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The authors would like to acknowledge financial support from Business Finland (7428/31/2022, PCMI project), the Academy of Finland; No. 343192 (SoMa), No. 327248 (ValueBiomat), and No. 327865 (Bioeconomy). The authors would also like to acknowledge the effort made by Dr. Ari Kankkunen on IR camera measurement. This study aimed to introduce a smart multifunctional textile composed of a phase change material, i.e., polyethylene glycol (PEG), with a potential for thermo-regulative biomedical application. PEG was efficiently form-stabilized with polycaprolactone, and the nanofibers mats were developed by electrospinning to overcome the PEG leakage issue during the phase change process. Gelatin and curcumin were also incorporated to enable the biomedical performance of the textiles. The results revealed that the electrospun nanofibers possessed randomly oriented morphology, sufficient water absorption capability, good mechanical properties, and excellent phase change performance. The fibers' diameter varied from 220 nm to 370 nm, with a tensile strength ranging from 10 to 30 MPa. Furthermore, the fabricated mats possessed a latent heat of 61.7 J/g and reliable energy absorption-release cyclability over 100 heating-cooling cycles. The curcumin-loaded textiles revealed an initial burst release followed by a sustained release over one week. They further presented a significant antioxidant activity of 81.23.7 ± 3.08 % after 24 h, introducing a great potential application as a biomedical dressing to diminish inflammation with a cooling effect.

RATIONALEThe ban of menthol cigarettes is one of the key strategies to promote smoking cessation in the United States. Menthol cigarettes are preferred by young beginning smokers for smoking initiation. Almost 90% of African American smokers use menthol cigarettes, a result of decades-long targeted industry marketing. Several states and municipalities already banned menthol cigarettes, most recently California, effective on December 21, 2022. In the weeks before California’s ban took effect, the tobacco industry introduced several “non-menthol” cigarette products in California, replacing previously mentholated brands. Here, we hypothesize that tobacco companies replaced menthol with synthetic cooling agents to create a cooling effect without using menthol. Similar to menthol, these agents activate the TRPM8 cold-menthol receptor in sensory neurons innervating the upper and lower airways.METHODSCalcium microfluorimetry in HEK293t cells expressing the TRPM8 cold/menthol receptors was used to determine sensory cooling activity of extracts prepared from these “non-menthol” cigarette brands, and compared to standard menthol cigarette extracts of the same brands. Specificity of receptor activity was validated using TRPM8-selective inhibitor, AMTB. Gas chromatography mass spectrometry (GCMS) was used to determine presence and amounts of any flavoring chemicals, including synthetic cooling agents, in the tobacco rods, wrapping paper, filters and crushable capsule (if present) of these “non-menthol” cigarettes.RESULTSCompared to equivalent menthol cigarette extracts, several California-marketed “non-menthol” cigarette extracts activated cold/menthol receptor TRPM8 at higher dilutions and with stronger efficacies, indicating substantial pharmacological activity to elicit robust cooling sensations. Synthetic cooling agent, WS-3, was detected in tobacco rods of several of these “non-menthol” cigarette brands. Crushable capsules added to certain “non-menthol” crush varieties contained neither WS-3 nor menthol but included several “sweet” flavorant chemicals, including vanillin, ethyl vanillin and anethole.CONCLUSIONTobacco companies have replaced menthol with the synthetic cooling agent, WS-3, in California-marketed “non-menthol” cigarettes. WS-3 creates a cooling sensation similar to menthol, but lacks menthol’s characteristic “minty” odor. The measured WS-3 content is sufficient to elicit cooling sensations in smokers, similar to menthol, that facilitate smoking initiation and act as a reinforcing cue. Regulators need to act quickly to prevent the tobacco industry from bypassing menthol bans by substituting menthol with synthetic cooling agents, and thereby thwarting smoking cessation efforts.

Pregnancy presents a unique risk to chemical researchers due to their occupational exposures to chemical, equipment, and physical hazards in chemical research laboratories across science, engineering, and technology disciplines. Understanding "risk" as a function of hazard, exposure, and vulnerability, this review aims to critically examine the state of the science for the risks and associated recommendations (or lack thereof) for pregnant researchers in chemical laboratories (labs). Commonly encountered hazards for pregnant lab workers include chemical hazards (organic solvents, heavy metals, engineered nanomaterials, and endocrine disruptors), radiation hazards (ionizing radiation producing equipment and materials and nonionizing radiation producing equipment), and other hazards related to the lab environment (excessive noise, excessive heat, psychosocial stress, strenuous physical work, and/or abnormal working hours). Lab relevant doses and routes of exposure in the chemical lab environment along with literature and governmental recommendations or resources for exposure mitigation are critically assessed. The specific windows of vulnerability based on stage of pregnancy are described for each hazard, if available. Finally, policy gaps for further scientific research are detailed to enhance future guidance to protect pregnant lab workers.

Advances in green chemistry over the past 25 years have improved sustainability in the development of new cosmetic and personal care products.

