Methyl Ethyl Ketone Research Articles

Swelling Behaviors of Natural Rubber/Solvent Systems Based on the Extended Modified Double Lattice Model

AbstractSwelling experiments are conducted on nonfiller natural rubber using four solvents (toluene, cyclohexane, tetrahydrofuran (THF), and methylethylketone (MEK)) over temperatures from 10 to 70 °C. Toluene, cyclohexane, and THF, classified as effective solvents, show swelling ratios between 3 and 7, influenced by the crosslink density of the rubber. MEK, however, has a lower ratio of 1.5 to 2. Temperature has a minor impact on swelling compared to the crosslink density. The study evaluates the Extended Modified Double Lattice (EMDL) model for its mixing contribution in polymer network swelling, aiming to improve the Flory–Hüggins (FH) model. The superiority of EMDL above FH is in the boundary condition at the unvulcanized state, the former aligning its interaction energy with values from solvent activities in primary linear polymer/solvent solutions, unlike the FH model. The EMDL model also accounts for oriented interactions in polar solvents through a secondary lattice, linking specific interaction energy with solvent dipole moments. The study observes a nonlinear correlation between crosslinking density and sulfur amount, proposing a nonrandom mixing at lower sulfur concentrations. This model shows strong alignment with experimental data, suggesting that replacing the FH model's mixing contribution with the EMDL model could improve results with minimal additional complexity.

Characterization of 2-Butanone Peroxide Oligomeric Profiles and Their Associated Gas-Phase and Solution-Phase Rearrangement Products by Electrospray Ionization Mass Spectrometry for Forensic Applications.

2-Butanone peroxide (also known as methyl ethyl ketone peroxide, MEKP) has applications as a cross-linker in the chemical industry and is also encountered as a homemade primary high explosive; therefore, it is of interest to both process chemists and forensic examiners. Specifically for forensic applications, we demonstrate that when traditional synthetic procedures, available to any hobbyist, are utilized to generate MEKP, oligomeric peroxide units (n ≤ 12), along with several other oligomeric byproduct distributions, are readily observed by liquid chromatography-mass spectrometry (LC-MS). These oligomeric byproducts correspond to the formation of methyl/ethyl ketone end group(s) at the oligomer end group (i.e., loss of ethanol(s) and/or methanol(s) from the oligomer termini). Based on the interpretation of the MS and MS/MS behavior along with the characterization of newly generated terminal alkyl ketone products, we propose that these byproducts are consistent with a Hock-like rearrangement of the primary MEKP distribution in the acidified reaction medium. Following a procedure for homemade preparation, triplicate lots were synthesized. Unique oligomeric and byproduct distributions provided discriminatory power between the synthetic lots. Furthermore, the distributions of MEKP oligomers and the various byproducts in the initiated MEKP match the intensity distributions observed in the intact material with remarkable accuracy. This observation suggests that the postinitiation residue of MEKP could be associated or dissociated from a separately collected intact material obtained during an investigation by examining these oligomeric and byproduct profiles.

Remnant polarization and structural arrangement in P(VDF-TrFE) electrospun fiber meshes affect osteogenic differentiation of human mesenchymal stromal cells

Many tissues and cells are influenced by mechano-electric stimulation, thus the application of piezoelectric materials has recently received considerable attention in tissue engineering. This report investigated electrospun fiber meshes based on poly(vinylidenefluoride-co-trifluoroethylene) [P(VDF-TrFE)] as instructive biomaterials for osteogenic differentiation of human mesenchymal stromal cells (hMSCs). The influence played by methyl ethyl ketone (MEK), used as a solvent in place of dimethylformamide (DMF)/acetone mixture, and the effect of rotating velocity of the electrospinning collector on fiber morphology, mechanical and piezoelectric properties were studied. The solvent had noticeable effects on morphology and piezoelectric properties of electrospun fibers, with MEK outperforming DMF/acetone. By increasing the collector velocity up to 4000 rpm, the fiber diameter reduced and the mutual alignment of the fibers increased, corresponding to enhanced mechanical properties and piezo-active β-phase content. However, as a consequence of the diverse mechanical properties of random and aligned fibrous architectures, which ultimately affected the piezoelectric properties, randomly-oriented fibers exhibited higher remnant piezoelectric properties (Vout and d31 piezoelectric coefficient) than aligned ones. On these scaffolds, hMSCs showed an excellent capability of early osteogenic differentiation, leading to high calcium production. Fiber surface topology, fiber mesh morphology and remnant piezoelectric properties played a determinant role on hMSC osteogenic commitment.

