Ethyl Sulfate Research Articles

Vapour–liquid equilibrium using quantum chemical molecular dynamics simulation and radial distribution function analysis

AbstractInstead of the classical molecular simulation widely implemented for estimating the vapour–liquid equilibrium (VLE), a quantum chemical (QC) molecular dynamics simulation was applied to the VLE estimation in three typical systems that include a deep eutectic solvent (DES) and an ionic liquid (IL). In addition, a radial distribution function (RDF) was derived from the QC simulation to examine the molecular behaviour in the liquid phase. A mean absolute error of 2.72% was obtained from the QC simulation compared to the experimental data. The RDF analysis explains the relative volatility increase of the acetic acid and water binary system with the propyl acetate solvent. This analysis indicated that the DES mixture comprising glycerol and choline chloride facilitated the separation of water and i‐propanol. The interaction between water and ethyl sulphate pair with the help of 1‐ethyl‐3‐methylimidazolium as an IL is stronger than that between ethanol and water, which explains how the IL improves ethanol and water separation in the vapour phase.

OH Radical Oxidation of Organosulfates in the Atmospheric Aqueous Phase.

Organosulfates (OS, ROSO3-), ubiquitous constituents of atmospheric particulate matter (PM), influence both the physicochemical and climatic properties of PM. Although the formation pathways of OS have been extensively researched, only a few studies have investigated the atmospheric fate of this class of compounds. Here, to better understand the reactivity and transformation of OS under cloudwater- and aerosol-relevant conditions, we investigate the hydroxyl radical (OH) oxidation bimolecular rate constants (kOS+OHII) and products of five atmospherically relevant OS as a function of pH and ionic strength: methyl sulfate (MeS), ethyl sulfate (EtS), propyl sulfate (PrS), hydroxyacetone sulfate (HaS) and phenyl sulfate (PhS). Our results show that OS are oxidized by OH with kOS+OHII between 108 - 109 M-1 s-1, which corresponds to atmospheric lifetimes of minutes in aqueous aerosol to days in cloudwater. We find that kOS+OHII increases with carbon chain length (MeS < EtS < PrS) and aromaticity (PrS < PhS), but does not depend on solution pH (2, 9). In addition, we find that whereas the OH reactivity of the aliphatic OS studied here decreases by ∼2× with increasing ionic strength (0-15 M), the reactivity of PhS decreases by ∼10×. The oxidation of EtS and PrS produced organic peroxides (ROOH) as first-generation oxidation products, which subsequently photolyzed; the oxidation of PhS resulted in hydroxylated aromatic products. These results highlight the need for inclusion of OS loss pathways in atmospheric models, and suggest caution in using ambient OS concentration measurements alone to estimate their production rates.

B-161 Liquid chromatography/mass spectrometry analysis of ethyl glucuronide and ethyl sulfate using a perfluorophenyl stationary phase

Abstract Background Ethyl glucuronide (EtG) and ethyl sulfate (EtS) are minor metabolites of ethanol that are excreted in urine. These two metabolites are often tested for to determine if an individual has recently consumed alcohol. EtG and EtS are very polar analytes, which make them difficult to chromatograph using reversed-phase chromatography. These analytes often elute early, which can lead to irreproducible results. When EtG and EtS are analyzed by LC/MS with a mobile phase that contains formic acid, the signal of these two analytes can be suppressed. This leads to increased LOQ and cutoffs. We examined the perfluorophenyl (PFP) stationary phase for its utility in analyzing EtG and EtS. This stationary phase has been shown to have greater retention of polar compounds than C18 reversed-phase columns. In addition, we compared the effect of formic acid to acetic acid on the separation. Methods Urine samples containing EtG and EtS were diluted 10:1, using 50mM acetic acid or 0.1% formic acid, into a 96-well microtiter filter plate containing a 0.2micron filter. Internal standards were added to the microtiter plate containing the urine samples. The samples were filtered through the filter plate and analyzed by LC/MS using the PFP column (50 x 2.7micron) with a 50mM acetic acid or 0.1% formic acid/acetonitrile mobile phase. The analytes were detected using negative mode ionization. The total analysis time was 4.5minutes. Results EtG and EtS showed improved retention using the PFP column. Retention times for EtG and EtS were 0.75 and 1.20 minutes respectively using the PFP column, compared to 0.4 and 0.3 minutes using the C18 column. The greater retention time improved the LOQ for both analytes.The LOQ for EtS and EtG were determined to be 125 and 250 ng/mL, respectively. Greater retention of EtG was observed by switching the modifier from formic acid to acetic acid. The retention time increased from 0.45 to 0.75 minutes. There was less signal suppression using acetic acid in place of formic acid. Improvement in peak shape was observed when the injection volume was reduced to 5microliters. The method was validated over a range of 250 to 10000 ng/mL for EtG and 125 to 5000 ng/mL for EtS. Acceptable linearity was obtained for both analytes. Accuracy was performed at three concentration levels. All three levels demonstrated acceptable accuracy with the difference between the measured and expected concentration being with in 20% of each other. Conclusions The PFP stationary can be used to test EtG and EtS. This stationary phase gave greater retention of EtS and EtG. The use of acetic acid improved the limit of detection by decreasing the ion suppression, which decreased the limit of detection. The assay was accurate and precise for both analytes, demonstrated in the validation.

