Advertisement

Analytical and Bioanalytical Chemistry

, Volume 404, Issue 8, pp 2259–2266 | Cite as

Development, validation, and application of a liquid chromatography–tandem mass spectrometry method for the determination of 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol in human hair

  • Li Yao
  • Jun YangEmail author
  • Ya-feng Guan
  • Bai-zhan Liu
  • Sai-jing Zheng
  • Wei-miao Wang
  • Xiao-lan Zhu
  • Zhi-dan Zhang
Original Paper

Abstract

The tobacco-specific nitrosamine metabolite 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanol (NNAL) is a valuable biomarker for human exposure to the carcinogenic nitrosamine 4-(methylnitrosamino)-1-(3-pyridyl)-1-butanone (NNK) in tobacco and tobacco smoke. In this work, an efficient and sensitive method for the analysis of NNAL in human hair was developed and validated. The hair sample was extracted by NaOH solution digestion, purified by C18 solid-phase extraction (SPE) and molecularly imprinted solid-phase extraction, further enriched by reverse-phase ultrasound-assisted dispersive liquid–liquid microextraction (USA-DLLME) into 1.0 % aqueous formic acid, and finally analyzed by liquid chromatography–electrospray ionization tandem mass spectrometry. Good linearity was obtained in the range of 0.24–10.0 pg/mg hair with a correlation coefficient of 0.9982, when 150 mg hair was analyzed. The limit of detection and lower limit of quantification were 0.08 and 0.24 pg/mg hair, respectively. Accuracies determined from hair samples spiked with three different levels of NNAL ranged between 87.3 and 107.7 %. Intra- and inter-day relative standard deviations varied from 4.1 to 8.5 % and from 6.9 to 11.3 %, respectively. Under the optimized conditions, an enrichment factor of 20 was obtained. Finally, the developed method was applied for the analysis of NNAL in smokers' hair. The proposed sample preparation procedure combining selectivity of two-step SPE and enrichment of DLLME significantly improves the purification and enrichment of the analyte and should be useful to analyze NNAL in hair samples for cancer risk evaluation and cancer prevention in relation to exposure to the tobacco-specific carcinogen NNK.

Figure

An efficient analytical method based on LC-MS/MS detection has been developed and applied for analyzing the tobacco-specific carcinogen NNK metabolite NNAL in smokers’ hair.

Keywords

4-(Methylnitrosamino)-1-(3-pyridyl)-1-butanol Molecularly imprinted polymers Solid-phase extraction Dispersive liquid–liquid microextraction Liquid chromatography tandem mass spectrometry Human hair 

Notes

Acknowledgments

The authors gratefully acknowledge the financial support from the Key Laboratory of Cigarette Smoke Research of China National Tobacco Corporation (SZBCW201100780) and the fundamental research funds for the central universities (WK2061020001).