Techno-economic viability of bio-based methyl ethyl ketone production from sugarcane using integrated fermentative and chemo-catalytic approach: Process integration using pinch technology

Butanediols are versatile platform chemicals that can be transformed into a spectrum of valuable products. This study examines the techno-commercial feasibility of an integrated biorefinery for fermentative production of 2,3-butanediol (BDO) from sucrose of sugarcane (SC), followed by chemo-catalytic upgrading of BDO to a carbon-conservative derivative, methyl ethyl ketone (MEK), with established commercial demand. The techno-economics of three process configurations are compared for downstream MEK separation from water and co-product, isobutyraldehyde (IBA): (I) heterogeneous azeotropic distillation of MEK-water and extractive separation of (II) MEK and (III) MEK-IBA from water using p-xylene as a solvent. The thermal efficiency of these manufacturing processes is further improved using pinch technology. The implementation of pinch technology reduces 8% of BDO and 9–10% of MEK production costs. Despite these improvements, raw material and utility costs remain substantial. The capital expenditure is notably higher for MEK production from SC than BDO alone due to additional processing steps. The extraction based MEK separation is the simplest process configuration despite marginally higher capital requirements and utility consumption with slightly higher production costs than MEK-water azeotropic distillation. Economic analysis suggests that bio-based BDO is cost-competitive with its petrochemical counterpart, with a minimum gross unitary selling price of US$ 1.54, assuming a 15% internal rate of return over five-year payback periods. However, renewable MEK is approximately 16–24% costlier than the petrochemical route. Future strategies must focus on reducing feedstock costs, improving BDO fermentation efficacy, and developing a low-cost downstream separation process to make renewable MEK commercially viable.

The optimisation of caffeic acid reactive extraction by trioctylphosphine oxide using response surface methodology

ABSTRACT Caffeic acid is a valuable product due to its wide-ranging utilities. Currently, caffeic acid can be produced via fermentation process using native or engineered microorganisms. The reactive extraction is a prominent technique that is used for the recovery of carboxylic acids. In this work, caffeic acid was recovered by an organophosphate (trioctylphosphine oxide) from its aqueous solution in the presence of different kinds of solvents namely 1-butanol, ethyl propionate, and ethyl methyl ketone. The values of reactive extraction parameters were optimised by Box–Behnken design. 98.19% The maximum extraction efficiency was obtained as 98.19% at the optimum conditions of 0.003 mol kg−1 caffeic acid concentration, 50% (v/v) trioctylphosphine oxide quantity, and 306.2 K in the presence of 1-butanol as the solvent. Our study is the first ever to examine the reactive extraction of caffeic acid, and therefore very important in modern scientific disciplines.

Emission factors and source profiles of volatile organic compounds from the automobile manufacturing industry

Controlling volatile organic compounds (VOCs) emitted from the automobile manufacturing industry requires establishing VOCs emission factors (EFs) and source profiles refinedly. In this study, 41 samples involved 32 VOCs discharge links were collected from three factories. The EFs and VOCs source profiles were estimated by the material balance method and weighted average method, respectively. The ozone formation potential (OFP) of the 110 VOCs species were calculated by the maximum incremental reactivity (MIR). According to estimations, the ranges of EFs were 0.23–1.66 kg VOCs/SUV car and 2.14–14.86 g VOCs/m2 painted area. EFs of six materials were firstly estimated, which are electrophoretic primer (152.31 ± 97.39 g VOCs/SUV car, 0.97 ± 0.38 g VOCs/m2 painted area), sealant (48.39 ± 26.20 g VOCs/SUV car, 0.46 ± 0.25 g VOCs/m2 painted area), floating coat (87.40 ± 75.63 g VOCs/SUV car, 0.86 ± 0.74 g VOCs/m2 painted area), colored paint (127.24 ± 168.24 g VOCs/SUV car, 1.25 ± 1.66 g VOCs/m2 painted area), varnish (205.46 ± 218.14 g VOCs/SUV car, 2.01 ± 2.15 g VOCs/m2 painted area), and cleaning solvent (328.54 ± 404.94 g VOCs/SUV car, 3.23 ± 3.98 g VOCs/m2 painted area). OVOCs (37.40–51.60 %) and aromatics (36.40–37.00 %) were the dominant components. n-Butyl acetate, 1,2,4-trimethylbenzene, undecane, n-hexanal, acetone, 1,2,3-trimethylbenzene, 1,3,5 -trimethylbenzene, m/p/o-xylene, 3-ethylbenzene, and 4-ethylbenzene were the major VOCs species, accounting for 68 % of total VOCs in the automobile manufacturing industry. Considering the OFP values of species, 1,2,4-trimethylbenzene, 1,3,5-trimethylbenzene, 1,2,3-trimethylbenzene, m/p-xylene, acetaldehyde, methyl ethyl ketone are the key active species that should be prioritized for control.