BackgroundUS sales of oral nicotine pouches (ONPs) have rapidly increased, with cool/mint-flavored ONPs the most popular. Restrictions on sales of flavored tobacco products have either been implemented or proposed by several US states and localities. Zyn, the most popular ONP brand, is marketing Zyn-”Chill” and Zyn-”Smooth” as “Flavor-Ban Approved”, probably to evade flavor bans. At present it is unclear whether these ONPs are indeed free of flavor additives that can impart pleasant sensations such as cooling.MethodsSensory cooling and irritant activities of “Flavor-Ban Approved” ONPs, Zyn-”Chill” and “Smooth”, along with “minty” varieties (Cool Mint, Peppermint, Spearmint, Menthol), were analyzed by Ca2+ microfluorimetry in HEK293 cells expressing the cold/menthol (TRPM8) or menthol/irritant receptor (TRPA1). Flavor chemical content of these ONPs was analyzed by GC/MS.ResultsZyn-”Chill” ONP extracts robustly activated TRPM8, with much higher efficacy (39-53%) than the mint-flavored ONPs. In contrast, mint-flavored ONP extracts elicited stronger TRPA1 irritant receptor responses than Zyn-”Chill” extracts. Chemical analysis demonstrated the presence of WS-3, an odorless synthetic cooling agent, in Zyn-”Chill” and several other mint-flavored Zyn-ONPsConclusionsSynthetic cooling agents such as WS-3 found in ‘Flavor-Ban Approved’ Zyn-“Chill” can provide a robust cooling sensation with reduced sensory irritancy, thereby increasing product appeal and use. The label “Flavor-Ban Approved” is misleading and may implicate health benefits. Regulators need to develop effective strategies for the control of odorless sensory additives used by the industry to bypass flavor bans.

Conventional phototrophic cultivation for microalgae production suffers from low and unstable biomass productivity due to limited and unreliable light transmission outdoors. Alternatively, the use of a renewable lignocellulose-derived carbon source, cellulosic hydrolysate, offers a cost-effective and sustainable pathway to cultivate microalgae heterotrophically with high algal growth rate and terminal density. In this study, we evaluate the feasibility of cellulosic hydrolysate-mediated heterotrophic cultivation (Cel-HC) for microalgae production by performing economic and environmental comparisons with phototrophic cultivation through techno-economic analysis and life cycle assessment. We estimate a minimum selling price (MSP) of 4722 USD/t for producing high-purity microalgae through Cel-HC considering annual biomass productivity of 300 t (dry weight), which is competitive with the conventional phototrophic raceway pond system. Revenues from the lignocellulose-derived co-products, xylose and fulvic acid fertilizer, could further reduce the MSP to 2976 USD/t, highlighting the advantages of simultaneously producing high-value products and biofuels in an integrated biorefinery scheme. Further, Cel-HC exhibits lower environmental impacts, such as cumulative energy demand and greenhouse gas emissions, than phototrophic systems, revealing its potential to reduce the carbon intensity of algae-derived commodities. Our results demonstrate the economic and environmental competitiveness of heterotrophic microalgae production based on renewable bio-feedstock of lignocellulose.

Paul T. Anastas is the Teresa and H. John Heinz III Professor in the Practice of Chemistry for the Environment. He has appointments in the School of the Environment and Yale School of Public Health. In addition, Prof. Anastas serves as the Director of the Center for Green Chemistry and Green Engineering at Yale. Anastas took public service leave from Yale to serve as the Assistant Administrator for the US Environmental Protection Agency and the Agency Science Advisor from 2009-2012. Julie B. Zimmerman holds joint appointments as a Professor in the Department of Chemical and Environmental Engineering and School of the Environment (YSE) at Yale University. She also serves at the Senior Associate Dean for Academic Affairs at YSE as well as the Deputy Director of Center for Green Chemistry & Green Engineering at Yale. Prior to joining the faculty at Yale, Zimmerman worked as an Program Manager in the Office of Research and Development at the US EPA.

Hassett W, Zimmerman J, Rollwagen-Bollens G, Bollens SM, Counihan TD. 2021. An experimental evaluation of the efficacy of imaging flow cytometry (FlowCam) for detecting invasive Dreissened and Corb...

Understanding the influence of biotic and abiotic factors on riverine phytoplankton dynamics is challenging, particularly as anthropogenic stressors such as eutrophication, invasive species, and climate change alter these relationships. We examined a 14 yr (January 2005 to December 2018) dataset of phytoplankton and water quality variables, along with zooplankton and nutrient concentrations, from the Columbia River (the largest river in the US Pacific Northwest) to identify seasonal and interannual patterns of phytoplankton assemblage structure and their environmental associations. Non-metric multidimensional scaling, cluster, and indicator species analyses revealed: (1) a diatom/flagellate cluster in spring/summer, associated with chlorophyll a, discharge, ciliates, and Sarcodina; (2) a cyanobacteria/chlorophyte cluster in late summer/early fall, associated with higher water temperatures, increased clarity, the invasive copepod Pseudodiaptomus forbesi, and veligers of the invasive Asian clam Corbicula fluminea; and (3) a mixed-taxa winter cluster of minimal abundance and biomass. Nutrients were not strongly associated with the observed structural patterns. Phytoplankton bloom duration varied interannually, between years with short springtime blooms vs. years when blooms extended across multiple months. Springtime blooms of the diatom Asterionella formosa decreased in recent years, giving way to blooms of a mixed diatom assemblage. Further, high temperature, low discharge, and more invasive zooplankton were associated with cyanobacterial blooms, suggesting that increased temperature and reduced river flows predicted due to climate change in the Pacific Northwest may lead to further impacts on the late summer/early fall Columbia River plankton community.

