Pitfalls in the Detection of Volatiles Associated with Heated Tobacco and e-Vapor Products When Using PTR-TOF-MS.

We investigated the applicability of proton transfer reaction-time-of-flight mass spectrometry (PTR-TOF-MS) for quantitative analysis of mixtures comprising glycerin, acetol, glycidol, acetaldehyde, acetone, and propylene glycol. While PTR-TOF-MS offers real-time simultaneous determination, the method selectivity is limited when analyzing compounds with identical elemental compositions or when labile compounds present in the mixture produce fragments that generate overlapping ions with other matrix components. In this study, we observed significant fragmentation of glycerin, acetol, glycidol, and propylene glycol during protonation via hydronium ions (H3O+). Nevertheless, specific ions generated by glycerin (m/z 93.055) and propylene glycol (m/z 77.060) enabled their selective detection. To thoroughly investigate the selectivity of the method, various mixtures containing both isotope-labeled and unlabeled compounds were utilized. The experimental findings demonstrated that when samples contained high levels of glycerin, it was not feasible to perform time-resolved analysis in H3O+ mode for acetaldehyde, acetol, and glycidol. To overcome the observed selectivity limitations associated with the H3O+ reagent ions, alternative ionization modes were investigated. The ammonium ion mode proved appropriate for analyzing propylene glycol (m/z 94.086) and acetone (m/z 76.076) mixtures. Concerning the nitric oxide mode, specific m/z were identified for acetaldehyde (m/z 43.018), acetone (m/z 88.039), glycidol (m/z 73.028), and propylene glycol (m/z 75.044). It was concluded that considering the presence of multiple product ions and the potential influence of other compounds, it is crucial to conduct a thorough selectivity assessment when employing PTR-TOF-MS as the sole method for analyzing compounds in complex matrices of unknown composition.

Human chemical signature: Investigation on the influence of human presence and selected activities on concentrations of airborne constituents.

There is growing evidence that the very presence of human beings in an enclosed environment can impact air quality by affecting the concentrations of certain airborne volatile organic compounds (VOC). This influence increases considerably when humans perform different activities, such as using toiletries, or simply eating and drinking. To understand the influence of these parameters on the concentrations of selected airborne constituents, a study was performed under simulated residential conditions in an environmentally-controlled exposure room. The human subjects either simply remained for a certain time in the exposure room, or performed pre-defined activities in the room (drinking wine, doing sport, using toiletries, and preparation of a meal containing melted cheese). The impact of each activity was assessed separately using our analytical platform and exposure room under controlled environmental conditions. The results showed that prolonged human presence leads to increased levels of isoprene, TVOCs, formaldehyde and, to a lesser extent, acetaldehyde. These outcomes were further supported by results of meta-analyses of data acquired during several internal studies performed over two years. Furthermore, it was seen that the indoor concentrations of several of the selected constituents rose when the recreational and daily living activities were performed. Indeed, an increase in acetaldehyde was observed for all tested conditions, and these higher indoor levels were especially notable during wine-drinking as well as cheese meal preparation. Formaldehyde increased during the sessions involving sport, using toiletries, and cheese meal preparation. Like acetaldehyde, acrolein, crotonaldehyde and particulate matter levels rose significantly during the cheese meal preparation session. In conclusion, prolonged human residence indoors and some recreational and daily living activities caused substantial emissions of several airborne pollutants under ventilation typical for residential environments.

Development and validation of a method for quantification of two tobacco-specific nitrosamines in indoor air.

