Study of the mainstream cigarette smoke aerosols by Fourier transform ion cyclotron resonance mass spectrometry coupled to laser/desorption and electrospray ionization – Additional insights on the heteroaromatic components

Abstract

Rationale:The chemical composition of the particulate phase of cigarette smoke inhaled by the active smoker is still poorly known in spite of its importance from a health point of view. A non-targeted approach is applied to cigarette smoke particles collected on a quartz filter to obtain an as complete as possible description of this complex mixture.Methods: A home-made smoking machine including devices for volatile organic compounds (VOCs) and particle sampling was used. The validation of the cigarette smoking and cigarette smoke collection procedures was conducted by the quantification of some compounds by gas chromatography/mass spectrometry (GC/MS). The particles were investigated by Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS) directly after their collection on quartz filters by laser/desorption ionization (LDI) or after extraction with CH 2 Cl 2 by electrospray ionization (ESI). Results: The determination of the benzene, toluene, ethylbenzene and xylenes (from 2 to 35 μg/cigarette) and nicotine (0.68 ± 0.05 mg/cigarette) validated the used sampling method. The complementarity of the LDI and ESI sources for the cigarette smoke analysis was established. The ESI analyses evidenced polar compounds and components with a pyridine group and LDI ensured the detection of polycondensed heteroaromatic species. Finally, this methodology was employed to characterize particles from cigarettes with or without flavoring additives. Conclusions: Some insights into the composition of cigarette smoke inhaled by active smokers have been obtained. The~1750 observed features revealed the huge complexity of cigarette smoke particles and the diversity of the possible associated health issues. Both heteroaromatic and highly oxygenated compounds produced by combustion and pyrolysis have been highlighted.

NMR Spectroscopy Identifies Chemicals in Cigarette Smoke Condensate That Impair Skeletal Muscle Mitochondrial Function

“…First, there are an estimated 8700 chemicals reported to be present in tobacco smoke [ 18 , 99 , 100 ], and the current study has only screened 34 chemicals identified as highly concentrated. Moreover, there are several tobacco smoke chemicals that are present in the gaseous state, are highly volatile, or lack protons, and thus are not detectable by NMR [ 18 , 21 , 99 , 101 , 102 , 103 , 104 , 105 , 106 ]. Second, there are likely toxic chemicals in CSC found within the low µM or nM concentration that were not detectable because of the sensitivity of NMR.…”

Nontargeted Analysis in Tobacco Research: Challenges and Opportunities

“…FTIR-MS in combination with LDI allows less sample preparation; however, it is amenable mainly to ionizing aromatic hydrocarbons. Therefore, to expand the range of detectable analytes, particularly polar compounds that may not be efficiently ionized by LDI, ESI was incorporated into the analytical approach . Also, nuclear magnetic resonance (NMR) spectroscopy has been utilized to profile the chemical composition of cigarette smoke condensate .…”

“…Even though the number of compounds in commercially available libraries for GC- and LC-MS (MS/MS, HRMS) has greatly increased in recent times more work still needs to be done to improve the spectral databases for improved compound identification. ,, Furthermore, alternative techniques such as in silico or de novo identification can be further explored to improve the detection of unknown compounds. , In addition, the difference in ionization methods used during spectral library build-up and experimental spectra generation often results in low matching factors during compound identification. , Because of this, there is no standard threshold value for the match factor used for tentative compound identification, and wide variations are in use among different researchers. This variability makes it difficult to compare interlaboratory results. − Also, issues with distinguishing between isomers during peak identification have been reported . Similarly, compound identification for NTA using NMR spectroscopy is also challenging.…”

Exhaled metabolic markers and relevant dysregulated pathways of lung cancer: a pilot study

“…Additionally, they have been detected in exhaled breath [ 30 ], especially they were reported as lung cancer markers in exhaled breath in a series of papers [ 31–34 ]. But many aromatic VOCs were also reported as results of cigarettes exposure [ 35 ], which made it doubtful whether they can be available lung cancer markers. In our view, even cigarette smoke may be the source of these molecules, their levels still make sense.…”