Characterization of Cigarette Tobacco by Direct Electrospray Ionization−Ion Trap Mass Spectrometry (ESI-ITMS) Analysis of the Aqueous ExtractA 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.

Analysis of Quinic Acid and of myo-Inositol in Tobacco

“…Analysis of quinic acid has also been reported in different materials, such as in tea (9), but quantitative information regarding the level of this compound in tobacco is scarce (4,10). A method for the joint analysis of myo-inositol and quinic acid in tobacco is described in this present study.…”

Laser desorption/ionization mass spectrometry for direct profiling and imaging of small molecules from raw biological materials

“…Notably, citric acid gave a predominant product ion at m/z 111 while quinic acid has specific product ions at m/z 85, 93 and 127, as reported previously. 66 By tandem MS it was confirmed that the peaks at m/z 191 were from quinic acid in apple while such peak came from citric acid in strawberry. Fig.…”

“…62 Spraying a matrix solution electrically or pneumatically, immersing the sample in matrix solution, and dispensing matrix solution by a piezoelectric microdispenser were suggested for generating homogeneous sample surface with matrixes. [63][64][65] Recently, Aerni and coworkers used acoustic droplet ejection 66 The laser source in this mass spectrometer is a fiber-optic guided N 2 laser (337 nm, and maximum 280 µJ/pulse before entering the optical fiber cable). The measured laser spot size is about 100 µm in diameter on the sample plate surface.…”

Rapid classification of enzymes in cleaning products by hydrolysis, mass spectrometry and linear discriminant analysis

“…Useful sample classification methods without previous chromatographic separation have been described by using mass spectrometry (MS). For this purpose, the samples have been directly infused into the mass spectrometer using an electrospray ionization (ESI)19–23 or an atmospheric‐pressure photoionization (APPI)24 ion source. Amino acid profiles obtained by protein hydrolysis have been used as fingerprints to classify protein‐binding media used in works of art according to their biological sources,22, 25 vegetable oils in accordance to their botanical origin,26 rice cultivars,27 and tea varieties,28 as well as to authenticate high quality beer 29.…”