Development of chemical ionization method in a GC-TOF mass spectrometer for accurate mass and isotope ratio measurement

Accurate mass 및 isotope ratio 측정을 위한 GC-TOF 질량분석기에서의 화학적 이온화방법

  • 정주희 (한국기초과학지원연구원 서울센터 분석연구부) ;
  • 나윤철 (한국기초과학지원연구원 서울센터 분석연구부) ;
  • 황금숙 (한국기초과학지원연구원 서울센터 분석연구부) ;
  • 신정화 (한국기초과학지원연구원 서울센터 분석연구부) ;
  • 안윤경 (한국기초과학지원연구원 서울센터 분석연구부)
  • Received : 2010.12.31
  • Accepted : 2011.01.10
  • Published : 2011.02.25


An accurate mass and isotope ratio were determined using a gas chromatography/time of flight mass spectrometer in CI positive mode for the identification of unknown metabolites. High mass tune was used to improve the ion intensity of $[M+H]^+$. Chromatographic resolution and dynamic range enhancement were performed to obtain more reliable accurate masses and correct isotope abundance ratios. Average absolute errors of mass and isotope ratios for 24 reference metabolite -TMS (trimethylsilyl) derivatives were 6.8 ppm, 1.5% of (M+1/M ratio) and 1.7% of (M+2/M ratio), respectively. The correct formulas of twenty one compound were retrieved within top-2 hit from the heuristic algorithm for elemental composition using each accurate mass and isotope abundance ratio.


  1. G. V. Silas, S. Mas, M. Kesson, J. Smedsgaard and J. Nielsen, Mass Spectrometry Reviews, 24, 613-646(2005).
  3. O. Fiehn, J. Kopka, P. Drmann, T. Altmann, R. N. Trethewey and L. Willmitzer, Nat. Biotechnol. 18, 1157-1161(2000).
  4. S. Strelkov, M. V. Elstermann and D. Schomburg, Bio. Chem., 385, 853-861(2004).
  5. C. Denkert, J. Budczies, T. Kind, W. Weichert, P. Tablack, J. Sehouli, S. Niesporek, D. Koensgen, M. Dietel and O. Fiehn, Cancer Res., 66(22), 10795-10804(2006).
  6. J. Lisec, N. Schauer, J. Kopka, L. Willmitzer and A. R. Fernie, Nature Protocols 1, 387-396(2006).
  7. D. Y. Lee and O. Fiehn, Plant Methods, 4, 1-13(2008).
  8. D. Herebian and B. Hanisch, F.-J. Marner, Metabolomics, 1(4), 317-324(2005).
  9. V. V. Tolstikov, Methods Mol. Biol., 544, 343-353(2009).
  10. A. Gordin, A. B. Fialkov and A. Amirav, Rapid Commun Mass Spectrom., 22(17), 2660-2666(2008).
  11. R. Flamini, A. D. Vedova, D. Cancian, A. Panighel and M. D. Rosso, J. Mass Spectrom., 42(5), 641-646(2007).
  12. Q. Kuangnan, D. J. Gary and E. E. Kathleen, Int. J. Mass Spectrom., 265, 230-236(2007).
  13. R. C. Jose and P. R. Paul, Organic Geochemistry, 30, 279-286(1999).
  14. W. Welthagen, S. Mitschke, F. Muhlberger and R. Zimmermann, J. Chromatogr. A., 1150, 54-61(2007).
  15. Z. Ralf, W. Werner and G. Thomas, J. Chromatogr. A., 1184, 296-308(2008).
  16. T. Kind and O. Fiehn, BMC Bioinformatics, 7, 234, 1-10(2006).
  17. T. Kind and O. Fiehn, BMC Bioinformatics, 8, 115, 1-20(2007).
  18. Y. Wang and M. Gu, Anal Chem., 82(17), 7055-62(2010).
  19. J. C. Erve, M. Gu, Y. Wang, W. DeMaio and R. E. Talaat, J. Am. Soc. Mass. Spectrom., 20(11) 2058-69(2009).
  20. M. Gu, Y. Wang, X. G. Zhao and Z. M. Gu, Rapid Commun Mass Spectrom., 20(5), 764-70(2006).
  22. T. Kind, G. Wohlgemuth, D. Y. Lee, Y. Lu, M. Palazoglu, S. Shahbaz and O. Fiehn, Anal. Chem., 81(24), 10038-10048(2009).
  23. O. Masaki, Y. Hiroyuki, F. Hirohiko, K. Satoshi, Y. Daisuke, O. K. Koji, M. Eizi, S. Kazuhiko and U. Nobuo, Nucl. Instr. and Meth. in Phys. Res. B 236(1) 377-382(2005).
  24. T. Kind, V. V. Tolstikov, O. Fiehn and R. H. Weiss, Anal. Biochem., 363, 185-195(2007).
  25. S. Abate, Y. G. Ahn,T. Kind, T. Cataldi and O. Fiehn, Rapid Commun Mass Spectrom., 24, 1172-1180(2010).