The invasive suspension-feeding Asian clam, Corbicula fluminea, is abundant and broadly distributed in temperate rivers and lakes, yet its feeding dynamics, including how feeding rate varies as a f...

Lysozyme is a naturally occurring enzyme with antimicrobial activity that has gained significant attention for its potential use in a range of industrial applications. Due to its low toxicity, lysozyme has been considered for use in food, packaging, medicine, medical device and cosmetics. In recent decades, researchers have been working towards extending the lifespan and bioactivity of lysozyme for use in these applications. The immobilization of lysozyme on solid supports has shown positive results as demonstrated by increased stability and extended half-life of the enzyme. In this scoping review, the materials and methods utilized for the immobilization of lysozyme and resulting bioactivities will be reviewed and discussed.

Nano-sized hematite (α-Fe2O3) is not well suited for magnetic heating via an alternating magnetic field (AMF) because it is not superparamagnetic—at its best, it is weakly ferromagnetic. However, manipulating the magnetic properties of nano-sized hematite (i.e., magnetic saturation (Ms), magnetic remanence (Mr), and coercivity (Hc)) can make them useful for nanomedicine (i.e., magnetic hyperthermia) and nanoelectronics (i.e., data storage). Herein we study the effects of size, shape, and crystallinity on hematite nanoparticles to experimentally determine the most crucial variable leading to enhancing the radio frequency (RF) heating properties. We present the synthesis, characterization, and magnetic behavior to determine the structure–property relationship between hematite nano-magnetism and RF heating. Increasing particle shape anisotropy had the largest effect on the specific adsorption rate (SAR) producing SAR values more than 6 × greater than the nanospheres (i.e., 45.6 ± 3 W/g of α-Fe2O3 nanorods vs. 6.89 W/g of α-Fe2O3 nanospheres), indicating α-Fe2O3 nanorods can be useful for magnetic hyperthermia.

The manufacture of goods from oil, coal, or gas to everyday consumer products comprises in more or less all cases at least one catalytic step. Compared to conventional hydrothermal catalysis, electrocatalysis possesses the advantage of mild operational conditions and high selectivity, yet the potential energy savings and climate change mitigation have rarely been assessed. This study conducted a life cycle assessment (LCA) for the electrocatalytic oxidation of crude glycerol to produce lactic acid, one of the most common platform chemicals. The LCA results demonstrated a 31% reduction in global warming potential (GWP) compared to the benchmark (bio- and chemocatalytic) processes. Additionally, electrocatalysis yielded a synergetic potential to mitigate climate change depending on the scenario. For example, electrocatalysis combined with a low-carbon-intensity grid can reduce GWP by 57% if the process yields lactic acid and lignocellulosic biofuel as compared to a conventional fossil-based system with functionally equivalent products. This illustrates the potential of electrocatalysis as an important contributor to climate change mitigation across multiple industries. A technoeconomic analysis (TEA) for electrocatalytic lactic acid production indicated considerable challenges in economic feasibility due to the significant upfront capital cost. This challenge could be largely addressed by enabling dual redox processing to produce separate streams of renewable chemicals and biofuels simultaneously.

While the antibacterial potency of metal and metal oxide engineered nanomaterials (MMO ENMs) has been well-established in the literature, the underlying mechanisms of antibacterial activity are regarded by many as uncertain, despite a considerable volume of publications on this subject. In order to illuminate sources of perceived uncertainty and disagreement, 318 articles pertaining to the mechanism of antimicrobial activity of Ag, Cu, CuO, TiO2 and ZnO ENMs were analyzed. The 318 studies all aimed to assess one or more of eight mechanistic questions, and both positive (i.e. affirmative) and negative conclusions were reported for each mechanistic question for each of the five core compositions. Differences in study design, including the exposure conditions and experimental methods used, were found to statistically significantly correlate with differences in reported mechanistic conclusions. Further analysis of studies which investigated two or more mechanisms revealed how assumptions about which mechanisms predominate for a given core composition may influence study design and, in turn, conclusions. Finally, 181 distinct experimental methods were identified, many of which are relatively untested and have not been evaluated in the published literature, while many frequently-used methods were found to have limitations that may obscure interpretation and mechanistic insight.