A sensitive and accurate method for the quantification of 1'-Demethyl-1'-nitrosonicotine (NNN) and 4-(methylnitrosamino)-1-(3-Pyridyl)-1-butanone (NNK) in indoor air was developed and validated. To this aim, a novel approach for the collection of two tobacco-specific nitrosamines, using silica sorbent cartridges followed by simplified sample preparation and isotope dilution liquid chromatography/electrospray ionization tandem mass spectrometry, was applied. This procedure led to a substantial improvement in terms of sensitivity and sample throughput as compared with methods using conventional trapping. For the validation, a matrix-based approach using an accuracy profile procedure was selected. The evaluated matrices were background air samples, environmental aerosols of a heat-not-burn tobacco product (Tobacco Heating System [THS] 2.2, commercialized under the brand IQOS®), a rechargeable electronic cigarette (Solaris®), and the environmental tobacco smoke (ETS) of a conventional cigarette (Marlboro Gold®). The method showed excellent recoveries, sensitivity, and precision. The limits of detection of the method for NNN and NNK were 0.0108 ng/m3 and 0.0136 ng/m3, respectively. The calibration range of the instrument spanned 0.2-60 ng/mL. The calculated lower working range limit (LWRL) of the method for NNN was 0.126 ng/m3, and the LWRL for NNK was 0.195 ng/m3. The method was applied to evaluate surrogate environmental aerosols generated using smoking machines. This model is reliable but gives a large overestimation of the possible impact of THS 2.2 and e-cigarettes on indoor air, because the retention of NNN and NNK in the body of the consumers is not taken into account. As a consequence, the values reported do not reflect a real-life setting. The contents of the two target compounds in the surrogate environmental aerosols were 0.0830 ±â€¯0.0153 ng/m3 of NNN and 0.0653 ±â€¯0.0138 ng/m3 of NNK for THS 2.2, 0.0561 ±â€¯0.0296 ng/m3 of NNN for e-cigarettes, and 0.816 ±â€¯0.109 ng/m3 of NNN and 4.13 ±â€¯1.04 ng/m3 NNK for cigarettes. These values correspond to 10% of the measured ETS concentration for NNN in environmental aerosols of THS 2.2 and 7% for those of e-cigarettes. For NNK, the value for the environmental aerosol of THS 2.2 was 2% of the ETS value.

A scattering methodology for droplet sizing of e-cigarette aerosols.

CONTEXT: Knowledge of the droplet size distribution of inhalable aerosols is important to predict aerosol deposition yield at various respiratory tract locations in human. Optical methodologies are usually preferred over the multi-stage cascade impactor for high-throughput measurements of aerosol particle/droplet size distributions. OBJECTIVE: Evaluate the Laser Aerosol Spectrometer technology based on Polystyrene Sphere Latex (PSL) calibration curve applied for the experimental determination of droplet size distributions in the diameter range typical of commercial e-cigarette aerosols (147-1361 nm). MATERIALS AND METHODS: This calibration procedure was tested for a TSI Laser Aerosol Spectrometer (LAS) operating at a wavelength of 633 nm and assessed against model di-ethyl-hexyl-sebacat (DEHS) droplets and e-cigarette aerosols. The PSL size response was measured, and intra- and between-day standard deviations calculated. RESULTS: DEHS droplet sizes were underestimated by 15-20% by the LAS when the PSL calibration curve was used; however, the intra- and between-day relative standard deviations were < 3%. This bias is attributed to the fact that the index of refraction of PSL calibrated particles is different in comparison to test aerosols. This 15-20% does not include the droplet evaporation component, which may reduce droplet size prior a measurement is performed. Aerosol concentration was measured accurately with a maximum uncertainty of 20%. Count median diameters and mass median aerodynamic diameters of selected e-cigarette aerosols ranged from 130-191 nm to 225-293 nm, respectively, similar to published values. DISCUSSION AND CONCLUSION: The LAS instrument can be used to measure e-cigarette aerosol droplet size distributions with a bias underestimating the expected value by 15-20% when using a precise PSL calibration curve. Controlled variability of DEHS size measurements can be achieved with the LAS system; however, this method can only be applied to test aerosols having a refractive index close to that of PSL particles used for calibration.

Comparison of the impact of the Tobacco Heating System 2.2 and a cigarette on indoor air quality.