References

  1. 1.
    Pfeifer GP, Denissenko MF, Olivier M, Tretyakova N, Hecht SS, Hainaut P (2002) Oncogene 21:7435–7451CrossRefGoogle Scholar
  2. 2.
    Hecht SS (2003) Nat Rev Cancer 3:733–744CrossRefGoogle Scholar
  3. 3.
    Shah KA, Halquist MS, Karnes HT (2009) J Chromatogr B 877:1575–1582CrossRefGoogle Scholar
  4. 4.
    Carmella SG, Han SM, Villalta PW, Hecht SS (2005) Cancer Epidemiol Biomarkers Prev 14:2669–2672CrossRefGoogle Scholar
  5. 5.
    Pan JW, Song Q, Shi HH, King M, Junga H, Zhou SL, Weng ND (2004) Rapid Commun Mass Spectrom 18:2549–2557CrossRefGoogle Scholar
  6. 6.
    Stepanov I, Hecht SS, Lindgren B, Jacob P, Wilson M, Benowitz NL (2007) Cancer Epidemiol Biomarkers Prev 16:1382–1386CrossRefGoogle Scholar
  7. 7.
    Jacob P, Havel C, Lee D-H, Yu L, Eisner MD, Benowitz NL (2008) Anal Chem 80:8115–8121CrossRefGoogle Scholar
  8. 8.
    Kempson IM, Lombi E (2011) Chem Soc Rev 40:3915–3940CrossRefGoogle Scholar
  9. 9.
    Srogi K (2006) Anal Lett 39:231–258CrossRefGoogle Scholar
  10. 10.
    Pragst F, Balikova MA (2006) Clin Chim Acta 370:17–49CrossRefGoogle Scholar
  11. 11.
    Zimmerman CL, Wu Z, Upadhyaya P, Hecht SS (2004) Carcinogenesis 25:1237–1242CrossRefGoogle Scholar
  12. 12.
    Carmella SG, Han SM, Fristad A, Yang YY, Hecht SS (2003) Cancer Epidemiol Biomarkers Prev 12:1257–1261Google Scholar
  13. 13.
    Bhat SH, Gelhaus SL, Mesaros C, Vachani A, Blair IA (2011) Rapid Commun Mass Spectrom 25:115–121CrossRefGoogle Scholar
  14. 14.
    Yang Y, Yu C, Zhou M, Pang N, Li N, Nie H, Liao J, Bai Y, Liu H (2011) J Chromatogr A 1218:6505–6510CrossRefGoogle Scholar
  15. 15.
    Lee HL, Wang C, Lin S, Hsieh DPH (2007) Talanta 73:76–80CrossRefGoogle Scholar
  16. 16.
    Byrd GD, Ogden MW (2003) J Mass Spectrom 38:98–107CrossRefGoogle Scholar
  17. 17.
    Fan JP, Zhang L, Zhang XH, Huang JZ, Tong S, Kong T, Tian ZY, Zhu JH (2012) Anal Bioanal Chem 402:1337–1346CrossRefGoogle Scholar
  18. 18.
    Ambrosini S, Shinde S, De Lorenzi E, Sellergren B (2012) Analyst 137:249–254CrossRefGoogle Scholar
  19. 19.
    Yan H, Qiao J, Wang H, Yang G, Row KH (2011) Analyst 136:2629–2634CrossRefGoogle Scholar
  20. 20.
    Yang J, Hu Y, Cai JB, Zhu XL, Su QD (2006) Anal Bioanal Chem 384:761–768CrossRefGoogle Scholar
  21. 21.
    Xia Y, McGuffey JE, Bhattacharyya S, Sellergren B, Yimaz E, Wang LQ, Bernert JT (2005) Anal Chem 77:7639–7645CrossRefGoogle Scholar
  22. 22.
    Cordero C, Zebelo SA, Gnavi G, Griglione A, Bicchi C, Maffei ME, Rubiolo P (2012) Anal Bioanal Chem 402:1941–1952CrossRefGoogle Scholar
  23. 23.
    Da Fonseca P, Bonato PS (2010) Anal Bioanal Chem 396:817–824CrossRefGoogle Scholar
  24. 24.
    Gao W, Chen G, Chen Y, Li N, Chen T, Hu Z (2011) J Chromatogr A 1218:5712–5717CrossRefGoogle Scholar
  25. 25.
    Costas-Mora I, Romero V, Pena-Pereira F, Lavilla I, Bendicho C (2011) Anal Chem 83:2388–2393CrossRefGoogle Scholar
  26. 26.
    Saleh A, Larsson E, Yamini Y, Jonsson JA (2011) J Chromatogr A 1218:1331–1339CrossRefGoogle Scholar
  27. 27.
    Simoes RA, Moraes de Oliveira AR, Bonato PS (2011) Anal Bioanal Chem 399:2435–2443CrossRefGoogle Scholar
  28. 28.
    Hashemi P, Raeisi F, Ghiasvand AR, Rahimi A (2010) Talanta 80:1926–1931CrossRefGoogle Scholar
  29. 29.
    Rezaee M, Assadi Y, Hosseinia M-RM, Aghaee E, Ahmadi F, Berijani S (2006) J Chromatogr A 1116:1–9CrossRefGoogle Scholar
  30. 30.
    Li P, Zhu X, Hong S, Tian Z, Yang J (2012) Anal Methods 4:995–1000CrossRefGoogle Scholar
  31. 31.
    Liao X, Liang B, Li Z, Li Y (2011) Analyst 136:4580–4586CrossRefGoogle Scholar
  32. 32.
    Yang CY, Ding WH (2012) Anal Bioanal Chem 402:1723–1730CrossRefGoogle Scholar
  33. 33.
    Xia Y, Zhi X, Wang X, Chen M, Cheng J (2012) Anal Bioanal Chem 402:1241–1247CrossRefGoogle Scholar
  34. 34.
    Montes R, Rodriguez I, Ramil M, Rubi E, Cela R (2009) J Chromatogr A 1216:5459–5466CrossRefGoogle Scholar
  35. 35.
    Liu B, Yan H, Qiao F, Geng Y (2011) J Chromatogr B 879:90–94CrossRefGoogle Scholar
  36. 36.
    Liu X, Li J, Zha Z, Zhang W, Lin K, Huang C, Wang X (2009) J Chromatogr A 1216:2220–2226CrossRefGoogle Scholar
  37. 37.
    Samadi S, Sereshti H, Assadi Y (2012) J Chromatogr A 1219:61–65CrossRefGoogle Scholar
  38. 38.
    Stepanov I, Feuer R, Jensen J, Hatsukami D, Hecht SS (2006) Cancer Epidemiol Biomarkers Prev 15:2378–2383CrossRefGoogle Scholar
  39. 39.
    Carmella SG, Le KA, Upadhyaya P, Hecht SS (2002) Chem Res Toxicol 15:545–550CrossRefGoogle Scholar
  40. 40.
    Wang WX, Yang TJ, Li ZG, Jong TT, Lee MR (2011) Anal Chim Acta 690:221–227CrossRefGoogle Scholar
  41. 41.
    Melwanki MB, Fuh M-R (2008) J Chromatogr A 1198:1–6CrossRefGoogle Scholar
  42. 42.
    Shah KA, Peoples MC, Halquist MS, Rutan SC, Karnes HT (2011) J Pharm Biomed Anal 54:368–378CrossRefGoogle Scholar

Copyright information

© Springer-Verlag 2012

Authors and Affiliations

  • Li Yao
    • 1
  • Jun Yang
    • 1
    Email author
  • Ya-feng Guan
    • 1
    • 2
  • Bai-zhan Liu
    • 3
  • Sai-jing Zheng
    • 3
  • Wei-miao Wang
    • 3
  • Xiao-lan Zhu
    • 1
  • Zhi-dan Zhang
    • 1
  1. 1.Department of ChemistryUniversity of Science and Technology of ChinaHefeiPeople’s Republic of China
  2. 2.Department of Micro-Instrumentation and Analytical Chemistry, Dalian Institute of Chemical PhysicsChinese Academy of SciencesDalianPeople’s Republic of China
  3. 3.Key Laboratory of Cigarette Smoke Research of China National Tobacco CorporationShanghaiPeople’s Republic of China

Personalised recommendations