Sesquiterpene lactones (SLs) are plant-derived compounds often used in traditional medicine against inflammation and cancer. This review focuses on the chemical and biological properties of SLs that ...lead to enhanced anticancer and anti-inflammatory effects. The chemical properties comprise alkylating center reactivity, lipophilicity, and molecular geometry and electronic features. SLs in clinical trials are artemisinin, thapsigargin and parthenolide and many of their synthetic derivatives. These drugs are selective toward tumor and cancer stem cells by targeting specific signaling pathways, which make them lead compounds in cancer clinical trials.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
IQOS is an emerging heated tobacco product marketed by Philip Morris International (PMI). Because the tobacco in IQOS is electrically heated and not combusted, PMI claims that it generates ...significantly lower toxicant levels than combustible cigarettes. To date, a few independent studies have addressed IQOS toxicant emissions, and none have reported reactive oxygen species (ROS), and the form of the nicotine emitted by the device.
In this study, IQOS aerosol was generated using a custom-made puffing machine. Two puffing regimens were used: Health Canada Intense and ISO. ROS, carbonyl compounds (CCs), and total nicotine and its partitioning between free-base and protonated forms were quantified in the IQOS aerosol by fluorescence, high-performance liquid chromatography, and gas chromatography, respectively. The same toxicants were also quantified in combustible cigarette aerosols for comparison. In addition, propylene glycol and vegetable glycerin were also measured in the IQOS tobacco and aerosol.
IQOS and combustible cigarettes were found to emit similar quantities of total and free-base nicotine. IQOS total ROS (6.26 ± 2.72 nmol H2O2/session) and CC emissions (472 ± 19 µg/session) were significant, but 85% and 77% lower than levels emitted by combustible cigarettes.
IQOS emits harmful constituents that are linked to cancer, pulmonary disease, and addiction in cigarette smokers. For a given nicotine intake, inhalation exposure to ROS and CCs from IQOS is likely to be significantly less than that for combustible cigarettes.
IQOS is PMI's new heated tobacco product. PMI claims that because IQOS heats and does not burn tobacco it generates low toxicant yields. We found that one IQOS stick can emit similar free-base and total nicotine yields as a combustible cigarette. A pack-a-day equivalent user of IQOS may experience significant inhalation exposure of ROS and CCs compared to background air. However, substituting IQOS for combustible cigarettes will likely result in far lower ROS and carbonyl inhalation exposure for a given daily nicotine intake.
Abstract
Introduction
Available in hundreds of device designs and thousands of flavors, electronic cigarette (ECIG) may have differing toxicant emission characteristics. This study assesses nicotine ...and carbonyl yields in the most popular brands in the U.S. market. These products included disposable, prefilled cartridge, and tank-based ECIGs.
Methods
Twenty-seven ECIG products of 10 brands were procured and their power outputs were measured. The e-liquids were characterized for pH, nicotine concentration, propylene glycol/vegetable glycerin (PG/VG) ratio, and water content. Aerosols were generated using a puffing machine and nicotine and carbonyls were, respectively, quantified using gas chromatograph and high-performance liquid chromatography. A multiregression model was used to interpret the data.
Results
Nicotine yields varied from 0.27 to 2.91 mg/15 puffs, a range corresponding to the nicotine yield of less than 1 to more than 3 combustible cigarettes. Nicotine yield was highly correlated with ECIG type and brand, liquid nicotine concentration, and PG/VG ratio, and to a lower significance with electrical power, but not with pH and water content. Carbonyls, including the carcinogen formaldehyde, were detected in all ECIG aerosols, with total carbonyl concentrations ranging from 3.72 to 48.85 µg/15 puffs. Unlike nicotine, carbonyl concentrations were mainly correlated with power.
Conclusion
In 15 puffs, some ECIG devices emit nicotine quantities that exceed those of tobacco cigarettes. Nicotine emissions vary widely across products but carbonyl emissions showed little variations. In spite of that ECIG users are exposed to toxicologically significant levels of carbonyl compounds, especially formaldehyde. Regression analysis showed the importance of design and e-liquid characteristics as determinants of nicotine and carbonyl emissions.