Introduction Waterpipe use remains popular among youth with the availability of flavored shisha tobacco being one of the main drivers of waterpipe use. Although waterpipe mainstream toxicant emissions are well understood, less is known about the carryover of flavorants such as vanillin, benzaldehyde, and eugenol. In this study, flavored waterpipe tobacco was analyzed for flavorants and nicotine, and subsequent carryover to mainstream smoke. Methods Flavorants vanillin, benzaldehyde, and eugenol, and nicotine were quantified in vanilla-, cherry-, and cinnamon-flavored shisha tobacco by gas chromatography/flame ionization detector and subsequently in waterpipe mainstream smoke generated by a smoking machine. The setup allowed for sampling before and after the water-filtration step. Results Flavorant and nicotine content in smoke was reduced 3- to 10-fold and 1.4- to 3.1-fold, respectively, due to water filtration. Per-puff content of filtered waterpipe mainstream smoke ranged from 13 to 46 µg/puff for nicotine and from 6 to 55 µg/puff for flavorants. Conclusions Although water filtration reduced flavor and nicotine content in waterpipe mainstream smoke, the detected flavorant concentrations were similar or higher to those previously reported in e-cigarette aerosol. Therefore, users could be drawn to waterpipes due to similar flavor appeal as popular e-cigarette products. Absolute nicotine content of waterpipe smoke was lower than in e-cigarette aerosol, but the differential use patterns of waterpipe (>100 puffs/session) and e-cigarette (mostly Implications Although waterpipe mainstream smoke is well characterized for toxicants content, little is known about carryover of molecules relevant for appeal and addiction: flavorants and nicotine. This study shows that flavorant content of waterpipe mainstream smoke is comparable or higher than e-cigarette aerosol flavorant content. Regulatory action to address tobacco use behaviors targeting the availability of flavors should also include other tobacco products such as flavored shisha tobacco.

Development of novel adsorbents often neglects the competitive adsorption between co-occurring oxo-anions, overestimating realistic pollutant removal potentials, and overlooking the need to improve selectivity of materials. This critical review focuses on adsorptive competition between commonly co-occurring oxo-anions in water and mechanistic approaches for the design and development of selective adsorbents. Six "target" oxo-anion pollutants (arsenate, arsenite, selenate, selenite, chromate, and perchlorate) were selected for study. Five "competing" co-occurring oxo-anions (phosphate, sulfate, bicarbonate, silicate, and nitrate) were selected due to their potential to compete with target oxo-anions for sorption sites resulting in decreased removal of the target oxo-anions. First, a comprehensive review of competition between target and competitor oxo-anions to sorb on commonly used, nonselective, metal (hydr)oxide materials is presented, and the strength of competition between each target and competitive oxo-anion pair is classified. This is followed by a critical discussion of the different equations and models used to quantify selectivity. Next, four mechanisms that have been successfully utilized in the development of selective adsorbents are reviewed: variation in surface complexation, Lewis acid/base hardness, steric hindrance, and electrostatic interactions. For each mechanism, the oxo-anions, both target and competitors, are ranked in terms of adsorptive attraction and technologies that exploit this mechanism are reviewed. Third, given the significant effort to evaluate these systems empirically, the potential to use computational quantum techniques, such as density functional theory (DFT), for modeling and prediction is explored. Finally, areas within the field of selective adsorption requiring further research are detailed with guidance on priorities for screening and defining selective adsorbents.

The application of molybdenum disulfide (MoS2) for water decontamination is expanded toward a novel approach for mercury removal using nanofibrous mats coated with MoS2. A bottom-up synthesis method for growing MoS2 on carbon nanofibers was employed to maximize the nanocomposite decontamination potential while minimizing the release of the nanomaterial to treated water. First, a co-polymer of polyacrylonitrile and polystyrene was electrospun as nanofibrous mats and pretreated to form pristine carbon fibers. Next, three solvothermal methods of controlled in situ MoS2 growth of different morphologies were achieved on the surface of the fibers using three different sets of precursors. Finally, these MoS2-enabled fibers were extensively characterized and evaluated for their mercuric removal efficiency. Two mercury removal mechanisms, including reduction-oxidation reactions and physicochemical adsorption, were elucidated. The two nanocomposites with the fastest (0.436 min-1 mg-1) and highest mercury removal (6258.7 mg g-1) were then further optimized through intercalation with poly(vinylpyrrolidone), which increased the MoS2 interlayer distance from 0.68 nm to more than 0.90 nm. The final, optimal fabrication technique (evaluated according to mercuric capacity, kinetics, and nanocomposite stability) demonstrated five times higher adsorption than the second-best method and obtained 70% of the theoretical mercury adsorption capacity of MoS2. Overall, results from this study indicate an alternative, advanced material to increase the efficiency of aqueous mercury removal while also providing the basis for other novel environmental applications such as selective sensing, disinfection, and photocatalysis.