B-260 Prevalence and Relative Distributions of Major Phosphatidylethanol (PEth) Homologs in a Large-Scale Clinical Study

Abstract Background Ethanol abuse remains a significant public health challenge in the United States. Detection of ethanol exposure is crucial for preventive, diagnostic, and therapeutic endeavors. Phosphatidylethanol (PEth) is a specific and direct ethanol biomarker. Compared to other metabolites, such as ethyl glucuronide and ethyl sulfate in urine (average 2-3 days), PEth in blood has a longer window of detection (average 1-2 weeks). Among the known 48 PEth homologs, PEth 16:0/18:1 (POPEth) and PEth 16:0/18:2 (PLPEth) are the most abundant species accounting for 37% to 46% and 26% to 28%, respectively. PLPEth is synthesized at a greater rate than POPEth, but POPEth has a longer half-life than PLPEth. The purpose of this study was to understand the prevalence and levels of POPEth and PLPEth in a large number of clinical specimens. Methods Briefly, lavender-top whole blood specimens were diluted with isotopically labeled internal standard (IS) in an organic buffer to precipitate proteins on an automated Hamilton platform. The mixture was centrifuged, and a supernatant portion isolated for injection onto a Sciex QTRAP 5500 liquid chromatography tandem mass spectrometry (LC-MS/MS) system using electrospray ionization (ESI) in negative mode. The assay was fully validated under CLIA regulations for lab developed tests: the analytical measurement range (AMR) was 10-400 ng/mL; the administrative reporting threshold for PEth positivity was 20 ng/mL based on clinical literature and a consensus among other United States laboratory methods. Results Precision of 4 QC levels was evaluated with between-run CV% (n=25) ranging from 1.6-6.3%, and accuracy across the AMR was achieved with 87-110%. No significant matrix effects were observed; variation in different whole blood specimens was corrected with IS normalization. No significant interferences were observed from 137 commonly seen prescription and nonprescription drugs and 6 other PEth homologs. Of the clinical specimens, most (20,833, 71.3%) were negative (&amp;lt;20 ng/mL) for both analytes. Meanwhile, 8,222 specimens (28.3%) were positive with either POPEth, or PLPEth or both ≥ 20ng/mL. There were 150 specimens excluded from the statistics due to interference challenges. Interestingly, 757 specimens (2.6%) were PLPEth negative and POPEth positive (mean value 40.1 ng/mL). Conversely, 62 specimens (0.2%) were POPEth negative and PLPEth positive (mean value 24.6 ng/mL). Among the specimens with both POPEth and PLPEth levels within the AMR, the average POPEth/PLPEth ratio was 1.4 supporting the overall prevalence of higher POPEth concentrations than PLPEth. However, the POPEth/PLPEth ratio varied widely, from 0.3 to 8.8, reflecting patient differences in PEth metabolism patterns. Conclusions To help verify probable ethanol abstinence, we have developed, validated, and deployed a high-throughput clinical assay for the major PEth homologs, POPEth and PLPEth. In a retrospective analysis of 29,205 clinical specimens: 71.3% of results were consistent with abstinence; 28.3% of the results were positive suggesting moderate alcohol consumption within the last 1-2 weeks. With POPEth most prevalent, yet variation observed, there were 62 specimens with PLPEth positive and negative for POPEth. This clinical PEth study including both POPEth and PLPEth provides greater sensitivity to identify ethanol exposure than only testing a single homolog.