Implications
Periodic surveying of characteristics of ECIG products available in the marketplace is valuable for understanding population-wide changes in ECIG use patterns over time.
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BFBNIB, NMLJ, NUK, PNG, UL, UM, UPUK
Objectives Waterpipe smoking using sweetened, flavoured tobacco products has become a widespread global phenomenon. In this paper, we review chemical, physical and biological properties of waterpipe ...smoke. Data sources Peer-reviewed publications indexed in major databases between 1991 and 2014. Search keywords included a combination of: waterpipe, narghile, hookah, shisha along with names of chemical compounds and classes of compounds, in addition to terms commonly used in cellular biology and aerosol sizing. Study selection The search was limited to articles published in English which reported novel data on waterpipe tobacco smoke (WTS) toxicant content, biological activity or particle size and which met various criteria for analytical rigour including: method specificity and selectivity, precision, accuracy and recovery, linearity, range, and stability. Data extraction Multiple researchers reviewed the reports and collectively agreed on which data were pertinent for inclusion. Data synthesis Waterpipe smoke contains significant concentrations of toxicants thought to cause dependence, heart disease, lung disease and cancer in cigarette smokers, and includes 27 known or suspected carcinogens. Waterpipe smoke is a respirable aerosol that induces cellular responses associated with pulmonary and arterial diseases. Except nicotine, smoke generated using tobacco-free preparations marketed for ‘health conscious’ users contains the same or greater doses of toxicants, with the same cellular effects as conventional products. Toxicant yield data from the analytical laboratory are consistent with studies of exposure biomarkers in waterpipe users. Conclusions A sufficient evidence base exists to support public health interventions that highlight the fact that WTS presents a serious inhalation hazard.
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BFBNIB, CEKLJ, CMK, NMLJ, NUK, PNG, SAZU, UL, UM, UPUK
As with other tobacco aerosols, nicotine delivery from e-cigarettes (ECIG) depends on the total nicotine and its partitioning between free-base (Nic) and protonated (NicH+) forms. Previous studies of ...ECIG nicotine emissions have generally reported “nicotine yield” without attention to whether the methods employed resulted in quantification of the total nicotine or only one of its forms, making reported results difficult to compare across studies or to evaluate against reported blood exposure. This study reports a convenient solvent extraction method for determining total nicotine and its partitioning in ECIG liquids and aerosols by gas chromatography. Commercial ECIG liquids and aerosols were analyzed, and it was found that most of the nicotine was in the Nic form, with aerosols exhibiting higher Nic fraction than the parent liquids. Apparent pH was found to correlate with nicotine partitioning and can provide a useful indirect measure when chromatography is unavailable. Finally, labeled ECIG liquid nicotine concentration in commercial products was often inconsistent with measured nicotine.
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IJS, KILJ, NUK, PNG, UL, UM
Recently, many electronic cigarettes (ECIGs) manufacturers have begun offering e-liquids, known as “nicotine salts”. These salts that have started gaining big popularity among users can be formed by ...adding weak acid to e-liquid mixtures consisting of propylene glycol (PG), vegetable glycerin (VG), flavors, and nicotine. The latter can exist in two forms: monoprotonated (mp) and freebase (fb) based on the pH of the matrix. Over the years, the determination of the fraction of fb was found important to policymakers as the prevalence of this form in ECIGs has been associated with the harshness sensory of inhalable aerosols. Liquid–liquid extraction (LLE), 1H NMR, and Henderson–Hasselback have been developed to deduce the fraction of fb; however, these methods were found to be time-consuming and have shown some challenges mainly due to the presence of a non-aqueous matrix consisting of PG and VG. This paper presents a quick non-aqueous pH measurement-based method that allows a quick determination of the fraction fb by just measuring the pH and the dielectric constant of the e-liquid. Then, by inputting these values into an established mathematical relationship, the fraction fb can be deduced. The relationship between pH, dielectric constant, and fb relies on knowing the values of the acidity dissociation constants of nicotine, which were determined for the first time in various PG/VG mixtures using a non-aqueous potentiometric titration. To validate the proposed method, the fraction fb was determined for commercials and lab-made nicotine salts utilizing the pH and LLE methods. The variation between the two methods was (<8.0%) for commercial e-liquids and lab-made nicotine salts containing lactic acid and salicylic acid. A larger discrepancy of up to 22% was observed for lab-made nicotine salts containing benzoic acid, which can be attributed to the stronger affinity of benzoic acid to toluene in the LLE method.