A new sustainable material for storing heat and releasing it on demand has been demonstrated for long-term latent heat storage (LLHS). The material consists of a high-latent-heat sugar alcohol phase change material (PCM) dispersed within ionic cross-linked matrices of polyvinyl alcohol (PVA). This material's unique property is the inhibition of undesired crystallization of the PCM during cooling due to the strong intermolecular interactions of the polymeric matrices, which leads to vitrification instead of crystallization. The release of latent heat can be controlled due to the PCM's stability below its cold-crystallization, which is triggered by reheating, as demonstrated by differential scanning calorimetry (DSC), optical microscopy (OM) and in situ X-ray diffraction (XRD). The addition of an ionic citrate cross-linker further tunes the vitrification and cold-crystallization properties of the PCM. Homogeneity and the presence of hydrogen bonding of the cold-crystalizing PCM (CC-PCM) were studied by scanningelectron microscopy-energy dispersive X-ray spectroscopy (SEM-EDX), Fourier transform infrared spectroscopy (FTIR) and XRD. Thermal stability was confirmed by thermogravimetric analysis (TGA) and 100 consecutive DSC heating-cooling cycles. The CC-PCM demonstrated high latent heat of fusion, up to 266 J g(-1), depending on the composition. As a super-adsorbent, PVA was able to swell and hold the liquid PCM resulting in form-stability and leakage-preventive properties above the melting temperature. Taken together, these results confirm that PVA matrices are promising for the thermal and structural stabilization of sugar alcohol PCMs, overcoming unexpected heat release and phase separation, and withstanding repeated melting-cooling cycles for LLHS.

Oxidation of inorganic molecules (e.g., arsenite (As(III)) to arsenate (As(V))) by Cu(II)–chitosan in the presence of dissolved oxygen is examined to elucidate the ability and mechanism of Cu(II)–chitosan and Cu(II)–n-TiO2–chitosan participation in Fenton-like reactions. To form the Cu(II)–chitosan complex, Cu(II) binds with the amine groups of the chitosan backbone resulting in a Cu(II)-complex with cationic behavior. Arsenic is then adsorbed to the copper binding site through a combination of Lewis acid–base coordinate bonding and electrostatics. As K-edge XANES indicate that arsenite is fully oxidized to arsenate when adsorbed to a Cu(II)–chitosan complex in the dark without introduction of a photo- or chemical-oxidant. The oxidation of arsenite by this complex is strongly controlled by the presence of dissolved oxygen as suggested by linear combination fitting where the % As(V) bound decreases from 100% ± 0.0% to 60.2 ± 0.1% upon removal of dissolved oxygen via the freeze pump thaw method. Cu K-edge XANES indicate that Cu(II) acts as a catalyst rather than a reactant, as it remains present as Cu(II) after As oxidation in each system condition examined. For Cu(II)–n-TiO2–chitosan, the amount of As(III) oxidized to As(V) is strongly controlled by the loading of Cu(II), with a higher loading of Cu(II) leading to more As(III) oxidized and bound on the surface of the adsorbent as As(V). As(III) removal by both Cu(II)–chitosan and Cu(II)–nTiO2–chitosan is significantly improved due to the Fenton-like oxidation of As(III) to As(V). For Cu(II)–n-TiO2–chitosan, higher loadings of Cu(II) relative to n-TiO2 lead to greater improvement of As(III) removal performance under oxic vs. anoxic conditions.

Currently, over a billion people around the world lack access to clean drinking water, industrial wastewater treatment and reuse is limited, and conventional water treatment systems cannot adequately treat all contaminants of concern. Nanotechnology-enabled water treatment (NWT) has begun to emerge as a viable option to address many of the problems facing the water treatment status quo, either through cost reducing performance enhancements or filling unmet niches. Advancements in fundamental nanoscience allow unprecedented use of catalysis and energy from across the broad electromagnetic spectrum, as well as unique physicochemical properties, to purify drinking water, treat industrial wastewater, and access unconventional water supplies. However, before fully adopting NWT, it is imperative that the devices are both safe and sustainable, enhancing acceptance from consumers, government, non-government organizations, and industry. We suggest that we are in a unique window of time to “do nano right” by making key sustainability considerations very early in nano-water technology development. To this end, we have developed a framework based on three guiding research questions aimed at understanding the breadth of sustainability considerations for NWT at each of the four major life cycle stages – extraction, production, use, and end-of-life. In following this framework, researchers and product developers can design nano-enabled water treatment devices that perform well and are both safe and sustainable. By presenting the current state of sustainable NWT and specifying gaps in the literature, the present review aims to further develop NWT to be the best alternative to conventional water treatment across a variety of sectors.

Introduction Menthol, through its cooling and pleasant sensory effects, facilitates smoking and tobacco product initiation, resulting in the high popularity of mint/menthol-flavored E-cigarettes. More recently, E-cigarette vendors started marketing synthetic cooling agents as additives that impart a cooling effect but lack a characteristic minty odor. Knowledge about content of synthetic coolants in US-marketed E-cigarette products and associated health risks is limited. Aims and Methods E-liquid vendor sites were searched with the terms “koolada”, “kool/cool”, “ice”, or WS-3/WS-23, denoting individual cooling agents, and relevant refill E-liquids were purchased. “Ice” flavor varieties of Puffbar, the most popular disposable E-cigarette brand, were compared with non-“Ice” varieties. E-liquids were characterized, and synthetic coolants quantified using GC/MS. Margin of exposure (MOE), a risk assessment parameter, was calculated to assess the risk associated with synthetic coolant exposure from E-cigarette use. Results WS-3 was detected in 24/25 refill E-liquids analyzed. All Puffbar flavor varieties contained either WS-23 (13/14) or WS-3 (5/14), in both “Ice”- and non-“Ice” flavors. Modeling consumption of WS-3 from vaped E-liquids, resulted in MOEs below the safe margin of 100 for most daily use scenarios. MOEs for WS-23 were Conclusions Synthetic cooling agents (WS-3/WS-23) were present in US-marketed E-cigarettes, at levels that may result in consumer exposures exceeding safety thresholds set by regulatory agencies. Synthetic coolants are not only found in mint- or menthol-flavored products but also in fruit- and candy-flavored products, including popular disposable E-cigarette products such as Puffbar. Implications Synthetic cooling agents are widely used in “kool/cool”- and “ice”-flavored E-liquids and in E-liquids without these labels, both as a potential replacement for menthol or to add cooling “notes” to nonmenthol flavors. These agents may be used to bypass current and future regulatory limits on menthol content in tobacco products, and not just E-cigarettes. Because synthetic cooling agents are odorless, they may not fall under the category of “characterizing flavor”, potentially circumventing regulatory measures based on this concept. Regulators need to consider the additional health risks associated with exposure to synthetic cooling agents.