Characteristics of Volatile Organic Compounds Distribution in Downtown Ansan Near Industrial Complexes

There are four industrial complexes located around Ansan City, which is one of the areas with the highest VOCs emissions in Gyeonggi region based on the emissions provided by the clean policy support system (CAPSS), Korea. In this study, proton transfer reaction time-of-flight mass spectrometer (PTR-TOF-MS) was used to determine the distribution of volatile organic compounds (VOCs) in urban areas near industrial complexes in Ansan City in 2023 (May to June). The PTR-TOF-MS was operated over the mass range of 10-400amu at a drift tube pressure of 2.3mbar and temperature 80<sup>o</sup>C (E/N ~ 130Td) that enabled the collection of VOC data at 0.1Hz resolution. The mixing ratio calculations for methanol, acetaldehyde, acetonitrile, acetone, acetic acid, dimethyl sulfide, isoprene, methyl vinyl ketone (MVK), methyl ethyl ketone (MEK), benzene, toluene, styrene, xylene, trimethylbenzene and pinene reported in this study were done using the sensitivity factors obtained from the PTR-TOF-MS calibrations. As a result of the intensive measurement in springtime, among the substances constituting VOCs, methanol was the most abundant with 16.27±7.13 ppb, followed by acetone, acetaldehyde, acetic acid, methyl ethyl ketone (MEK), toluene, and xylene. VOCs compositions were dominated by oxidized VOCs, with CxHyO1 at 74%, CxHyO2 at 11%, aromatic CxHy at 10.5%, and CxHyN at 3.1%, respectively. As a result of the diurnal variations and conditional probability function (CPF) analysis, it was found that toluene and MEK were locally greatly influenced by industrial complexes distributed around Ansan City. Related with the ozone creating contribution, the ratio of VOCs to nitrogen oxide (NOx) was 6.5 (1.4 to 18.2), which appeared in the NOx-limited (4:1) and the VOCs-limited (15:1). Therefore it is suggested that the management of emission source NOx and VOCs are very important for the reduction of ozone in Ansan.

The synthesis and research of a novel organosilicon-modified waterborne blocked polyisocyanate crosslinker with a semi-interpenetrating network structure

The organosilicon intermediate containing hydrophilic tertiary amines was synthesized from N-Methylmonoethanolamine (MEA) and (3-glycidyloxypropyl) trimethoxy silane (GPTMS), followed by neutralization with acetic acid (Ac). Meanwhile, a polyurethane (PU) prepolymer was prepared by sequentially polymerizing hexamethylene diisocyanate trimer (HT-100) with polyethylene glycol (PEG-600) and methoxy polyethylene glycol (MPEG), and then chain extended by the intermediate. Ultimately, methyl ethyl ketone oxime (MEKO) was selected to block the remaining NCO group, forming a branched polyisocyanate crosslinker. Subsequently, a linear polyisocyanate crosslinker was prepared in the same system by polymerizing hexamethylene diisocyanate (HDI) with the intermediate. Consequently, an organosilicon-modified waterborne blocked polyisocyanate crosslinker with a semi-interpenetrating network structure was obtained and further processed through hydrolysis to obtain the corresponding crosslinker containing silanol groups. The structure and thermal properties of the crosslinkers were analyzed using 1H NMR, FT-IR, TG, and DTG. Furthermore, the comprehensive mechanical properties of the cured films were investigated. The results indicate that the crosslinker system containing silanol groups exhibits superior performance. When the films' maximum adhesion and the wiping resistance were optimized at 1.97 MPa and 72 times, respectively, the impact resistance still maintained above 85 cm.

