5-Methoxysalicylic acid and spermine: A new matrix for the matrix-assisted laser desorption/ionization mass spectrometry analysis of oligonucleotides



5-Methoxysalicylic acid (MSA) is demonstrated to be a useful matrix for matrix-assisted laser desorption/ionization time-of-flight (TOF) mass spectrometry of oligonucleotides, when desorption/ionization without fragmentation is desired. When MSA is combined with the additive spermine, the need for desalting is reduced. The MSA/spermine matrix yields linear TOF mass spectra with improved resolution, less fragmentation, and less intense alkali ion adduct peaks than those spectra obtained using 3-hydroxypicolinic acid and 6-aza-2-thiothymine with spermine or diammonium hydrogen citrate as additives. Instrumental conditions are discussed to improve the spectral resolution, specifically the use of longer delay times in the delayed-extraction ion source.


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  1. 1.
    Karas, M.; Bachmann, D.; Bahr, U.; Hillenkamp, F. Int. J. Mass Spectrom. Ion Processes 1987, 78, 53–68.CrossRefGoogle Scholar
  2. 2.
    Nordhoff, E.; Kirpekar, F.; Roepstorff, P. Mass Spectrom. Rev. 1996, 15, 67–138.CrossRefGoogle Scholar
  3. 3.
    Limbach, P. A. Mass Spectom. Rev. 1996, 15, 297–336.CrossRefGoogle Scholar
  4. 4.
    Zhang, L.-K.; Gross, M. L. J. Am. Soc. Mass Spectrom. 2000, 11, 854–865.CrossRefGoogle Scholar
  5. 5.
    Asara, J.; Allison, J. Anal. Chem. 1999, 71, 2866–2870.CrossRefGoogle Scholar
  6. 6.
    Roskey, M. T.; Juhasz, P.; Smirnov, I. P.; Takach, E. J.; Martin, S. A.; Haff, L. A. Proc. Natl. Acad. Sci. USA 1996, 93, 4724–4729.CrossRefGoogle Scholar
  7. 7.
    Lavine, G.; Allison, J. J. Mass Spectrom. 1999, 34, 741–748.CrossRefGoogle Scholar
  8. 8.
    Currie, G.; Yates, J. III. J. Am. Soc. Mass Spectrom. 1993, 4, 955–963.CrossRefGoogle Scholar
  9. 9.
    Nordhoff, E.; Cramer, R.; Karas, M.; Hillenkamp, F.; Kirpekar, F.; Kristiansen, K.; Roepstorff, P. Nucleic Acids Res. 1993, 21, 3347–3357.CrossRefGoogle Scholar
  10. 10.
    Juhasz, P.; Roskey, M. T.; Smirnov, I. P.; Haff, L. A.; Vestal, M. L.; Martin, S. A. Anal. Chem. 1996, 68, 941–946.CrossRefGoogle Scholar
  11. 11.
    Koomen, J. M.; Russell, D. H. J. Mass Spectrom. 2000, 35, 1025–1034.CrossRefGoogle Scholar
  12. 12.
    Griffin, T. J.; Smith, L. M. Anal. Chem. 2000, 72, 3298–3302.CrossRefGoogle Scholar
  13. 13.
    Fei, Z.; Smith, L. M. Rapid Commun. Mass Spectrom. 2000, 14, 950–959.CrossRefGoogle Scholar
  14. 14.
    Börnsen, K. O.; Schär, M.; Widmer, H. M. Chimica 1990, 44, 412–416.Google Scholar
  15. 15.
    Hillenkamp, F.; Karas, M.; Ingendoh, A.; Stahl, B. In Biological Mass Spectrometry; Burlingame, A.; McCloskey, J. A., Eds.; Elsevier Scientific: Amsterdam, 1990; p 49.Google Scholar
  16. 16.