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IJS, KILJ, NUK, PNG, UL, UM
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•ECIG heating filament wires were found to have a strong catalytic effect.•Carbonyl formation chemistry is catalyzed at temperatures that are well below those expected during “dry ...puffing”.•New nichrome wires were the least reactive, but when aged they exhibited the highest reactivity.•Results suggest that catalysis by ECIG filaments may partially explain the wide ranges of carbonyls.
Carbonyls, a class of compounds strongly linked to pulmonary disease in smokers, are probably the most reported non-nicotine toxicants found in electronic cigarette (ECIG) aerosols. Reported emissions vary from negligible quantities to those far exceeding combustible cigarettes. Observations of high emissions are commonly attributed to “dry puffing”, whereby the ECIG heating filament runs dry of liquid and reaches temperatures that induce thermal degradation of the ECIG vapor components at the filament’s metal surface. Using a pyrolysis flow reactor, in this study we examined the potential role of surface chemistry in the formation of carbonyl compounds in ECIGs, and whether the different commercially available filament materials could potentially impact their toxicant emissions through catalysis. This information could inform nascent efforts to regulate the design of ECIGs for public health ends.
Nitrogen or air saturated with propylene glycol vapor was drawn through a temperature and residence-time controlled tubular quartz pyrolysis flow reactor in which nichrome, Kanthal, or stainless steel ECIG heating filament wires were inserted. A control condition with no inserted wire was also included. Concentrations of carbonyl products at the reactor outlet were measured as a function of temperature, heating filament wire material, and carrier gas composition (N2 vs air). Carbonyls were sampled using DNPH cartridges and analyzed by HPLC.
ECIG heating filament wires were found to have a strong catalytic effect. Carbonyl formation initiated at temperatures lower than 250 °C in the presence of the metallic wires, compared to 460 °C without them. Carbonyl formation was found to be a function of the material of construction, and whether the wire was new or aged. New nichrome wires were the least reactive, but when aged they exhibited the highest reactivity. Carbonyls were formed via dehydration or oxidation reactions of PG.
Carbonyl formation chemistry is catalyzed by commonly used ECIG heating filament materials, at temperatures that are well below those expected during “dry puffing”. The variability in the distribution and yield of carbonyl compounds across ECIG filament materials suggests that this heretofore unaccounted variable may partially explain the wide ranges reported in the literature to date. More importantly, it suggests that ECIG construction materials may be an important variable for regulations designed to protect public health.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK, ZRSKP
In this study, we examine the oxidative potential of airborne particulate matter (PM) in Beirut, Lebanon, as influenced by dust events originating in the Sahara and Arabian deserts. Segregated fine ...(<2.5 μm) and coarse (2.5–10 μm) PM samples collected during dust events, as well as during non-dust periods, were analyzed for chemical composition, and the in vitro alveolar macrophage (AM) assay was utilized to determine the oxidative potential of both types of samples. We performed Spearman rank-order correlation analysis between individual chemical components and the oxidative potential of PM to examine the impact of the changes in PM chemical composition due to the occurrence of dust events on overall PM oxidative potential. Our findings revealed that the oxidative potential of Beirut's urban PM during non-dust periods was much higher than during dust episodes for fine PM. Our findings also indicated that tracers of tailpipe emissions (i.e., elemental (EC) and organic carbon (OC)), non-tailpipe emissions (i.e., heavy metals including Cu, Zn, As, Cd, and Pb), and secondary organic aerosols (SOA) (i.e., water-soluble organic carbon, WSOC) were significantly associated with the oxidative potential of PM during dust days and non-dust periods. However, the contribution of desert dust aerosols to Beirut's indigenous PM composition did not exacerbate its oxidative potential, as indicated by the negative correlations between the oxidative potential of PM and the concentrations of crustal elements that were enriched during the dust days. This suggests that aerosols generated during Saharan and Arabian dust events pose no additional health risk to the population due to PM-triggered reactive oxygen species formation. These results significantly contribute to our understanding of the effects of desert dust aerosols on the composition and oxidative potential of PM in several countries throughout the entire Middle East region that are impacted by dust events in the Sahara and Arabian deserts.
