Meng, C. K.; Wong, S. F.; Whitehouse, C. M. Science 1989, 246, 64–71.

    Article  CAS  Google Scholar 

  16. Dole, M.; Mack, L. L.; Hines, R. L.; Mobley, R. C.; Ferguson, L. D.; Alice, M. B. J. Chem. Phys. 1968, 49, 2240.

    Article  CAS  Google Scholar 

  17. Whitehouse, C. M.; Dreyer, R. N.; Yamashita, M.; Fenn, J. B. Anal. Chem. 1985, 57, 675.

    Article  CAS  Google Scholar 

  18. Wong, S. F.; Meng, C. K.; Fenn, J. B. J. Phys. Chem. 1988, 92, 546.

    Article  CAS  Google Scholar 

  19. Fenn, J. B.; Mann, M.; Meng, C. K.; Wong, S. F., Mass Spectrom. Rev. 1990, 9, 37–70.

    Article  CAS  Google Scholar 

  20. Thomson, B. A.; Iribarne, J. V. J. Chem. Phys. 1979, 71, 4451–4463.

    Article  CAS  Google Scholar 

  21. Mann, M. Org. Mass Spectrom. 1990, 25, 575–587.

    Article  CAS  Google Scholar 

  22. Smith, R. D.; Loo, J.; Edmonds, C. G.; Barinaga, C. J.; Udseth, H. R. Anal. Chem. 1990, 62, 882.

    Article  CAS  Google Scholar 

  23. Tanaka, K.; Waki, H.; Ido, Y.; Akita, S.; Yoshida, Y.; Yoshida, T. Rapid Commun. Mass Spectrom. 1988, 2, 151.

    Article  CAS  Google Scholar 

  24. Karas, M.; Hillenkamp, F. Anal. Chem. 1988, 60, 2299.

    Article  CAS  Google Scholar 

  25. Bahr, U.; Deppe, A.; Karas, M.; Hillenkamp, F.; Giessman, U. Anal. Chem. 1992, 64, 2866.

    Article  CAS  Google Scholar 

  26. Beavis, R.; Chait, B. Anal. Chem. 1990, 62, 1836.

    Article  CAS  Google Scholar 

  27. Benninghoven A. Angew. Chem. Int. Ed. Engl. 1994, 33, 1023.

    Article  Google Scholar 

  28. Cotter R. J.; Honovich J. P.; Olthoff J. K.; Lattimer R. P. Macromolecules 1986, 19, 2996.

    Article  CAS  Google Scholar 

  29. McEwen, C. N.; Simonsick, W. J., Jr. Larsen, B. S.; Ute, K.; Hatada, K.; J. Am. Soc. Mass Spectrom. 1995, 6, 906.

    Article  CAS  Google Scholar 

  30. O’Brien, P. B.; McLafferty, F. W. J. Am. Chem. Soc. 1995, 117, 12826.

    Article  Google Scholar 

  31. Danis, P.; Karr, D.; Mayer, F.; Holle, A.; Watson, C. Org. Mass Spectrom. 1992, 27, 843.

    Article  CAS  Google Scholar 

  32. Danis, P.; Karr, D. Org. Mass Spectrom. 1993, 28, 923.

    Article  CAS  Google Scholar 

  33. Bürger, M.; Müller, H.; Seebach, D.; Börsen, O.; Schär, M.; Widmer, M. Macromolecules 1993, 26, 4783.

    Article  Google Scholar 

  34. Blais, J.; Tessier, M.; Bolbach, G.; Remaud, B.; Rozes, L.; Guittard, J.; Brunot, A.; Maréchal, E.; Tabet, J. Int. J. Mass Spectrom. Ion Proc. 1995, 144, 131.

    Article  CAS  Google Scholar 

  35. Hanton, S. D.; Parees, D. M.; Goldschmidt, R. J.; King, R.; Owens, K. Proceedings of the 43rd ASMS Conference on Mass Spectrometry and Allied Topics, Atlanta, GA, 1995; 19.

  36. King, R. C.; Owens, K. G.; Hanton, S. D. Proceedings of the 43rd ASMS Conference on Mass Spectrometry and Allied Topics, Atlanta, GA, 1995; 1238.

  37. King, R. C.; Goldschmidt, R. J.; Xiong, Y.; Owens, K. G.; Hanton, S. D. Proceedings of the 43rd ASMS Conference on Mass Spectrometry and Allied Topics, Atlanta, GA, 1995; 689.

  38. Lloyd, P.; Suddaby, K.; Varney, J.; Scrivener, E.; Derrick, P.; Haddleton, D. Euro. Mass Spectrom. 1995, 1, 293.

    Article  CAS  Google Scholar 

  39. Belu, A.; DeSimone, J.; Linton, R.; Lange, G.; Friedman, R. J. Am. Soc. Mass Spectrom. 1996, 7, 11.

    Article  CAS  Google Scholar 

  40. Bletsos, I. V.; Hercules, D. M.; van Leyen, D.; Benninghoven, A. Macromolecules 1987, 20, 407.

    Article  CAS  Google Scholar 

  41. Benninghoven, A. Angew Chem. Int. Ed. Engl. 1994, 33, 1023.

    Article  Google Scholar 

  42. Pachuta, S. J.; Cooks, R. G. Chem. Rev. 1987, 87, 647.

    Article  CAS  Google Scholar 

  43. Wandass, J. H.; Schmitt, R. L.; Gardella, J. A., Jr. J. Appl. Surf. Sci. 1989, 40, 85.

    Article  CAS  Google Scholar 

  44. Benninghoven, A.; Jaspers, D.; Sichtermann, W. Appl. Phys. 1976, 11, 35.

    Article  CAS  Google Scholar 

  45. Grade, H.; Winograd, N.; Cooks, R. G. J. Am. Chem. Soc. 1977, 99, 7725.

    Article  CAS  Google Scholar 

  46. Benninghoven, A.; Rudenauer, F. G.; Werner, H. W. Secondary Ion Mass Spectrometry—Basic Concepts, Instrumental Aspects, Applications and Trends; Wiley: New York, 1987.