    Parr, G. R.; Fitzgerald, M. C.; Smith, L. M. Rapid Commun. Mass Spectrom. 1992, 6, 369–372.CrossRefGoogle Scholar
  17. 17.
    Spengler, B.; Pan, Y.; Cotter, R. J.; Kan, L. S. Rapid Commun. Mass Spectrom. 1990, 4, 99–102.CrossRefGoogle Scholar
  18. 18.
    Wu, K. J.; Steding, A.; Becker, C. H. Rapid Commun. Mass Spectrom. 1993, 7, 142–146.CrossRefGoogle Scholar
  19. 19.
    Lecchi, P.; Le, H. M. T.; Pannell, L. K. Nucleic Acids Res. 1995, 23, 1276–1277.CrossRefGoogle Scholar
  20. 20.
    Kirpekar, F.; Berkenkamp, S.; Hillenkamp, F. Anal. Chem. 1999, 71, 2334–2339.CrossRefGoogle Scholar
  21. 21.
    Berkenkamp, S.; Kirpekar, F.; Hillenkamp, F. Science 1998, 281, 260–262.CrossRefGoogle Scholar
  22. 22.
    Nordhoff, E.; Ingendoh, A.; Cramer, R.; Overberg, A.; Stahl, B.; Karas, M.; Hillenkamp, F.; Crain, P. F. Rapid Commun. Mass Spectrom. 1992, 6, 771–776.CrossRefGoogle Scholar
  23. 23.
    Li, Y. C. I.; Cheng, S. W.; Chan, T. W. D. Rapid Commun. Mass Spectrom. 1998, 12, 993–998.CrossRefGoogle Scholar
  24. 24.
    Pieles, U.; Zürcher, W.; Schär, M.; Möser, H. E. Nucleic Acid Res. 1993, 21, 3191–3196.CrossRefGoogle Scholar
  25. 25.
    Asara, J. M.; Hess, J. S.; Lozada, E.; Dunbar, K. R.; Allison, J. J. Am. Chem. Soc. 2000, 122, 8–13.CrossRefGoogle Scholar
  26. 26.
    Gusev, A. I.; Wilkinson, W. R.; Proctor, A.; Hercules, D. M. Anal. Chem. 1995, 67, 1034–1041.CrossRefGoogle Scholar
  27. 27.
    Tang, X.; Dreifuss, P.; Vertes, A. Rapid Commun. Mass Spectrom. 1995, 9, 1141–1147.CrossRefGoogle Scholar
  28. 28.
    Gusev, A. I.; Wilkinson, W. R.; Protor, A.; Hercules, D. M. Fresenius J. Anal. Chem. 1996, 354, 455–463.Google Scholar
  29. 29.
    McLuckey, S. A.; Van Berkel, J.; Glish, G. L. J. Am. Soc. Mass Spectrom. 1992, 3, 60–70.CrossRefGoogle Scholar
  30. 30.
    Zhu, Y. F.; Chung, C. N.; Taranenko, N. I.; Allman, S. L.; Martin, S. A.; Haff, L.; Chen, C. H. Rapid. Commun. Mass Spectrom. 1996, 10, 383–688.CrossRefGoogle Scholar
  31. 31.
    Zhu, L.; Parr, G.; Fitzgerald, M. C.; Nelson, C. M.; Smith, L. M. J. Am. Chem. Soc. 1995, 117, 6048–6056.CrossRefGoogle Scholar
  32. 32.
    Applied Biosystems. Models 392 and 394 DNA/RNA Synthesizers User’s Manual, Part 902351, Document Revision B. Norwalk, CT, March 1994.Google Scholar
  33. 33.
    Vertes, A.; Gijbels, R.; Levine, R. D. Rapid Commun. Mass Spectrom. 1990, 4, 228–233.CrossRefGoogle Scholar
  34. 34.
    Nordhoff, E.; Karas, M.; Cramer, R.; Hahner, S.; Hillenkamp, F.; Kirpekar, F.; Lezius, A.; Muth, J.; Meier, C.; Engels, J. W. J. Mass Spectrom. 1993, 30, 99–112.CrossRefGoogle Scholar

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© American Society for Mass Spectrometry 2001

Authors and Affiliations

  1. 1.Department of ChemistryMichigan State UniversityEast LansingUSA

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