•Saharan and Arabian Desert dust events affect indigenous Beirut PM composition.•Coarse ambient PM contributes negligibly to oxidative potential of total PM.•Fine ambient PM was the dominant contributor to oxidative potential of total PM.•Oxidative potential of total PM was reduced during dust events.•Dust aerosol PM contributions pose no added health risk due to redox-active species.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK, ZRSKP
An analytical method for the determination of 16 polycyclic aromatic hydrocarbons (PAHs) in the mainstream of narghile smoke is presented. The smoke was generated using a digital waterpipe smoking ...machine connected to the mouthpiece of a narghile that was loaded with 10g of a popular flavored tobacco and kept alight with quick-light charcoal briquettes that are commonly used for this purpose. A standard smoking regimen consisting of 171 puffs of 530ml volume and 2.6s duration spaced 17s apart was used, and the smoke condensates were collected on glass fiber filters. PAHs were extracted with toluene assisted by sonication. For purification, the extract was passed through a silica cartridge and eluted with hexane. The eluent was preconcentrated, reconstituted in acetonitrile, and analyzed using a GC–MS–SICP method. The method showed good selectivity, repeatability, accuracy and sensitivity. The limit of detection ranged from 15 to 96ng for benzoapyrene and indeno1,2,3-cdpyrene, respectively. It was found that a single narghile smoking session delivers approximately 50 times the quantities of carcinogenic 4- and 5-membered ring PAHs as a single 1R4F cigarette smoked using the FTC protocol. The pattern of PAH concentrations suggested that formation pathways differ from those of the cigarette, possibly reflecting the differing combustion conditions of the two smoking devices.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UL, UM, UPCLJ, UPUK
To assess particle oxidative potential in the greater Beirut area, size-resolved PM10–2.5, PM2.5–0.25 and PM0.25 samples were collected at near-freeway and urban background sites. Metals and trace ...elements, including Mn, Cr, Cu, Ba, Mo and Sb, displayed increased levels and crustal enrichment factors at the roadway, indicating their vehicular origin. These elements in addition to Co, V, Ni and Zn were mostly distributed in PM2.5–0.25 and PM0.25 at both sites, with moderate-to-high water-solubility (>30%). The presence of these metals, mainly air toxics, in small size ranges constitutes an added health risk. Of particular concern are elements with strong correlations (R≥0.70) with reactive oxygen species (ROS)-activity, measured by a cellular assay. In PM10–2.5, road dust component Mn and soil-related element Co were highly correlated with ROS-activity. In PM2.5–0.25, vehicular abrasion element Cu and soil-derived component Co were highly associated with ROS-activity. In PM0.25, V and Ni, originating from fuel oil combustion, strongly correlated with ROS formation. ROS-activity displayed a particle-size dependency, with lowest activity associated with PM10–2.5. On a per air volume basis, size-resolved ROS-activity was 1.5–2.8 times greater at the roadside than background location, indicating that exposure to redox-active species may be greatest near the freeway. Size-fractionated PM intrinsic activity (i.e. PM mass-normalized) was comparable at both sites, possibly suggesting a similarity in the sources of ROS-active species. Relative to other urban settings, while the intrinsic redox activity of PM10–2.5 in Beirut is comparable to that measured at an urban site in Los Angeles (LA), its PM0.25-induced ROS-activity is ~2.3-fold greater. Moreover, the intrinsic ROS-activity of ambient PM2.5 in Beirut is comparable to that reported in Milan-Italy, but 3.1-times PM2.5 activity in the heavily-polluted Lahore-Pakistan. Lastly, findings suggest a dominant role of transition metals in generating ROS compared to organic carbon in the LA area.
•Per air volume basis, ROS-activity was greater at the freeway than at background site.•Size-resolved PM intrinsic ROS-activity was generally comparable at both sites.•In PM2.5–10, Mn and Co were highly associated with ROS-activity.•In PM2.5–0.25, Cu and Co were highly correlated with ROS production.•In PM0.25, V and Ni strongly correlated with ROS formation.
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
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