Simultaneous determination of four ethanol biomarkers in blood: avalidated method for use in forensic toxicology in 257 postmortem samples

Purpose: Ethyl alcohol is the most widely and legally available intoxicating substance. However, excessive consumption is associated with numerous negative social consequences, including the potential for significant health risks. Rapid and simple diagnosis of alcohol use is necessary to initiate appropriate and effective treatment and is critical in forensic toxicological analysis. Ethanol biomarkers have clinical utility in the detection, diagnosis, and treatment of alcohol use disorders. Materials and Methods: An analytical method for the simultaneous determination of four different alcohol biomarkers ethyl glucuronide (EtG), ethyl sulphate (EtS), N-acetyltaurine (NAcT), and 16:0/18:1-phosphatidyl ethanol (PEth) in blood samples from forensic cases was developed, validated and verified for the accurate monitoring of alcohol abuse and dependence. Analyses were performed using a liquid chromatography-mass spectrometry system. Results: 257 blood and vitreous samples were collected from 255 male and 2 female subjects aged 16-80 years (average 44±14.82) from the Forensic Medicine Council of Turkey and analyzed for ethanol biomarkers and calculated ethanol concentrations. A total of 257 blood samples were found to contain ethanol, with concentrations ranging from 12.0 to 444.0 mg/dL. Vitreous concentrations ranged from 23 mg/dL to 597 mg/dL. The limit of detection (LOD) for EtG, EtS, NAcT, and PEth were 3.1, 3.9, 7.3, and 5.7 ng/mL respectively in blood samples. The limit of quantification (LOQ) for EtG, EtS, NAcT, and PEth were 7.8, 8.4, 18.3, and 13.1 ng/mL, respectively in blood samples. Conclusion: The method has potential in forensic toxicology as an invaluable tool for the accurate and simultaneous identification of biomarkers of alcohol use and dependence in different biological samples.

Formation of Uranyl Peroxide Compounds via Dissolution of Studtite, [(UO2)(O2)(H2O)2](H2O)2, in Ionic Liquids.

Four uranyl peroxide compounds with novel structures were formed following the dissolution of studtite, [(UO2)(O2)(H2O)2](H2O)2, in imidazolium-based ionic liquids. The compounds were characterized using single crystal X-ray diffraction (SCXRD), powder X-ray diffraction (PXRD), Raman and infrared (IR) spectroscopy, and scanning electron microscopy (SEM) with energy-dispersive X-ray spectroscopy (EDS). The ionic liquids used in the experiments were 1-ethyl-3-methylimidazolium (EMIm) diethyl phosphate, EMIm ethyl sulfate, and EMIm acetate. Each of the four uranyl peroxide compounds contain components from the ionic liquids as terminal ligands on uranyl peroxide molecular units, bridging ligands in uranyl peroxide sheet structures, or charge balancing cations located in the interstitial space. The studtite dissolved in and reacted with the ionic liquids, producing unique crystal structures depending on the anionic component of the ionic liquid, the temperature at which the synthesis was performed, and the introduction of additional ionic species into the solution. This is the first report of studtite dissolving in and reacting with ionic liquids to form uranyl peroxide compounds, which has the potential to vastly increase the number of synthetic routes for the formation of uranyl peroxide clusters and uranyl peroxide cage clusters.

Assessing the impact of stricter drink driving policy on alcohol consumption in a population of Hanoi, Vietnam using wastewater analysis.

On 1 January 2020, Vietnam introduced a new law with harsher fines and penalties for driving under the influence of alcohol. Reports of empty beer restaurants following this implementation suggested the new law has the potential to reduce population-level alcohol consumption. This pilot study aims to quantify short-term changes in alcohol consumption levels after the implementation of the new law and assess whether it could lead to a reduction in total alcohol consumption in the population. Wastewater samples were collected from two sites along a sewage canal in Hanoi during two periods: Period 1 (15 December 2018 to 14 January 2019) and Period 2 (15 December 2019 to 14 January 2020). Ethyl sulfate, a specific metabolite of alcohol, was quantified to monitor the trend of alcohol consumption. Both interrupted time series and controlled interrupted time series approaches were utilised, with Period 1 and Period 2 serving as the control and intervention periods, respectively. Our analysis indicated that the implementation of the new law did not result in an immediate and significant reduction in alcohol consumption at the population level. Meanwhile, there was no significant difference in alcohol consumption between weekdays and weekends both before and after the implementation of the new law. Long-term monitoring is needed to assess the impact of stricter DUI policy on alcohol consumption in the urban areas of Vietnam.

