New Methodologies for Qualitative and Semi-Quantitative Determination of Carbon-Centered Free Radicals in Cigarette Smoke Using Liquid ChromatographyTandem Mass Spectrometry and Gas Chromatography-Mass Selective Detection

Open access

Abstract

Several approaches were explored to develop a high throughput procedure for relative determination of 14 different carbon-centered free radicals, both acyl and alkylaminocarbonyl type, in cigarette smoke. Two trapping procedures using 3-cyano-2,2,5,5-tetramethyl-1-pyrrolidinyloxy, or 3-cyanoproxyl radical (3-CNP) were designed for this study: a) trapping in solution and b) trapping on a solid support which was a Cambridge filter pad. Fresh whole smoke and vapor phase smoke from mainstream cigarette smoke from Kentucky Reference Cigarettes 2R4F, as partitioned via an unadulterated Cambridge filter pad, were transferred into each trapping system in separate experiments. The 3-CNP coated Cambridge filter pad approach was shown to be superior to the impinger procedure as described in this study. Gas chromatography coupled with mass selective detection (GC-MS) was employed for the first time as an alternate means of detecting several relatively highly concentrated radical adducts. Liquid chromatography tandem mass spectrometry (LC-MS/MS) with precursor ion monitoring and selected ion monitoring (SIM) was used for detecting the large array of radicals, including several not previously reported: formyl, crotonyl, acrolein, aminocarbonyl, and anilinocarbonyl radicals. Relative quantitation was achieved using as external calibration standards of 4-(1-pyrrolidino)benzaldehyde and nicotine. It was determined that the yield of carbon-centered free radicals by reference cigarette 2R4F was approximately 265 nmoles/cigarette at 35 mL puff/60 sec interval/2 sec duration smoking conditions.

If the inline PDF is not rendering correctly, you can download the PDF file here.

  • 1. Hecht S. S.: Tobacco carcinogens their biomarkers and tobacco-induced cancer; Nat. Rev. Cancer. 3 (2003) 733–744.

  • 2. Hecht S. S.: Tobacco smoke carcinogens and lung cancer; J. Natl. Cancer Inst. 91 (1999) 1194!1210.

  • 3. Pryor W. A.: Cigarette smoke radicals and the role of free radicals in chemical carcinogenicity; Environ. Health Perspect. 105 (1997) 875–882.

  • 4. Pryor W. A. B. J. Hales P. I. Premovic and D. F. Church: The radicals in cigarette tar: their nature and suggested physiological implications; Science. 220 (1983) 425–427.

  • 5. Pryor W. A. K. Stone L-Y Zang and E. Bermudez: Fractionation of aqueous cigarette tar extracts: fractions that contain the tar radical cause DNA damage; Chem. Res. Toxicol. 11 (1998) 441–448.

  • 6. Alexandrov. K. M. Rojas and C. Rolando: DNA damage by benzo[a]pyrene in human cells is increased by cigarette smoke and decreased by a filter containing rosemary extract which lowers free radicals; Cancer Res. 66 (2006) 11938–11945.

  • 7. Wooten J. B. S. Chouchane and T. E. McGrath: Tobacco Smoke Constituents Affecting Oxidative Stress; in: Cigarette Smoke and Oxidative Stress edited by B. B. Halliwell and H. E. Paulsen Chap. 2 Berlin Springer 2006 pp. 5–15.

  • 8. Pryor W. A. K. Terauchi and W. H. Davis: Electron spin resonance (ESR) study of cigarette smoke by use of spin trapping techniques; Environ. Health Perspect. 16 (1976) 161–175.

  • 9. Pryor W. A. K. Terauchi and D. F. Church: ESR spin-trapping study of the radicals produced in nitrogen oxide (NOx)/olefin reactions: a mechanism for the production of the apparently long-lived radicals in gas-phase cigarette smoke; J. Am. Chem. Soc. 106 (1984) 5073–5079.

  • 10. Pryor W. A. D. G. Prier and D. F. Church: Electron-spin resonance study of mainstream and sidestream cigarette smoke: nature of the free radicals in gas-phase smoke and in cigarette tar; Environ. Health Perspect. 47 (1983) 345–355.

  • 11. Church D. F. and W. A. Pryor: Free-radical chemistry of cigarette smoke and its toxicological implications; Environ. Health Perspect. 64 (1985) 11–126.

