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Chromatography–mass spectrometry determination of alkyl methylphosphonic acids in urine

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Abstract

The potentials of different chromatography–mass spectrometry methods for the determination of alkyl methylphosphonic acids (AMPAs)—the chemical markers of nerve agents in urine—are compared. The gas chromatography–mass spectrometry (GC–MS) characteristics of various volatile AMPA derivatives are studied. The preference of perfluorobenzyl derivatives over methyl, trimethylsilyl and tert-butyldimethylsilyl esters for the GC–MS determination of AMPAs in urine is demonstrated. An optimal technique for the determination of AMPAs in urine is HPLC combined with high-resolution MS2 mass spectrometry with the isotope–labeled forms of target compounds as internal standards. The detection limits of AMPAs in the proposed analytical procedures vary from 0.1 to 1.0 ng/mL.

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References

  1. Munro, N.B., Talmage, S.S., Griffin, L.C., Waters, A.P., Watson, A.P., King, J.F., and Hauschhild, V., Environ. Health Perspect., 1999, vol. 107, no. 12, p. 933.

    Article  CAS  Google Scholar 

  2. Koryagina, N.L., Savel’eva, E.I., Khlebnikova, N.S., Kopeikin, V.A., Koneva, V.Yu., and Radilov, A.S., Toksikol. Vestn., 2014, no. 4, p. 39.

    Google Scholar 

  3. Riches, J., Morton, I., Read, R.W., and Black, R.M., J. Chromatogr. B: Anal. Technol. Biomed. Life Sci., 2005, vol. 816, nos. 1–2, p. 251.

    Article  CAS  Google Scholar 

  4. Black, R.M., Read, R.W., and Ivie, G.W., Bull. Environ. Contam. Toxicol., 1980, vol. 24, no. 1, p. 40.

    Article  Google Scholar 

  5. Black, R.M., J. Anal. Toxicol., 2008, vol. 32, no. 1, p. 2.

    Article  CAS  Google Scholar 

  6. Rastegaev, O.Yu., Chupis, V.N., Simonenko, N.S., and Chernikov, S.N., RF Patent 2398759, 2010. http://bd.patent.su/2398000-2398999/pat/servl/servlet2de5. html. Cited March 16, 2015.

    Google Scholar 

  7. Karakashev, G.V., Krivorotova, N.V., Morozova, T.E., Koryagina, N.L., Savel’eva, E.I., and Kopeikin, V.A., Certificate of Attestation no. 222.0183/0 doi 1.00258/2012, 2012. FR.1.39.2012.13710.1.00258/2012

    Google Scholar 

  8. Polletini, A., J. Chromatogr. B: Biomed. Sci. Appl., 1999, vol. 733, nos. 1–2, p. 47.

    Article  Google Scholar 

  9. Black, R.M. and Muir, R.W., J. Chromatogr. A, 2003, vol. 1000, nos. 1–2, p. 253.

    Article  CAS  Google Scholar 

  10. Palit, M., Gupta, A.K., Jain, R., and Raza, S.K., J. Chromatogr. A, 2004, vol. 1043, no. 2, p. 275.

    Article  CAS  Google Scholar 

  11. Driskell, W.J., Shih, M., Needham, L.L., and Barr, D.B., J. Anal. Toxicol., 2002, vol. 26, no. 1, p. 6.

    Article  CAS  Google Scholar 

  12. Koryagina, N.L., Savel’eva, E.I., Khlebnikova, N.S., and Radilov, A.S., Abstracts of Papers, Nauch.-praktich. seminar “Analiz otravlyayushchikh veshchestv: razrabotka i primenenie metodov” (Sci.-Practical Seminar “Analysis of Toxic Substances: Development and Application of Methods), St. Petersburg, 2006, p. 73.

    Google Scholar 

  13. Savelieva, E.I., Koryagina, N.L., Khlebnikova, N.S., Feld, V.E., and Radilov, A.S., in Proc. the Sixth Int. Chemical and Biological Medical Treatment Symposium, Spiez, Switzerland, 2006, p. 64.

    Google Scholar 

  14. Koryagina, N.L., Extended Abstract of Cand. Sci. (Chem.) Dissertation, St. Petersburg, 2007.

    Google Scholar 

  15. Rosenfeld, J.M., Solid-phase analytical derivatization: enhancement of sensitivity and selectivity of analysis, J. Chromatogr. A, 1999, vol. 843, nos. 1–2, p. 19.