The transcription factor Nrf2a induces a cellular antioxidant response and provides protection against chemical-induced oxidative stress, as well as playing a critical role in development and disease. Zebrafish are a powerful model to study the role of Nrf2a in these processes but have been limited by reliance on transient gene knockdown techniques or mutants with only partial functional alteration. We developed several lines of zebrafish carrying different null (loss of function, LOF) or hyperactive (gain of function, GOF) mutations to facilitate our understanding of the Nrf2a pathway in protecting against oxidative stress. The mutants confirmed Nrf2a dependence for induction of the antioxidant genes gclc, gstp, prdx1, and gpx1a and identified a role for Nrf2a in the baseline expression of these genes, as well as for sod1. Specifically, the 4-fold induction of gstp by tert-butyl hydroperoxide (tBHP) in wild type fish was abolished in LOF mutants. In addition, baseline gstp expression in GOF mutants increased by 12.6-fold and in LOF mutants was 0.8-fold relative to wild type. Nrf2a LOF mutants showed increased sensitivity to the acute toxicity of cumene hydroperoxide (CHP) and tBHP throughout the first 4 days of development. Conversely, GOF mutants were less sensitive to CHP toxicity during the first 4 days of development and were protected against the toxicity of both hydroperoxides after 4 dpf. Neither gain nor loss of Nrf2a modulated the toxicity of R-(−)-carvone (CAR), despite the ability of this compound to potently induce Nrf2a-dependent antioxidant genes. Similar to other species, GOF zebrafish mutants exhibited significant growth and survival defects. In summary, these new genetic tools can be used to facilitate the identification of downstream gene targets of Nrf2a, better define the role of Nrf2a in the toxicity of environmental chemicals, and further the study of diseases involving altered Nrf2a function.

Sustainable molecular design of less hazardous chemicals promises to reduce risks to public health and the environment. Computational chemistry modeling coupled with alternative toxicology models (e.g., larval fish) present unique high-throughput opportunities to understand structural characteristics eliciting adverse outcomes. Numerous environmental contaminants with reactive properties can elicit oxidative stress, an important toxicological response associated with diverse adverse outcomes (i.e., cancer, diabetes, neurodegenerative disorders, etc.). We examined a common chemical mechanism (bimolecular nucleophilic substitution (SN2)) associated with oxidative stress using property-based computational modeling coupled with acute (mortality) and sublethal (glutathione, photomotor behavior) responses in the zebrafish (Danio rerio) and the fathead minnow (Pimephales promelas) models to identify whether relationships exist among biological responses and molecular attributes of industrial chemicals. Following standardized methods, embryonic zebrafish and larval fathead minnows were exposed separately to eight different SN2 compounds for 96 h. Acute and sublethal responses were compared to computationally derived in silico chemical descriptors. Specifically, frontier molecular orbital energies were significantly related to acute LC50 values and photomotor response (PMR) no observed effect concentrations (NOECs) in both fathead minnow and zebrafish. This reactivity index, LC50 values, and PMR NOECs were also significantly related to whole body glutathione (GSH) levels, suggesting that acute and chronic toxicity results from protein adduct formation for SN2 electrophiles. Shared refractory locomotor response patterns among study compounds and two alternative vertebrate models appear informative of electrophilic properties associated with oxidative stress for SN2 chemicals. Electrophilic parameters derived from frontier molecular orbitals were predictive of experimental in vivo acute and sublethal toxicity. These observations provide important implications for identifying and designing less hazardous industrial chemicals with reduced potential to elicit oxidative stress through bimolecular nucleophilic substitution.