Synthesis, solvent role in TD-DFT (IEFPCM model), fluorescence and reactivity properties, topology and molecular docking studies on sulfathiazole derivative

A new class of Schiff base, 4-(butan-2-ylideneamino)-N-(thiazol-2-yl) benzenesulfonamide (EMKTH) was synthesized from sulfathiazole by simple condensation with methyl ethyl ketone. The molecular structure was characterized by infrared, 1H and 13C NMR, and UV–visible spectroscopic studies. These results were compared with theoretical values. Density functional theory (DFT) calculations were performed to determine the structure and reactivity of the molecule. Further, HOMO-LUMO, MEP, and NBO calculations were performed on this system to examine the electronic and chemical properties of this EMKTH system. The UV spectra were analyzed at ambient temperature to determine the electronic absorption maximum using TD-DFT. In the UV study, there was more solvent interaction in the solvent phase than in the gas phase, which is where the maximum wavelength was observed. Docking simulations were performed on the target protein (1W3R) in order to evaluate the binding affinity of EMKTH. It was found that the target protein had a larger energy of −3.99 kcal/mol. The findings showed that there is a significant correlation between the experimental and theoretical values. The molecule's effective charge transfer mechanism, which accounts for its high chemical reactivity, was suggested by a small orbital gap. The synthesized molecule EMKTH exhibited both intra- and intermolecular charge transfer capabilities in line with the NBO results. Analysis of the EMKTH compound's molecular electrostatic potential (MEP) revealed its reactive sites.

Mechanism and Kinetics of Selective Aerobic Oxidation of n-Butane to Methyl Ethyl Ketone Catalyzed by Cu(HPTB)/NHPI

Mechanism and Kinetics of Selective Aerobic Oxidation of <i>n</i>-Butane to Methyl Ethyl Ketone Catalyzed by Cu(HPTB)/NHPI

Influence of updated isoprene oxidation mechanisms on the formation of intermediate and secondary products in MCM v3.3.1

In this study, we developed an observation based photochemical box model with the measurement data collected at a suburban site (i.e., the Xianghe, XH site) of the Beijing-Tianjin-Hebei (BTH) region and the latest version of the Master Chemical Mechanism (MCM v3.3.1), which newly incorporated 498 reaction for the additional 155 species with the oxidation of isoprene by the OH radical. The influence of updated isoprene degradation on the radical budgets, formation of intermediate and secondary products by comparing the simulation results in the original version (MCM v3.2) was firstly analyzed to estimate whether the updates of precursors could influence the model performance on its evolution pathways and related products. The results demonstrated that though the input of isoprene could significantly decrease or increase the concentrations of OH and HO2 radicals in the model simulation, respectively, the difference in the simulated concentrations of these radicals with isoprene oxidation before and after the updates was not statistically significant. For intermediate products, the simulated concentrations of formaldehyde and methacrolein (MACR) did not significantly alter before and after the updates, while the abundance of methyl vinyl ketone (MVK) reduced obviously (the maximum reduction of 31%) due to lower reaction coefficient between ISOPBO2 and NO and the lower branching ratios caused by the newly added pathways involving CISOPA and TISOPA in the updated scheme. On the other hand, the simulation concentrations of acrolein (ACR), glyoxal (Gly) and methylglyoxal (Mgly) increased significantly after the model updates. The dominant pathway for the increment of ACR was the decomposition of CH2CHCH2O produced by PE4E2CO, while those of Gly and Mgly were associated with radicals of C537O and PACLOOA that were both from the new intermediate radical of CISOPC. In addition, 39 isoprene oxidation products among the 155 new added species were identified to partition in the formation of secondary organic aerosol (SOA), which were coupled in the gas-particle partitioning module to optimize the formation of SOA, contributing 1.15 μg m−3 to the increase of SOA mean concentration. The updates of isoprene degradation further resulted in the significant change for its sensitivity in SOA formation, making it as the secondary important SOA precursor at the XH site. Last but not the least, the influence on photochemical ozone formation related to updates of isoprene degradation was ignorable. Overall, the above results confirmed the insufficient description of the degradation of precursors indeed limited the simulation of the intermediate and secondary products, highlighting the needs of exploring and parameterizing the precursor degradation processes for better understanding of their behaviors and SOA formation in the atmosphere.

Increasing the Dissolution Rate of Polystyrene Waste in Solvent-Based Recycling.