    Article  CAS  Google Scholar 

  16. Kataoka, M. and Seto, Y., Discriminative determination of alkyl methylphosphonates and methylphosphonate in blood plasma and urine by gas chromatographymass spectrometry after tert-butyldimethylsilylation, J. Chromatogr. B: Anal. Technol. Biomed. Life Sci., 2003, vol. 795, no. 1, p. 123.

    Article  CAS  Google Scholar 

  17. Sega, G.A., Tomkins, B.A., and Griest, W.H., J. Chromatogr. A, 1997, vol. 790, nos. 1–2, p. 143.

    Article  CAS  Google Scholar 

  18. Noort, D., Benschtop, H.P., and Black, R.M., Toxicol. Appl. Pharmacol., 2002, vol. 184, no. 2, p. 116.

    Article  CAS  Google Scholar 

  19. Polhuijs, M., Langenberg, J.P. and Benschop, H.P., Toxicol. Appl. Pharmacol., 1997, vol. 146, no. 1, p. 156.

    Article  Google Scholar 

  20. Nagao, M., Takatori, T., Matsuda, Y., Nakajima, M., Iwase, H., and Iwadate, K., Toxicol. Appl. Pharmacol., 1997, vol. 144, no. 1, p. 198.

    Article  CAS  Google Scholar 

  21. Nakajima, T., Sasaki, K., Ozawa, H., Sekijima, Y., Morita, H., Fukushima, Y., and Yanagisawa, N., Arch. Toxicol., 1998, vol. 72, no. 9, p. 601.

    Article  CAS  Google Scholar 

  22. Noort, D., Hulst, A.G., Platenburg, D.H.J.M., Polhuijs, M., and Benschop, H.P., Arch. Toxicol., 1998, vol. 72, no. 10, p. 671.

    Article  CAS  Google Scholar 

  23. Purdon, J.G., Pagotto, J.G., and Miller, R.K., J. Chromatogr. A, 1989, vol. 475, no. 2, p. 261.

    Article  CAS  Google Scholar 

  24. Savel’eva, E.I., Gustyleva, L.K., Orlova, O.I., Khlebnikova, N.S., Koryagina, N.L., and Radilov, A.S., Russ. J. Appl. Chem., 2014, vol. 87, no. 8, p. 1003.

    Article  Google Scholar 

  25. Read, R.W. and Black, R.M., J. Chromatogr. A, 1999, vol. 862, no. 2, p. 169.

    Article  CAS  Google Scholar 

  26. Black, R.M. and Read, R.W., J. Chromatogr. A, 1998, vol. 794, nos. 1–2, p. 233.

    Article  CAS  Google Scholar 

  27. Mercier, J.-P., Morin, Ph., and Dreux, М., Chimia, 1999, vol. 53, no. 10, p. 511.

    CAS  Google Scholar 

  28. Mercier, J.-P., Morin, Ph., Dreux, M., and Tambut’e, A., J. Chromatogr. A, 1999, vol. 849, no. 1, p. 197.

    Article  CAS  Google Scholar 

  29. Kostiainen, R., Bruins, A.P., and Hakkinen, V.M.A., J. Chromatogr. A, 1993, vol. 634, no. 1, p. 113.

    Article  CAS  Google Scholar 

  30. Minami, M., Hui, D.-M., Katsumata, M., Inagaki, H., and Boulet, C.A., J. Chromatogr. B: Biomed. Sci. Appl., 1997, vo. 695, no. 2, p. 237.

    Article  CAS  Google Scholar 

  31. D’Agostino Hancock, J.R. and Provost, L.R., J. Chromatogr. A, 1999, vol. 837, nos. 1–2, p. 93.

    Article  Google Scholar 

  32. Rybal’chenko, I.V., Bolotov, S.L., and Rodchenkov, G.M., Mass-Spektrom., 2011, vol. 8, no. 1, p. 45.

    Google Scholar 

  33. Rodin, I.A., Braun, A.V., Stavrianidi, A.N., Shpigun, O.A., and Rybal’chenko, I.V., Analitika Kontrol’, 2012, vol. 16, no. 3, p. 254.

    Google Scholar 

  34. Rodin, I., Braun, A., Stavrianidi, A., Baygildiev, Т., and Shpigun, О., J. Anal. Toxicol., 2015, vol. 39, no. 1, p. 69.