BackgroundMenthol, through its cooling and pleasant sensory effects, facilitates smoking and tobacco product initiation, resulting in the high popularity of mint/menthol-flavored E-cigarettes. More recently, E-cigarette vendors started marketing synthetic cooling agents as additives that impart a cooling effect but lack a characteristic minty odor. Knowledge about content of synthetic coolants in US-marketed E-cigarette products and associated health risks is limited.MethodsE-liquid vendor sites were searched with the terms “koolada”, “kool/cool”, “ice”, or WS-3/WS-23, denoting individual cooling agents, and relevant refill E-liquids were purchased. “Ice” flavor varieties of Puffbar, the most popular disposable E-cigarette brand, were compared with non-”Ice” varieties. E-liquids were characterized, and synthetic coolants quantified using GC/MS. Margin of exposure (MOE), a risk assessment parameter, was calculated to assess the risk associated with synthetic coolant exposure from E-cigarette use.ResultsWS-3 was detected in 24/25 refill E-liquids analyzed. All Puffbar flavor varieties contained either WS-23 (13/14) or WS-3 (5/14), in both “Ice”- and non-”Ice” flavors. Modeling consumption of WS-3 from vaped E-liquids, resulted in MOEs below the safe margin of 100 for most daily use scenarios. MOEs for WS-23 were ConclusionsSynthetic cooling agents (WS-3/WS-23) were present in US-marketed E-cigarettes, at levels that may result in consumer exposures exceeding safety thresholds set by regulatory agencies. Synthetic coolants are not only found in mint-or menthol-flavored products, but also in fruit- and candy-flavored products, including popular disposable E-cigarette products such as Puffbar.ImplicationsSynthetic cooling agents are widely used in “kool/cool”- and “ice”-flavored E-liquids and in E-liquids without these labels, both as a potential replacement for menthol or to add cooling ‘notes’ to non-menthol flavors. These agents may be used to bypass current and future regulatory limits on menthol content in tobacco products, and not just E-cigarettes. Since synthetic cooling agents are odorless, they may not fall under the category of “characterizing flavor”, potentially circumventing regulatory measures based on this concept. Regulators need to consider the additional health risks associated with exposure to synthetic cooling agents.

Background‘Juul’ is the dominant US e-cigarette brand and was recently introduced to Canada, UK, France, Germany and Italy, with several flavours available across countries. US/Canadian products are sold with 5%, 3% and 1.5% (Canada only) nicotine content, whereas European Union (EU) regulation limits nicotine content to 1.7%. The differential nicotine content raises the question if flavour profiles and Juul device power output differ between countries.Methods‘Mint’, ‘Vanilla’ and ‘Mango’ e-liquids from all six countries were purchased in 2019 and analysed by GC/MS for their principal flavourant and nicotine content. In addition, device power specifications were compared for devices purchased from the respective countries.ResultsCompositions of Juul e-liquids from the USA and Canada were identical and differed from the EU-marketed liquids, in which principal flavourant concentrations were significantly lower. EU Juul ‘Mint’ e-liquids contained a synthetic coolant, N-ethyl-p-menthane-3-carboxamide (WS-3), absent in US/Canadian products. US/Canadian ‘Mango’ e-liquid contained triethyl-citrate, an emulsifier. Nicotine contents matched label information, and devices had identical power specifications.ConclusionsTested US/Canadian Juul e-liquids contained higher flavour concentrations than EU products, likely reflecting adaptation to user preferences. In EU, ‘Mint’ e-liquid, menthol is partially substituted with the synthetic coolant WS-3 that elicits a cooling effect like menthol but lacks its distinct ‘minty’ odour. The inhalational safety of WS-3 is unknown. The use of an emulsifier in US/Canadian ‘Mango’ Juul e-liquid may be necessary to keep the product homogeneous. Similar power specifications of devices between countries suggest that nicotine aerosol delivery is likely proportional to the e-liquid nicotine content.

Water stress is often evaluated by scarcity: the share of available water supply being consumed by humans. However, some consumptive uses of water are more or less flexible than others, depending on the costs or effects associated with their curtailment. Here, we estimate the share of global water consumption over the period 1980–2016 from the relatively inflexible demands of irrigating perennial crops, cooling thermal power plants, storing water in reservoirs and supplying basic water for humans and livestock. We then construct a water stress index that integrates the share of runoff being consumed (scarcity), the share of consumption in these inflexible categories (flexibility) and the historical variability of runoff weighted by storage capacity (variability), and use our index to evaluate the trends in water stress of global major river basins on six continents. We find that the 10% most stressed basins encompass ~19%, 19% and 35% of global population, thermal electricity generation and irrigated calorie production, respectively, and some of these basins also experience the largest increases in our identified stress indexes over the study period. Water consumption intensities (water used per unit of goods or service produced) vary by orders of magnitude across and within continents, with highly stressed basins in some cases characterized by high water consumption intensities. Our results thus point to targeted water mitigation opportunities (for example, relocating crops and switching cooling technologies) for highly stressed basins. Water consumption does not put a constant stress on available supplies, but is instead a function of flexibility in demands for food, water and energy. This analysis looks at 36 years of water consumption around the globe to identify basins under the most stress, and how they can lower their intensive uses.

