Application of Time-of-Flight Mass Spectrometry with Laser-Based Photoionization Methods for Time-Resolved On-Line Analysis of Mainstream Cigarette Smoke

• Published in: Analytical chemistry (Washington) Vol. 77; no. 8; pp. 2288 - 2296
• Main Authors: Mitschke, Stefan, Adam, Thomas, Streibel, Thorsten, Baker, Richard R, Zimmermann, Ralf
• Format: Journal Article
• Language: English
• Published: Washington, DC American Chemical Society 15.04.2005
• Subjects: Analytical chemistry; Chemical compounds; Chemistry; Cigarettes; Exact sciences and technology; Mass spectrometry; Spectrometric and optical methods; Time resolution; Tobacco smoke; Photoionization; Aliphatic compound; Time of flight method; Aromatic compound; Feasibility; Sampling; Memory effect; Multiphoton ionization; Mass spectrometry
• ISSN: 0003-2700; 1520-6882
• DOI: 10.1021/ac050075r

The application of soft photoionization mass spectrometry methods (PIMS) for cigarette mainstream smoke analysis is demonstrated. Resonance-enhanced multiphoton ionization (REMPI) at 260 nm and vacuum ultraviolet light single-photon ionization (SPI) at 118 nm were used in combination with time-of-flight mass spectrometry (TOFMS). An optimized smoking machine with reduced memory effects of smoke components was constructed, which in combination with the REMPI/SPI-TOFMS instrument allows PIMS smoke analysis with a time resolution of up to 10 Hz. The complementary character of both PIMS methods is demonstrated. SPI allows the detection of various aliphatic and aromatic compounds in smoke up to ∼120 m/z while REMPI is well suited for aromatic compounds. The capability of the instrument coupled to the novel sampling system for puff-by-puff resolved measurements is demonstrated. The feasibility of using the experimental system for intrapuff smoke measurements is also shown. Two main patterns of puff-by-puff behaviors are observed for different smoke constituents. The first group exhibits a constant increase in smoke constituent yield from the first to the last puff. The second group shows a high yield of the constituent in the first puff, with lower and constant or slowly increasing yields in the following puffs. A third group cannot be clearly classified and is a combination of both observed profiles.