    Article  CAS  Google Scholar 

  35. Hayes, T.L., Kenny, D.V., and Hernon-Kenny, L., J. Med. Chem. Def., 2004, vol. 2, no. 1, p. 1.

    Google Scholar 

  36. Recommended operating procedures for analysis in the verification of chemical disarmament, Vanninen, P., Ed., Helsinki: Univ. Helsinki, 2011.

  37. Savel’eva, E.I., Koryagina, N.L., Kopeikin, V.A., Sorokoumov, P.N., and Koneva, V.Yu., Certificate of Attestation no. 222.0255/0, 2014. doi 1.00258/2014

    Google Scholar 

  38. Black, R.M., Historical and perspectives of bioanalytical methods for chemical warfare, J. Chromatogr. B: Anal. Technol. Biomed. Life Sci., 2010, vol. 878, nos. 17–18, p. 1207.

    Article  CAS  Google Scholar 

  39. Doorn, J.A., Talley, T.T., Thompson, C.M., and Richardson, R.J., Chem. Res. Toxicol., 2001, vol. 14, no. 7, p. 807.

    Article  CAS  Google Scholar 

  40. Worek, F., Thiermann, H., Szinicz, L., and Eyer, P., Biochem. Pharmacol., 2004, vol. 68, no. 11, p. 2237.

    Article  CAS  Google Scholar 

  41. Aurbek, N., Thiermann, H., Szinicz, L., Eyer, P., and Worek, F., Toxicology, 2006, vol. 224, nos. 1–2, p. 91.

    Article  CAS  Google Scholar 

  42. Black, R.M., Harrison, J.M., and Read, R.W., Arch. Toxicol., 1999, vol. 73, no. 2, p. 123.

    Article  CAS  Google Scholar 

  43. Koryagina, N.L., Savel’eva, E.I., Khlebnikova, N.S., Orlova, O.I., et al., Abstracts of Pappers, Konf. “Khimicheskaya bezopasnost’ Rossiiskoi Federatsii v sovremennykh usloviyakh” (Conf. on Chemical Security of the Russian Federation in Modern Conditions), St. Petersburg, 2010, p. 157.

    Google Scholar 

  44. Koryagina, N., Savelieva, E., Radilov, A., Khlebnikova, N., Orlova, O., Kopeykin, V., and Gustyleva, L., in Proc. 13th Annual Meeting of the Israel Analytical Chemistry Society Conference and Exhibition, Tel Aviv, Israel, 2010, p. 124.

    Google Scholar 

  45. Morozova, T.E., Karakashev, G.V., Koryagina, N.L., and Ukolova, E.S., in Proc. 1st Int. Conf. on Urine Omics, Caparica, Portugal, 2013, p. 170.

    Google Scholar 

  46. Morozova, T.E., Karakashev, G.V., Koryagina, N.L., and Ukolova, E.S., Abstracts of Papers, Nauch. konf. “Analiticheskaya khromatografiya i kapillyarnyi elektroforez” (Sci. Conf. on Analytical Chromatography and Capillary Electrophoresis), Krasnodar, 2013, p. 33.

    Google Scholar 

  47. MR (Methodological Guidelines) 1.2.028-12: Confirmation of the Interaction of Organophosphorus Agents on the Body by the Results of Urine Analysis Using HPLC–MS/MS, Moscow, 2012.

  48. MR (Methodological Guidelines) 1.2.028-12: Confirmation of the Effects of Toxic Substances on the Body according to the Results of Analysis of Biological Samples in the Participation of the Russian Federation in the Investigation of the Technical Secretariat of the Organization for the Prohibition of Chemical Weapons of Possible Cases of Application of Chemical Weapons, Moscow, 2012.

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Correspondence to N. L. Koryagina.

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Original Russian Text © N.L. Koryagina, E.I. Savel’eva, N.S. Khlebnikova, A.I. Ukolov, E.S. Ukolova, G.V. Karakashev, A.S. Radilov, 2015, published in Mass-spektrometriya, 2015, Vol. 12, No. 4, pp. 236–246.

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Koryagina, N.L., Savel’eva, E.I., Khlebnikova, N.S. et al. Chromatography–mass spectrometry determination of alkyl methylphosphonic acids in urine. J Anal Chem 71, 1309–1318 (2016). https://doi.org/10.1134/S1061934816140069

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