The impact of the Tobacco Heating System 2.2 (THS 2.2) on indoor air quality was evaluated in an environmentally controlled room using ventilation conditions recommended for simulating "Office", "Residential" and "Hospitality" environments and was compared with smoking a lit-end cigarette (Marlboro Gold) under identical experimental conditions. The concentrations of eighteen indoor air constituents (respirable suspended particles (RSP) < 2.5 µm in diameter), ultraviolet particulate matter (UVPM), fluorescent particulate matter (FPM), solanesol, 3-ethenylpyridine, nicotine, 1,3-butadiene, acrylonitrile, benzene, isoprene, toluene, acetaldehyde, acrolein, crotonaldehyde, formaldehyde, carbon monoxide, nitrogen oxide, and combined oxides of nitrogen) were measured. In simulations evaluating THS 2.2, the concentrations of most studied analytes did not exceed the background concentrations determined when non-smoking panelists were present in the environmentally controlled room under equivalent conditions. Only acetaldehyde and nicotine concentrations were increased above background concentrations in the "Office" (3.65 and 1.10 µg/m(3)), "Residential" (5.09 and 1.81 µg/m(3)) and "Hospitality" (1.40 and 0.66 µg/m(3)) simulations, respectively. Smoking Marlboro Gold resulted in greater increases in the concentrations of acetaldehyde (58.8, 83.8 and 33.1 µg/m(3)) and nicotine (34.7, 29.1 and 34.6 µg/m(3)) as well as all other measured indoor air constituents in the "Office", "Residential" and "Hospitality" simulations, respectively.

Validation of selected analytical methods using accuracy profiles to assess the impact of a Tobacco Heating System on indoor air quality.

Studies in environmentally controlled rooms have been used over the years to assess the impact of environmental tobacco smoke on indoor air quality. As new tobacco products are developed, it is important to determine their impact on air quality when used indoors. Before such an assessment can take place it is essential that the analytical methods used to assess indoor air quality are validated and shown to be fit for their intended purpose. Consequently, for this assessment, an environmentally controlled room was built and seven analytical methods, representing eighteen analytes, were validated. The validations were carried out with smoking machines using a matrix-based approach applying the accuracy profile procedure. The performances of the methods were compared for all three matrices under investigation: background air samples, the environmental aerosol of Tobacco Heating System THS 2.2, a heat-not-burn tobacco product developed by Philip Morris International, and the environmental tobacco smoke of a cigarette. The environmental aerosol generated by the THS 2.2 device did not have any appreciable impact on the performances of the methods. The comparison between the background and THS 2.2 environmental aerosol samples generated by smoking machines showed that only five compounds were higher when THS 2.2 was used in the environmentally controlled room. Regarding environmental tobacco smoke from cigarettes, the yields of all analytes were clearly above those obtained with the other two air sample types.

Large-scale synthesis and resolution of TRISPHAT [tris(tetrachlorobenzenediolato) phosphate(V)] anion.

Both enantiomers of TRISPHAT anion can be obtained on a multigram scale through a novel resolution procedure. The Lambda enantiomer is isolated as the tri-n-butylammonium salt, [(n)()Bu(3)NH][Lambda-1], which is soluble in pure CHCl(3) and CH(2)Cl(2). The Delta enantiomer is prepared as the cinchonidinium derivative, which is only soluble in polar solvent mixtures (>7.5% DMSO in CHCl(3)).

Synthetic routes for a new family of chiral tetradentate ligands containing pyridine rings.

A series of new tetradentate ligands containing two bipyridine groups or two pyridine moieties carrying amine substituents has been synthesised either from 5'- and 6'-substituted chiral bipyridines, or from chiral pyridine derivatives. These precursors have been prepared from (-)-alpha-pinene or (-)-myrtenal, respectively. The structures of three tetradentate-, and of five chiral bipyridine ligands have been determined by X-ray diffraction.