Solvent-based recycling of plastic waste is a promising approach for cleaning polymer chains without breaking them. However, the time required to actually dissolve the polymer in a lab environment can take hours. Different factors play a role in polymer dissolution, including temperature, turbulence, and solvent properties. This work provides insights into bottlenecks and opportunities to increase the dissolution rate of polystyrene in solvents. The paper starts with a broad solvent screening in which the dissolution times are compared. Based on the experimental results, a multiple regression model is constructed, which shows that within several solvent properties, the viscosity of the solvent is the major contributor to the dissolution time, followed by the hydrogen, polar, and dispersion bonding (solubility) parameters. These results also indicate that cyclohexene, 2-pentanone, ethylbenzene, and methyl ethyl ketone are solvents that allow fast dissolution. Next, the dissolution kinetics of polystyrene in cyclohexene in a lab-scale reactor and a baffled reactor are investigated. The effects of temperature, particle size, impeller speed, and impeller type were studied. The results show that increased turbulence in a baffled reactor can decrease the dissolution time from 40 to 7 min compared to a lab-scale reactor, indicating the importance of a proper reactor design. The application of a first-order kinetic model confirms that dissolution in a baffled reactor is at least 5-fold faster than that in a lab-scale reactor. Finally, the dissolution kinetics of a real waste sample reveal that, in optimized conditions, full dissolution occurs after 5 min.

Light oxygenated volatile organic compound concentrations in an Eastern Mediterranean urban atmosphere rivalling those in megacities

Highly resolved measurements of primary and secondary oxygenated volatile organic compounds (OVOCs) by proton-transfer-reaction mass spectrometry (PTR-MS) and the AMOVOC sampler (Airborne Measurements Of VOC) were performed in Beirut, Lebanon, during the ECOCEM (Emissions and Chemistry of Organic Carbon in the East Mediterranean) experiments. The OVOC concentrations (0.15–7.0 ppb) rival those reported for international megacities like Paris, Tokyo, or São Paulo (0.3–6.5 ppb). This study highlights the seasonal variability of OVOCs, the potential role of background pollution on OVOC concentrations, traffic emissions of OVOCs, and the secondary production of OVOCs during both summer and winter.The primary and secondary OVOC fractions were estimated using two methods based on the night-time emission ratio and photochemical age. Our calculations coupled with a correlation analysis revealed the following: firstly, background concentrations contributed significantly, especially for longer-lived OVOCs, such as methanol and acetone (30%–80%). Secondly, secondary production in summer increased up to 60%, except for methanol and isoprene oxidation products, i.e., for methacrolein and methyl vinyl ketone. Thirdly, the secondary production in the Eastern Mediterranean persisted in winter, and finally, strong primary traffic emissions dominated the primary biogenic emissions.Finally, the emission ratios were used to evaluate the global anthropogenic emission inventories downscaled to Lebanon. Although limited to two individual non-lumped species (formaldehyde and acetone), the emission ratios compared well, within a factor of 2. However, the emissions of aldehydes and ketones from the CAMS, Edgar, and MACCITY inventories showed discrepancies of up to three orders of magnitude. This demonstrates a need for improved OVOC representation in emission inventories, considering the atmospheric relevance and abundance of OVOCs and their use in volatile chemical products.

Coupled condensation—hydrogenation processing of ethyl methyl ketone to 5-methylheptan-3-one on Pd/C catalyst

Coupled condensation—hydrogenation processing of ethyl methyl ketone to 5-methylheptan-3-one on Pd/C catalyst

Practical organic electronic noses using semi-permeable polymer membranes

Electronic noses (E-noses) mimic olfactory organs and quantify volatile organic compounds (VOCs), emulating the sense of smell, with applications in real-time monitoring of VOCs in food, healthcare, and law enforcement industries. Organic field-effect transistor (OFET) based sensors can be fabricated in large arrays by economical processes, however, lack the selectivity necessary to differentiate wide varieties of VOCs. Here, we explore the use of permeable polymer membranes with OFET sensors to improve their selectivity. Acylated poly(vinyl alcohol) (PVA) derivatives were synthesized, characterized, and evaluated in OFET vapor sensors as tunable membranes. Sensors with and without acylated PVA membranes were tested with VOC analytes. By monitoring drain current over time, we found that membranes dramatically changed responses to different analytes. We show that VOCs including methanol, ethanol, hexane, toluene, tetrahydrofuran, methyl ethyl ketone, and ethyl acetate can all be detected and differentiated with much greater selectivity than sensors without membranes. In particular, methanol and ethanol, which are difficult to differentiate in vapor sensors, showed significant quantitative differences in the initial slope (0.0403 s−1 vs 0.0192 s−1 respectively; 6 σ) and decay constants (5.5 s vs 15.9 s respectively; 26 σ) of their current vs time responses, allowing methanol and ethanol to be differentiated with 100 % confidence. This approach enables the economical fabrication of large varieties of unique organic vapor sensors by simply changing the membrane layer and results in an outstanding level of selectivity for OFET vapor sensors.