Subcellular effects of imidazolium-based ionic liquids with varying anions on the marine bivalve Mytilus galloprovincialis

Green Chemistry involves applying a set of principles aimed at minimizing the use of hazardous substances in the design, production, and application of chemical products. In recent decades, Ionic Liquids (ILs) have emerged as more environmentally friendly substitutes for traditional organic solvents. This preference is primarily due to their low vapor pressure, which results in minimal atmospheric pollution and enhanced industrial safety. However, existing literature highlights the toxicity of ILs towards aquatic invertebrates. Consequently, this study points to assess the biochemical effects of a selection of ILs through an in vitro approach. Specifically, digestive gland and gill cellular fractions (S9) of the marine bivalve Mytilus galloprovincialis were exposed to varying concentrations (0.05–2 μM) of three ILs featuring identical cations but different anions. The ILs tested were 1-ethyl-3-methylimidazolium octanoate ([EMIM][Oct]), 1-ethyl-3-methylimidazolium acetate ([EMIM][OAc]), and 1-ethyl-3-methylimidazolium ethyl sulfate ([EMIM][EtSO4]). The results indicate that [EMIM][Oct] induces higher toxicity in both S9 tissues, highlighting a strong effect of the anion. Overall, antioxidant and biotransformation defenses were significantly altered for all three ILs assessed. While acetylcholinesterase activity was significantly inhibited of about half of control activity, indicating neurotoxic damage as part of the toxicity mode of action of these ILs, neither lipid peroxidation nor alterations to DNA integrity were observed (≥100 %). This study supports the use of in vitro techniques as important tools capable of generating reliable ecotoxicological data, which can be further considered as a screening before in vivo testing and used for in silico modeling.

The international prevalence of prenatal alcohol use obtained via meconium biomarkers: A systematic literature review.

Fetal alcohol exposure is a growing public health concern. However, ascertaining its true extent remains challenging as maternal self-reports may lack validity. Increasingly, interest has turned to more objective measures of prenatal alcohol use (PAU) of which one, meconium, is recognized as a valuable tool. This review assesses both the international prevalence of PAU obtained using meconium biomarkers in general maternity populations and, when feasible, the level of agreement between meconium biomarkers and self-reported PAU. A systematic literature search for studies reporting the prevalence of PAU, as determined by meconium biomarker testing, was conducted using multiple electronic databases from 1990 to 2023. Seventeen studies were identified for inclusion and evaluated for methodological quality. Using fatty acid ethyl esters (FAEEs) meconium biomarkers, PAU prevalence varied from 2.4% to 44%. Rates based on EtG (ethyl glucuronide) analysis ranged from 0% to 16.3%, and EtS (ethyl sulfate) analysis from 7.8% to 16.7%. Studies were of moderate quality with high heterogeneity. Prevalence rates based on self-report data ranged from 0% to 46.4%. When reported, none of the reviewed studies identified agreement between meconium-based and self-report-based PAU prevalence rates. Using both self-reports to detect early pregnancy alcohol use, and meconium biomarkers to detect the occurrence of alcohol use later in pregnancy, may provide a more complete picture of PAU prevalence. Furthermore, research is warranted to develop stringent guidance on the ascertainment, storage, analysis, and reporting required in this field.

Estimating alcohol and tobacco consumption of university students and urban population in Ho Chi Minh City by wastewater analysis.

The quantitative measurement of urinary biomarkers in wastewater has emerged as a robust tool for estimating alcohol and tobacco consumption in populations. In this study, we applied the wastewater-based epidemiology (WBE) approach to compare alcohol and tobacco use between university students and urban inhabitants in Ho Chi Minh City, Vietnam. Ethyl sulfate and cotinine serve as markers for alcohol and tobacco use, respectively. Our findings reveal that urban inhabitants aged 15 and above consume 1.56 ± 0.23 mL of pure ethanol and 2.8 ± 0.33 mg of nicotine per day, while university students consume 0.69 ± 0.13 mL of pure alcohol and 1.2 ± 0.2mg of nicotine per day. This indicates that, on average, students consume less alcohol and tobacco compared with urban adults. A Monte Carlo simulation indicated that, on average, university students in our study smoke 1.5 cigarettes per day, while urban residents aged 15 and above smoke 4.3 cigarettes per day. Considering the smoking prevalence, a student smoker in this study consumes 6.5 cigarettes per day, a level high enough to establish addiction. On the other hand, alcohol use estimation is significantly lower than previous survey-based reports, likely due to degradation within on-site septic tanks. Future research should aim to extend the sampling period to capture seasonal variations and improve the understanding of tobacco and alcohol consumption patterns. The results from this study are crucial for decision-makers in Ho Chi Minh City to develop effective public health strategies and interventions. PRACTITIONER POINTS: Wastewater-based approach is applicable to estimate the tobacco consumption in Ho Chi Minh City. Each current smoker in the urban area of Ho Chi Minh City smokes nearly a package a day. The estimated consumption for student smokers in U-town is 6.5 cigarettes per day, a level high enough to establish addiction. The existence of septic tanks within Vietnam's drainage systems prevents reliable estimation of alcohol consumption for the entire population.