  • 12. Pryor W. A.: Cigarette smoke and the involvement of free radical reactions in chemical carcinogenesis; J. Cancer Suppl. 8 (1987) 19–23.

  • 13. Baker R. R.: Production Chemistry Chemistry and Technology; in: Tobacoo edited by E. L. Davis M. T. Nielson Oxford Blackwell Science 1999 pp. 398–439.

  • 14. Baum S. L. I. G. M. Anderson R. R. Baker D. M. Murphy and C. C. Rowlands: Electron spin resonance and spin trap investigation of free radicals in cigarette smoke: development of a quantification procedure; Anal. Chim. Acta. 481 (2002) 1–13.

  • 15. Blakley R. L. D. D. Henry and C. J. Smith: Lack of correlation between cigarette mainstream smoke particulate phase radicals and hydroquinone yield; Food Chem. Toxicol. 39 (2001) 401–406.

  • 16. Borgerding M. F. R. L. Blakley L. S. Winkler D. D. Henry G. L. Bowman and D. H. Smith: Methodology for the determination of free radicals in mainstream vapor phase cigarette smoke in: Proceedings of the Paper Presented at the 47th Tobacco Chemists Research conference Lexington KY USA 1995 Programme Booklet and Abstracts (abstract no. 58).

  • 17. Flicker T. M. and S. A. Green: Detection and separation of gas-phase carbon-centered radicals from cgarette smoke and Diesel Exhaust; Anal. Chem. 70 (1998) 2008–2012.

  • 18. Flicker T. M. and S. A. Green: Comparison of gas-phase free-radical populations in tobacco smoke and model systems by HPLC; Environ. Health Perspect. 109 (2001) 765–771.

  • 19. Bartalis J. W. G. Chan and J. B. Wooten: A new look at radicals in cigarette smoke; Anal. Chem. 79 (2007) 5103–5106.

  • 20. Bartalis J. Y. L. Zhao J. W. Flora J. B. Paine and J. B. Wooten: Carbon-centered radicals in cigarette smoke: acyl and alkylaminocarbonyl radicals; Anal. Chem. 81 (2009) 631–641.

  • 21. Emami I. D. Masselot S. Le Gac and C. Rolando: A new and efficient method for detecting free radicals by LC-MS/MS. Application to the optimization of a cigarette filter which remove free radicals in cigarette smoke; CORESTA Congress 2002 New Orleans USA Abstr. SSPT 39 p. 18 (accessed August 2010) http://www.coresta.org/Past_Abstracts/NewOrleans 2002-SmokeTech.pdf

  • 22. Rolando C. F. Cantais and I. Emami: Precise identification of free radicals in cigarette smoke by exact mass measurement using nano-LC nano-ESI FT-MS/MS; CORESTA Congress 2006 Paris France Abstr. SSPT 54 p. 25 (accessed August 2010) http://www.coresta.org/Past_Abstracts/Paris2006-SmokeTech-Oct06.pdf

  • 23. Le Faouder P. C. Tokarski I. Emami and C. Rolando: Identification and quantitation of free radical content in cigarette smoke using nano-LC nano-ESI FT-MS/MS; CORESTA Congress 2008 Shanghai China Abstr. SSPT 32 p. 17 (accessed August 2010) http://www.coresta.org/Past_Abstracts/Shanghai2008-SmokeTech.pdf

  • 24. Moldoveanu S. C. W. M. Coleman III and J. M. Wilkins: Determination of Carbonyl Compounds in Exhaled Cigarette Smoke; Beitr. Tabakforsch. Int. 22 (2007) 346–352.

  • 25. Pryor W. A. M. Tamura M. M. Dooley P. Premovic B. J. Hales and D. F. Church: In: Oxy Radicals and their Scavenger Systems. Volume II: Cellular and Medical Aspects; edited by R. A. Greenwald and G. Cohen New York NY Elsevier 1983.

Search
Journal information
Impact Factor


CiteScore 2018: 0.69

SCImago Journal Rank (SJR) 2018: 0.295
Source Normalized Impact per Paper (SNIP) 2018: 0.491

Cited By
Metrics
All Time Past Year Past 30 Days
Abstract Views 0 0 0
Full Text Views 226 118 4
PDF Downloads 91 62 3