The Effect of Fiber Layer Orientation on the Properties of Hybrid Kenaf/Fiberglass Polyester Matrix Composite

A hybrid composite is a combination of two or more reinforced in a matrix. Hybrid composite will give better properties as compared to individual fiber-reinforced polymer composites. This research aims to study the effect of different fiber layer orientations on the properties of hybrid kenaf/fiberglass polyester matrix composite. Two types of the composite were produced which are Sample 1, the fiber layer orientation is fiberglass, kenaf fiber, kenaf fiber and fiberglass (FG-K-K-FG), and Sample 2, the fiber layer orientation is fiberglass, kenaf fiber, fiberglass, and kenaf fiber (FG-K-FG-K). The composite is manufactured using the hand lay-up technique and hot pressed. 50 g of unsaturated polyester resin and 12 g of hardener, Methyl Ethyl Ketone Peroxide (MEKP) were mixed and applied on top of every layer of fiber before being compressed at 100°C for 10 minutes. The properties of the hybrid composite were determined by completing five types of tests which are tensile test, impact test, water absorption test, thermogravimetric analysis (TGA), and scanning electron microscope (SEM). The results showed that Sample 2 (FG-K-FG-K) has higher tensile strength compared to Sample 1 (FG-K-K-FG) with the value of 30.97 MPa and 0.23 MPa respectively. For the water absorption test, Sample 1 (FG-K-K-FG) with a value of 239.21% has the highest water absorption properties compared to Sample 2 (FG-K-FG-K) with a value of 180.22%. Samples 1 and 2 have no obvious differences in terms of their thermal stability characteristics for the TGA test. For SEM, it is observed that both samples showed an attachment of adhesive between fiber layers and matrix. The overall conclusion is Sample 2 (FG-K-FG-K) has high mechanical properties but needs improvement for low water absorption.

Customizing reformulated gasoline using biofuel-additives to replace aromatics

Understanding the thermophysical and dynamic characteristics of hydrocarbon blends is crucial for optimizing engine performance and emissions control. By investigating the properties of blends with diverse biomass-derived oxygenates (BDO) as green fuel additives, we aim to mitigate toxic aromatic compounds in both conventional and reformulated gasoline. Experimental verification of prior molecular dynamics (MD) simulation results on gasoline+alkyl levulinate blends establishes the validity of our gasoline model, establishing MD simulations as a powerful tool for investigating blend properties. Subsequent MD simulations estimate the density, viscosity, and compressibility of three gasoline formulations blended with four BDOs (butanol, dimethyl ether, methyl ethyl ketone, and methyl pentanoate). At the molecular level, these BDOs exhibit similar solvation environments in blends, except for butanol, which influences their dynamic properties. Methyl pentanoate and butanol emerge as potent candidates for green fuel integration in conventional gasoline, albeit with limited effectiveness in low-aromatic content fuel corresponding to aromatic mole fraction of 0-0.16. Introducing butyl levulinate significantly enhances valid compositions from 18% in binary blends to 70% in ternary blends, with 100% success in one of the reformulated gasoline formulations.