    Google Scholar 

  47. Madhusudanan, K. P.; Dhami, T. S.; Katiyar, S.; Suryawanski, S. N. Org. Mass Spectrom. 1994, 29, 238.

    Article  CAS  Google Scholar 

  48. Montaudo G.; Montaudo M. S.; Puglisi C.; Samperi F. Macromolecules 1995, 28, 4562.

    Article  CAS  Google Scholar 

  49. Cody, R. B.; Finch, J. W. Proceedings of the 42nd ASMS Conference on Mass Spectrometry and Allied Topics, Chicago, IL, 1994; 522.

  50. Hunt, S. M.; Binns, M. R.; Sheil, M. M. J. Appl. Polym. Sci. 1995, 56, 1589–1597.

    Article  CAS  Google Scholar 

  51. Prokai, L.; Simonsick, Jr., W. J. Rapid Commun. Mass Spectrom. 1993, 7, 853.

    Article  CAS  Google Scholar 

  52. Kallos, J.; Tomalia, D. A.; Hedstrand, D. M.; Lewis, S.; Zhou, J. Rapid Commun. Mass Spectrom. 1991, 5, 383.

    Article  CAS  Google Scholar 

  53. Fenn, J. B.; Mann, M.; Meng, C. K.; Wong, S. F.; Whitehouse, C. M. Science 1989, 246, 64–71.

    Article  CAS  Google Scholar 

  54. Sherrard, K. B.; Marriott, P. J.; McCormick, M. J.; Colton, R.; Smith, G. Anal. Chem. 1994, 66, 3394–3399.

    Article  CAS  Google Scholar 

  55. Schultz, G. A.; Alexander, IV, J. N. Proceedings of the 42nd ASMS Conference on Mass Spectrometry and Allied Topics, Chicago, IL, 1994; 174.

  56. Parees, D. M.; Hanton, S. D.; Willcox, D. A.; Cornelio Clark, P. A. Polym. Preprints 1996, 37, 321.

    CAS  Google Scholar 

  57. Lattimer, R. P. Int. J. Mass Spectrom. Ion Proc. 1983/1984, 55, 221.

    Article  Google Scholar 

  58. Cornelio Clark, P. A.; Hanton, S. D.; Parees, D. M. Proceedings of the 44th ASMS Conference on Mass Spectrometry and Allied Topics, Portland, OR, 1996; 893.

  59. Hanton, S. D.; Parees, D. M.; Hanley, B. F.; King, R. C.; Owens, K. G. Proceedings of the 43rd ASMS Conference on Mass Spectrometry and Allied Topics, Atlanta, GA, 1995; 952.

  60. Saucy, D. A.; Huby, F. J.; Zhu, L. Proceedings of the International GPC Symposium ’96, San Diego, CA, 1996; 57.

  61. Parees, D. M.; Karwacki, E. J.; Tiedge, W. F.; Chakel, J.; Reich, F. Presentation at the 6th Sanibel Conference on Mass Spectrometry: Mass Spectrometry in Polymers and Materials Science, Sanibel, FL, January, 1994.

  62. Purcell, K. F.; Kotz, J. C. Inorganic Chemistry; Saunders: Philadelphia, 1977; p 198.

    Google Scholar 

  63. Pederson, C. J. J. Am. Chem. Soc. 1967, 89, 2495.

    Article  Google Scholar 

  64. Pederson, C. J. J. Am. Chem. Soc. 1967, 89, 7017.

    Article  Google Scholar 

  65. Wu, H.-F.; Brodbelt, J. S. Inclusion Phenom. Macromol. Recogn. Chem. 1994, 18, 37.

    Article  CAS  Google Scholar 

  66. von Helden, G.; Wyttenbach, T.; Bowers, M. T. Science 1995, 267, 1483.

    Article  Google Scholar 

  67. Lee, S.; Wyttenbach, T.; von Helden, G.; Bowers, M. T. J. Am. Chem. Soc. 1995, 117, 10159.

    Article  CAS  Google Scholar 

  68. von Helden, G.; Wyttenbach, T.; Bowers, M. T. Int. J. Mass Spectrom. Ion Proc. 1995, 146/147, 349.

    Article  Google Scholar 

  69. Wavefunction Inc., Spartan 4. 0, Irvine, CA, 1995.

  70. Xiong, H. Y. Ph. D. Thesis, Drexel University, 1997.

  71. Grob, K. Classical Split and Splitless Injection in Capillary GC, 2nd ed. Huethig: New York, 1988.

    Google Scholar 

  72. Miszkiewicz, W.; Szymanowski, J. Cr. Rev. Anal. Chem. 1996, 25, 203.

    Article  CAS  Google Scholar 

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Correspondence to David M. Parees.

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An erratum to this article is available at http://dx.doi.org/10.1016/S1044-0305(98)00040-3.

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Parees, D.M., Hanton, S.D., Clark, P.A.C. et al. Comparison of mass spectrometric techniques for generating molecular weight information on a class of ethoxylated oligomers. J Am Soc Mass Spectrom 9, 282–291 (1998). https://doi.org/10.1016/S1044-0305(97)00291-2

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  • DOI: https://doi.org/10.1016/S1044-0305(97)00291-2

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