Quantitation and Stability of Nicotine in Canadian Vaping Liquids.

Electronic cigarettes (e-cigarettes, vaping products) have become increasingly popular, with recent increases in use associated with closed systems delivering higher concentrations of nicotine. Most vaping products designed as an alternative to combustible cigarettes contain nicotine. A number of published studies have examined the reported concentrations of nicotine in vaping liquids (e-liquids) and found discrepancies between labelled and measured levels. Some discrepancy can also be explained by the lack of stability of nicotine in these types of products. Recently, a chemical analysis method for the quantitative determination of low and high levels of nicotine in vaping liquids was developed. This method uses dilution with acetonitrile prior to analysis with gas chromatograph mass spectrometry (GC-MS) in single ion monitoring mode (SIM). The developed method was validated using a laboratory-prepared vaping liquid as well as commercially available, nicotine-free products fortified with nicotine in the laboratory. The method detection limit (MDL) and the limit of quantitation (LOQ) for nicotine were calculated to be 0.002 mg/mL and 0.006 mg/mL, respectively. The newly developed method was applied to quantify nicotine in commercially available vaping liquids of various flavour profiles and across a wide range of nicotine concentrations, including those with nicotine salts. Furthermore, a subset of vaping liquids were analyzed to elucidate nicotine stability in various product subtypes. After a period of six months of accelerated storage to mimic one year, the overall mean percent of the original nicotine concentration remaining in the salt-based vaping products was 85% (minimum 64%, maximum 99%) while in the free-base nicotine products it was 74% (minimum 31%, maximum 106%). Nicotine stability in vaping liquids was found to be influenced by the nicotine form (pH) of formulation and its chemical composition. Non-targeted, qualitative analysis of chemical composition of vaping products showed that most constituents were identified and found to be remaining in the products following stability trials; however, three new compounds were tentatively identified in some vaping liquids at the end of the stability trials. Stability studies and the accurate quantitation of nicotine in vaping products can help inform product standards related to the safety, quality and utility of vaping products as a smoking cessation tool.

Vitamin E Acetate Determination in Vaping Liquids and Non-targeted Analysis of Vaping Emissions of Diluents of Concern, Vitamin E Acetate and Medium-Chain Triglycerides Oil.

During the summer of 2019, cases of lung injury associated with vaping emerged in North America, including among individuals who reported exclusive use of nicotine vaping liquids. Once vitamin E acetate was identified as a potential causative agent a quantitative method based on a simple sample dilution, separation by gas chromatography and analysis by triple quadrupole mass spectrometry (GC MSMS) was developed. Method detection limit (MDL) and limit of quantification (LOQ) were determined at 0.159 µg/mL and 0.505 µg/mL, respectively. The analysis was performed on a subset of 203 commercially sourced nicotine containing vaping liquids of various flavour profile and nicotine range (nicotine free-59 mg/mL) from an internal inventory. The target analyte, Vitamin E Acetate, was not detected in any samples analyzed, as expected, given the reported detection in literature and high association of the chemical with cannabis and not nicotine containing vaping products.

Open Characterization of Vaping Liquids in Canada: Chemical Profiles and Trends.

Currently, there is a lack of comprehensive data on the diversity of chemicals present in vaping liquids. To address this gap, a non-targeted analysis of 825 vaping liquids collected between 2017 and 2019 from Canadian retailers was conducted. Prior to mass spectrometry analysis, samples were diluted 1:500 v/v with methanol or acetonitrile. Chemical compound separation and analysis was carried out using gas chromatography and triple quadrupole mass spectrometry (GC-MS/MS) systems operated in the full scan mode and mass range of 35-450 m/z. Mass spectrum for each sample was obtained in electron ionization at 70 eV and processed. Non-targeted identification workflow included use of automated mass spectral deconvolution and identification system (AMDIS), where required, as well as a number of commercially available spectral libraries. In order to validate identities, an in-house database of expected compounds previously detected in vaping liquids was used along with genuine analytical standards for compounds of interest. This resulted in a dataset of over 1,500 unique detected chemicals. Approximately half of these chemical compounds were detected only once in a single product and not in multiple products analyzed. For any sample analyzed, on average, 40% of the chemical constituents appeared to have flavouring properties. The remainder were nicotine and related alkaloids, processing, degradation or indirect additives, natural extractives and compounds with unknown roles. Data published here from the project on the Open Characterization of vaping liquids is unique as it offers a detailed understanding of products' flavour chemical profiles, the presence and frequency of chemicals of potential health concern, as well as trends and changes in products' chemical complexity over a three-year period. Non-targeted chemical surveillance such as this present valuable tools to public health officials and researchers in responding to emergent issues such as vaping associated lung injury or informing chemical based strategies which may be aimed at addressing product safety or appeal.

Evidence for initiation of thermal reactions of alkenes with hydrogen-terminated silicon by surface-catalyzed thermal decomposition of the reactant.

New insights into the mechanism of thermal reactions of alkenes with hydrogen terminated silicon are presented. Scanning tunneling microscopy (STM) imaging at the early stages of the reaction of 1-decene with H/Si(111) at 150 degrees C confirm this reaction occurs via a propagating radical chain mechanism. In addition, evidence is presented for an initiation mechanism involving degradation of hydrocarbon molecules catalyzed by the silanol surface of Schlenk tubes commonly used in carrying out these reactions. Hydrogen-terminated silicon surfaces are found to be unstable in the "inert" solvent dodecane when heated at 150 degrees C in a Pyrex Schlenk tube. By contrast, the surfaces were significantly more stable at the same temperature when reactions were carried out in Teflon (polytetrafluoroethylene or PTFE). The thermal reaction of decene with H/Si(111) was found to proceed more rapidly in Pyrex than in PTFE, consistent with an impurity-based initiation mechanism.

Reaction of alkenes with hydrogen-terminated and photooxidized silicon surfaces. A comparison of thermal and photochemical processes.

Reagentless micropatterning of hydrogen-terminated Si(111) via UV irradiation through a photomask has proven to be a convenient strategy for the preparation of ordered bicomponent monolayers. The success of this technique relies upon the differential rate of reaction of an alkene with the hydrogen-terminated and photooxidized regions of the surface. Monolayer formation can be accomplished under either thermal or photochemical conditions. It was observed that, after 3 h, reaction in neat alkene solution irradiation (Rayonet, 300 nm) afforded the expected patterned surface, while thermal conditions (150 degrees C) resulted in a partial loss of pattern fidelity. Monolayer properties and formation were studied on oxidized and hydrogen-terminated silicon under thermal and photochemical initiation, by contact angle, ellipsometry, Fourier transform infrared spectroscopy, high-resolution electron energy loss spectroscopy, and X-ray photoelectron spectroscopy. Results show that alkenes add to silanol groups on the silica surface in a manner consistent with acid catalysis: once attached to the surface, the silica oxidized the hydrocarbon.