Persistent and potentially toxic inorganic oxoanions (e.g., arsenic and selenium) are one class of contaminants of concern in drinking water for which treatment technologies must be improved. Effective removal of these oxoanions is made difficult by the varying adsorption affinity of the different oxidation states, as well as the presence of background ions with similar chemical structure and behavior that strongly compete for adsorption sites, greatly reducing removal efficiencies. Recent studies pointing to the negative health effects of inorganic oxoanion contaminants have resulted or are expected to result in new regulations lowering their allowable maximum concentration level (MCL) in drinking water. While these regulations are intended to protect human and environmental health, they must also allow for balanced economic costs. As such, the MCLs are often set at levels that are not as health protective due to high treatment costs that continue to present a significant challenge for small (500-3300 people) to very small (25-500 people) communities. In this Account, we focus on the development of novel cost-effective, sustainable, and efficient multifunctional and selective adsorbents that offer solutions to the above challenges through two platforms: nanoenabled and transition-metal cross-linked chitosan (TMCC) and crystal facet engineered nanometal oxides (NMO). These complementary platforms offer treatment solutions at different scales and flow rates (e.g., in a point-of-use device versus a small-scale community system). Multifunctional adsorbents combine processes that traditionally require multiple steps offering the potential for reducing treatment time and costs. Development of selective adsorbents can greatly increase removal efficiencies of target contaminants by either promoting their adsorption or hindering adsorption of competitive ions. The following sections describe (1) synthesis of novel nanoenabled waste sourced bioadsorbents; (2) development of multifunctional adsorbents to simultaneously photo-oxidize arsenite and adsorb arsenate; (3) development of a selective adsorbent for removal of arsenate and selenite over phosphate; (4) investigations of the conventional wisdom that increased surface area yields increased oxoanion removal using selenium sorption on nanohematite as a case study; and (5) crystal engineering of nanohematite to promote selenite adsorption. The novel technologies developed through these research efforts can serve as templates for the creation of future adsorbents tailored for use targeting other oxoanion contaminants of interest.

As the commercial use of nano metal oxides, including iron oxides, becomes more prevalent, there is a need to understand functionality as it relates to the inherent properties of the nanomaterial. Many applications of nanomaterials rely on adsorption, ranging from catalysis to aqueous remediation. In this paper, adsorption of selenium (Se), an aqueous contaminant, is used as a model sorbate to elucidate the relationships of structure, property, and (adsorptive) function of nano-hematite (nα-Fe 2O 3). As such, six nα-Fe 2O 3 particles were synthesized controlling for size, shape and surface area without capping agents. Sorbent characteristics of the six particles were then assessed for their impact on selenite (HSeO 3 −) and selenate (SeO 4 2−) adsorption capacity and mechanism. Mechanism was assessed using in-situ attenuated total reflectance-Fourier transform infrared (ATR-FTIR) spectroscopy and extended X-ray absorption fine edge spectroscopy (EXAFS). Regression analyses were then performed to determine which characteristics best describe adsorption capacity and binding mechanisms of Se on nα-Fe 2O 3. The results demonstrate that crystal surface structure, specifically presence of the {0 1 2} facet promotes adsorption of Se and the presence of {0 1 2} facets promotes SeO 4 2− sorption to a greater extent than HSeO 3 −. The data further indicates that {1 1 0} facets bind HSeO 3 − with binuclear complexes while {0 1 2} facets bind HSeO 3 − via mononuclear inner-sphere complexes. Specific nα-Fe 2O 3 facets also likely direct the ratio of inner to outer-sphere complexes in SeO 4 2− adsorption.

We herein report an efficient aerobic oxidative cleavage of meso-hydrobenzoin to benzaldehyde using a heterogeneous earth-abundant metal oxide catalyst. The reaction can be carried out at 70 °C in ethanol and uses a balloon filled with O2 as oxidant. Reagents are simple and have long shelf lives, and the whole laboratory exercise can be done in 120 min, which makes it highly implementable to standard undergraduate organic curriculum. meso-Hydrobenzoin cleaves exclusively to benzaldehyde, which gives off a nice almond smell, and generates water as the only byproduct. The exercise also compares the present methodology with two other conventional diol oxidative cleavage protocols to illustrate the use of atom economy and E-factor. This laboratory exercise is suitable for second-year undergraduates because it does not require any prerequisites while demonstrating the concepts of catalysis, ease of separation, atom economy, E-factor, earth-abundant material utilization, and biomass transformation.

Comparative life-cycle assessment (LCA) of pharmaceutical drugs would enable clinicians to choose alternatives with lower environmental impact from options offering equivalent efficacies and compar...

Metal oxide nanoparticles are emerging as important contributors in a variety of applications including water treatment, catalytic transformations, and energy generation and storage, among others. Controlling size and shape is of significant interest in the nanotechnology community as these are critical in determining nanoparticle performance, impacting properties such as reactivity, conductivity, and magnetic behavior. In addition to employing green solvents, supercritical fluid nanoparticle synthesis is a robust and facile method to meet the need to control size and shape for a variety of metal oxide nanoparticles. Supercritical water, supercritical ethanol, and supercritical carbon dioxide solvent systems offer tunable properties that allow for control of nanoparticle size and shape. This review investigates the synthesis routes, the mechanisms for size and shape control, and unique characteristics particular to each green solvent. Finally, a decision tree is developed to facilitate synthetic route design for the intended nano metal oxide composition, size, and shape that highlights the need for consideration of energy and life cycle impacts.