Elucidating contributions of volatile organic compounds to ozone formation using random forest during COVID-19 pandemic: A case study in China

Ozone has been reported to increase despite nitrogen oxides reductions during the COVID-19 pandemic, and ozone formation needs to be revisited using volatile organic compounds (VOCs), which are rarely measured during the pandemic. Here, a total of 98 VOCs species were monitored in an economy-active city in China from January 2021 to August 2022 to assess contributions to ozone formation during the pandemic. Total VOCs concentrations were 35.55 ± 21.47 ppb during the entire period, among which alkanes account for the largest fraction (13.78 ppb, 38.0%), followed by aromatics (6.16 ppb, 16.8%) and oxygenated VOCs (OVOCs, 5.69 ppb, 15.7%). Most VOCs groups (e.g., alkenes, OVOCs) and individual species (e.g., isoprene, methyl vinyl ketone) display obvious seasonal and diurnal variations, which are related to their sources and reactivities. No weekend effects of VOCs suggest limited influences from traffic emissions during pandemic. Aromatics and alkenes are the major contributors (39% and 33%) to ozone formation potential, largely driven by o/m/p-xylene (21%), ethylene (15%), toluene (9%). Secondary organic aerosol formation potential is dominated by toluene (>50%) despite its low proportion (5%). Further inclusion of VOCs and meteorology in the Random Forest model shows good ozone prediction performance (R2 = 0.77–0.86, RMSE = 11.95–19.91 μg/m3, MAE = 8.89–14.58 μg/m3). VOCs and NO2 contribute >50% of total importance with the largest difference in importance ratio of VOCs/NO2 in the summer and winter, implying ozone formation regime may vary. No seasonal variations in importance of meteorology are observed, while importance of other variables (e.g., PM2.5) is highest in the summer. This work identifies critical VOCs groups and species for ozone formation during the pandemic, and demonstrates the feasibility of machine learning algorithms in elucidation of ozone formation mechanisms.

Using Machine Learning to Overcome Interfering Oxygen Effects in a Graphene Volatile Organic Compound Sensor.

Discriminating between volatile organic compounds (VOCs) for applications including disease diagnosis and environmental monitoring, is often complicated by the presence of interfering compounds such as oxygen. Graphene sensors are effective at detecting VOCs; however, they are also known to be highly sensitive to oxygen. Therefore, the combined effects of each of these gases on graphene sensors must be understood. In this work, we use graphene variable capacitor (varactor) sensors to examine the cross-selectivity of oxygen at 3 concentrations and 3 VOCs (ethanol, methanol, and methyl ethyl ketone) at 5 concentrations each. The sensor responses exhibit distinct shapes dependent on the relative concentrations in mixtures of oxygen and VOCs. Because the entire response shape is therefore informative for distinguishing between each gas mixture, a classification algorithm that utilizes entire sequences of data is needed. Accordingly, a long short-term memory (LSTM) network is used to classify the mixtures and VOC concentrations. The model achieves 100% accurate classification of the VOC type, even in the presence of varying levels of oxygen. When the VOC type and VOC concentration are classified, we show that the sensors can provide VOC concentration resolution within approximately 200 ppm. Throughout this work, we also demonstrate that an effective gas mixture classification can be achieved, even while the sensors exhibit varied drift patterns typical of graphene sensors. This is made possible due to the data analysis and machine learning methods employed.

Methyl vinyl ketone and its analogs covalently modify PI3K and alter physiological functions by inhibiting PI3K signaling

Reactive carbonyl species (RCS), which are abundant in the environment and are produced in vivo under stress, covalently bind to nucleophilic residues such as cysteine (Cys) in proteins. Disruption of protein function by RCS exposure is predicted to play a role in the development of various diseases such as cancer and metabolic disorders, but most studies on RCS have been limited to simple cytotoxicity validation, leaving their target proteins and resulting physiological changes unknown. In this study, we focused on methyl vinyl ketone (MVK), which is one of the main RCS found in cigarette smoke and exhaust gas. We found that MVK suppressed phosphatidylinositol-3 kinase (PI3K)–Akt signaling, which regulates processes involved in cellular homeostasis, including cell proliferation, autophagy, and glucose metabolism. Interestingly, MVK inhibits the interaction between the epidermal growth factor (EGF) receptor and PI3K. Cys656 in the SH2 domain of the PI3K p85 subunit, which is the covalently binding site of MVK, is important for this interaction. Suppression of PI3K–Akt signaling by MVK reversed EGF-induced negative regulation of autophagy, and attenuated glucose uptake. Furthermore, we analyzed the effects of the 23 RCS compounds with structures similar to MVK and showed that their analogs also suppressed PI3K–Akt signaling in a manner that correlated with their similarities to MVK. Our study demonstrates the mechanism of MVK and its analogs in suppressing PI3K–Akt signaling and modulating physiological functions, providing a model for future studies analyzing environmental reactive species.