Confirmation of ethanol administration in racing greyhounds by LC-MS-MS.

Ethanol is a prohibited substance in professional animal racing as its administration causes physiological effects such as depression of the central nervous system. Regulation of potential doping agents, including those that inhibit performance, is critical to ensure integrity and animal welfare in greyhound racing, but the detection of ethanol is complicated by dietary and/or environmental exposure. In response, a reliable analytical method capable of detecting recent ethanol administration in greyhound urine samples was validated and implemented. Liquid chromatography-tandem mass spectrometry (LC-MS-MS) was used to investigate the variation in urinary ethanol metabolites; ethyl-β-D glucuronide (EG; = 1.0μg/ml, = 3.3μg/ml) and ethyl sulfate (ES; = 0.9μg/ml, = 1.9μg/ml) levels from a reference population of 202 racing greyhounds. These were compared to urine samples collected following administration of ethanol to one male and one female greyhound. Results were used to establish a threshold within the national rules of greyhound racing: and > 20 μg/ml in urine are defensible criteria to confirm ethanol administration to greyhounds. Case studies of competition samples are provided to demonstrate the forensic translation of this work.

Two-step synthesis of tungsten disulfide and its evaluation as electrocatalyst for hydrogen evolution reaction (HER)

The development of affordable alternative energies has gained great interest in recent years. Among them, hydrogen evolution reaction (HER) from water splitting has become of great interest as a source of clean energy. This work aims to develop WS2 synthesized from WO3 prepared by a hydrothermal method assisted by ionic liquid (IL) 1-ethyl-3-methylimidazolium ethyl sulfate [EMIM][EtSO4]), and followed by a heat treatment under nitrogen (N2) atmosphere. Different proportions of IL were used to assess the effect in the WS2 morphology to improve the performance towards the HER in an acidic medium. The resulting compounds were characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM) with energy dispersive spectroscopy, and electrochemical techniques such as cyclic voltammetry (CV), linear sweep voltammetry (LSV), electrochemical impedance spectroscopy (EIS) and chronoamperometric measurements. WS2 synthesized from WO3 employing IL depicted superior electrocatalytic performance for the HER compared to WS2 prepared without IL. The WS2 sample that involved 2 mL of IL (WS2-2) presented the smaller particle size and the largest crystallite size, two key parameters to perform adequate redox processes: in addition, this sample showed the lowest overpotential value (120 mV), a Tafel slope of 85 mV/dec, and the lowest charge transfer resistance value. These results showed that using the appropriate proportion of ionic liquid as an additive helps to generate smaller WS2 particles, thus generating higher current density, and reducing the overpotential value enhancing the electrocatalytic performance to carry out the HER.

Mesoporous silica supported ionic liquid materials with high efficacy for CO2 adsorption studies

CO2 capture from industrial processes and power plants, contribute to curbing global warming and advancing sustainability efforts. This study involves the design and synthesis of novel mesoporous silica supported ionic liquid based adsorbents for carbon dioxide capture. Utilization of MSILs delves into the efficiency and mechanisms of CO2 adsorption, offering insights for sustainable carbon capture technologies in combating greenhouse gas emissions. 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-ethyl-3-methylimidazolium ethyl sulfate and 1-ethyl-3-methylimidazolium methylsulfate ionic liquids were anchored on the surface of mesoporous silica which then led to highly efficient adsorbent material. Simple, efficient and cost saving methodology was performed to synthesize such highly efficient CO2 adsorbent materials. In addition, we theoretically predicted the favorable interaction mechanism of chosen molecular entities for CO2 adsorption using density functional theory (DFT) analysis. Theoretical results depict the strong interaction of molecular entities with CO2 gas molecules which is clearly evident from the experimental findings.

