title: Characterization of cigarette tobacco by direct electrospray ionization-ion trap mass spectrometry (ESI-ITMS) analysis of the aqueous extract--a novel and simple approach.
abstract: In support of the efforts to combat smuggling, as well as illegal sale and distribution of cigarettes, an analytical approach for the characterization of tobacco has been proposed and evaluated. It involves aqueous extraction of the filler tobaccos followed by direct analysis of the extracts by electrospray ionization-ion trap mass spectrometry (ESI-ITMS) in the negative mode. Typically, the deprotonated ions, [M - H](-), of organic acids (malic, citric, caffeic, quinic acid) and polyphenols (chlorogenic acid, rutin, scopoletin) were detected. MS/MS spectra of the ion at m/z 191, which is the [M - H](-) of quinic acid, citric acid, and scopoletin, and a fragment ion of chlorogenic acid were acquired. Significant differences in the MS and MS/MS spectra were observed between counterfeit samples and the corresponding authentic brand name cigarettes. Analysis of 25 commercial cigarettes showed that straight Virginia blends were readily distinguished from the blended products containing different tobacco types (Virginia, burley, and Oriental). The former exhibited consistently higher relative abundances of m/z 353 (chlorogenic acid) to m/z 133 (malic acid) in the MS spectra (0.9-1.2 vs 0.4-0.6) and higher intensity ratios of m/z 176 (scopoletin) to m/z 173 (0.4-0.8 vs 0.1-0.3) and of m/z 127 (quinic acid) to m/z 173 (0.7-1.0 vs 0.3-0.5) in the MS/MS spectra. Evidence is presented to demonstrate that the spectral differences were related not only to the tobacco type (Virginia, burley and Oriental) but also to the tobacco part (stem, lamina) used in the manufacture of the cigarettes.
authors.affiliation: Laboratory and Scientific Services Directorate, Canada Border Services Agency, 79 Bentley Avenue, Ottawa, Ontario, Canada K1A 0L8. Rachel.Ng@ccra-adrc.gc.ca
authors.forename: Lay-Keow
authors.initials: LK
authors.lastname: Ng
authors.forename: Pierre
authors.initials: P
authors.lastname: Lafontaine
authors.forename: Micheline
authors.initials: M
authors.lastname: Vanier
mesh_terms: D002109:Caffeic Acids / Q000032:analysis; D019343:Citric Acid / Q000032:analysis; D005419:Flavonoids / Q000032:analysis; D008293:Malates / Q000032:analysis; D010636:Phenols / Q000032:analysis; D059808:Polyphenols; D011801:Quinic Acid / Q000032:analysis; D012907:Smoking; D021241:Spectrometry, Mass, Electrospray Ionization / Q000379:methods*
chemical_list: D002109:Caffeic Acids; D005419:Flavonoids; D008293:Malates; D010636:Phenols; D059808:Polyphenols; D011801:Quinic Acid; D019343:Citric Acid; C030298:malic acid; C040048:caffeic acid