Analysis of small alkylamines in mainstream cigarette smoke
Small alkylamines, such as monomethylamine (MMA) and trimethylamine (TMA), are present in cigarette smoke at low levels as known combustion by-products of plant materials and are used in analytical determinations for primary aromatic amines. Analysis of these constituents may be of interest for tobacco-related product characterization. Due to characteristics such as high volatility, hydrophilicity, and low molecular weight, these constituents present a significant challenge for quantitation; methodology in the literature for these analytes in cigarette smoke as a matrix is limited. In order to develop a robust quantitative method, several platforms were explored including IC, GC-NPD, GC-MS, GC-MS/MS and LC-MS/MS. Each platform presented challenges with regard to selectivity and/or sensitivity and complexity of sample preparation needed. We found that both analytes were present at 2-20 times lower levels than ammonia for both ISO and Health Canada intense smoking regimes and that mass spectroscopy detection provided the highest advantages for sensitivity and selectivity. MMA was found to require derivatization due to its low molecular weight and sensitivity issues by MS when measured directly. Stable calibration curves and good recoveries were obtained for 3R4F and 1R6F cigarettes. We would like to present our novel approaches to analysis to achieve higher sensitivity and selectivity, and to discuss platform limitations and comparisons.