Quality assurance and quality control of atmospheric organosulfates measured using hydrophilic interaction liquid chromatography (HILIC)

Abstract. ​​​​​​​As a crucial constituent of fine particulate matter (PM2.5), secondary organic aerosols (SOAs) influence public health, regional air quality, and global climate patterns. This paper highlights the use of hydrophilic interaction liquid chromatography (HILIC) which effectively retains strongly polar analytes that might exhibit incomplete or no retention in reverse chromatography, resulting in superior separation efficiency. A HILIC column was used to analyze six standards, environmental standards (1648a and 1649b), and samples collected in urban environments in Guangzhou in the Pearl River Delta region, which serve as valuable reference points for evaluating the organic composition of the atmospheric environment. The results indicate a high degree of accuracy in the analytical method. Sodium octyl-d17 sulfate serves as the internal standard, with a linear correlation coefficient of the six standards, boasting a linear correlation coefficient r ranging from 0.993–0.9991 and a slope, k, of the linear equation from 0.966–1.882. The instrument detection limits (IDLs) are established at 0.03–0.20 µg mL−1, while the method detection limits (MDLs) fall within the range of 0.30–1.75 ng m−3, demonstrating the method's exceptional sensitivity. Since isoprene-derived organosulfates (iOSs) are highly polar due to containing a hydrophilic bond to the hydroxyl group and a hydrophobic bond to the sulfate, and as such showed strong retention using this method, this technique employs sodium ethyl sulfate and sodium octyl sulfate standards for semi-quantitative compound analysis of iOSs. The error in sample analysis (EA) ranged from 12.25 %–95.26 %, and the two standards maintained a consistent recovery rate between 116 %–131 % and 86.4 %–127 %. These findings indicate a high level of precision when semi-quantifying compounds with similar structural characteristics, affirming the analysis method's minimal relative error and underscoring its repeatability, process stability, and the reliability of its results for iOSs. To enhance the method's reliability assessment, the study analyzed polar organic components of standard particulate matter samples (1648a and 1649b), providing precise determinations of several iOSs using this method. Methyltetrol sulfate (m/z 215, C5H11SO7-) is the highest concentration in the ambient samples, up to 67.3 ng m−3 in the daytime. These results serve as valuable reference points for assessing the organic composition of the atmospheric environment.

Retrospective Data Analysis Reveals Unusual Metabolism Pattern of Ethanol in Pediatrics as Compared to Adult and Geriatric Populations.

About 95% of consumed ethanol is metabolized by oxidative pathways. Less than 1% is metabolized via nonoxidative pathways: glucuronidation, sulfation, and the formation of fatty acid esters of ethanol. In neonates, the glucuronidation pathway has been reported to be underdeveloped but matures with age. This work compared the test results of patients' random urine samples submitted to our facility for ethyl glucuronide (EtG) and ethyl sulfate (EtS) measurements across pediatric and adult populations. Test results (n = 63 498) from urine samples tested for EtG and EtS by quantitative liquid chromatography-tandem mass spectrometry at our facility were utilized for this study. EtG and EtS concentrations were compared across the age partitions 0 to 17 years (pediatric), 18 to 80 years (adult), and 81 to 100 years (geriatric). Eight pediatric patients from a tertiary academic hospital contributed clinical context via abstracted clinical information. Across the individual age partitions, 60% to 65% of patients had both EtG and EtS present in urine. Approximately 5% to 10% of patients had only EtG, and 25% to 35% had neither metabolite present. The lowest percentages (<1.5%) had EtS present in the absence of EtG. Markedly, no pediatric patients had only EtS present; compared to the adult population, this was statistically significant (Fisher exact test, P = 0.025). From the data presented in this work, EtG is more prevalent relative to EtS in urine samples of patients assessed for ethanol exposure.

Impact of an Ionic Liquid Solution on Horseradish Peroxidase Activity.

Horseradish peroxidase (HRP) is an enzyme that oxidizes pollutants from wastewater. A previous report indicated that peroxidases can have an enhancement in initial enzymatic activity in an aqueous solution of 0.26 M 1-ethyl-3-methylimidazolium ethyl sulfate ([EMIm][EtSO4]) at neutral pH. However, the atomistic details remain elusive. In the enzymatic landscape of HRP, compound II (Cpd II) plays a key role and involves a histidine (H42) residue. Cpd II exists as oxoferryl (2a) or hydroxoferryl (2b(FeIV)) forms, where 2a is the predominantly observed form in experimental studies. Intriguingly, the ferric 2b(FeIII) form seen in synthetic complexes has not been observed in HRP. Here, we have investigated the structure and dynamics of HRP in pure water and aqueous [EMIm][EtSO4] (0.26 M), as well as the reaction mechanism of 2a to 2b conversion using polarizable molecular dynamics (MD) simulations and quantum mechanics/molecular mechanics (QM/MM) calculations. When HRP is solvated in aq [EMIm][EtSO4], the catalytic water displaces, and H42 directly orients over the ferryl moiety, allowing a direct proton transfer (PT) with a significant energy barrier reduction. Conversely, in neat water, the reaction of 2a to 2b follows the previously reported mechanism. We further investigated the deprotonated form of H42. Analysis of the electric fields at the active site indicates that the aq [EMIm][EtSO4] medium facilitates the reaction by providing a more favorable environment compared with the system solvated in neat water. Overall, the atomic level supports the previous experimental observations and underscores the importance of favorable electric fields in the active site to promote catalysis.

Evaluation of harmful drinking among professional drivers by direct ethanol biomarkers and its relation with psychological distress

Objective This study aimed to evaluate the alcohol consumption among professional truck and bus drivers using direct ethanol biomarkers, and to explore its relationship with anxiety, depression, and stress. Methods The assessment of potential harmful drinking was conducted through the measurement of direct biomarkers: phosphatidylethanol (PEth), ethyl glucuronide (EtG), and ethyl sulfate (EtS), using dried blood spots (DBS). Additionally, self-reported data from the Alcohol Use Disorders Identification Test (AUDIT-C) were used. Emotional states, including depression, anxiety, and stress, were evaluated using the Depression, Anxiety, and Stress Scale (DASS-21). Results A total of 97 drivers participated in the study, with the majority being male (96%) and identified as truck drivers (75.3%). Among them, 43.3% reported working more than 10 h daily. The majority of volunteers exhibited normal levels of stress (81.4%), anxiety (83%), and depression (86.6%). According to the AUDIT-C assessment, 30.9% were categorized as having a moderate risk, while 11.3% were deemed to be at high risk for harmful alcohol consumption behavior. Ethyl glucuronide (EtG) and ethyl sulfate (EtS) levels, indicating recent ethanol consumption, were detected in 14.4% of the drivers. In contrast, the long half-life metabolite PEth (16:0-18:1) was present in 88.7% of the volunteers. A moderate correlation (rs = 0.45, p < .01) was observed between PEth levels and AUDIT-C scores. The Receiver Operating Characteristic (ROC) curve, utilizing a PEth threshold of ≥ 59.0 ng ml−1, displayed 78% sensitivity and 73% specificity in effectively distinguishing high risk for alcohol intake. Notably, no significant associations were found between alcohol consumption and levels of stress, depression, and anxiety. Conclusions The study findings indicate a noteworthy proportion of drivers engaging in regular alcohol consumption alongside a demanding workload. Notably, PEth measurements highlighted an underreporting within the AUDIT-C self-reports. These results lend robust support for the utilization of biomarkers in assessing alcohol consumption patterns among drivers.

New Insights into the Hygroscopic Character of Ionic Liquids: Study of Fourteen Representatives of Five Cation and Four Anion Families.

Over the past three decades, the synthesis of new ionic liquids (ILs) and the expansion of their use in newer applications have grown exponentially. From the beginning of this vertiginous period, it was known that many of them were hygroscopic, which in some cases limited their use or altered the value of their measured physical properties with all the problems that this entails. In an earlier article, we addressed the hygroscopic grade achieved by the ILs 1-ethyl-3-methylimidazolium chloride, 1-ethyl-3-methylimidazolium bromide, 1-ethyl-3-methylimidazolium methyl sulfate, 1-ethyl-3-methylimidazolium ethyl sulfate, 1-ethyl-3-methylpyridinium ethyl sulfate, 1-ethyl-3-methylimidazolium tosylate, 1-ethyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylimidazolium tetrafluoroborate, 1-dodecyl-3-methylimidazolium tetrafluoroborate, 1-butyl-3-methylpyridinium tetrafluoroborate, 1-butyl-1-methylpiperidinium bis(trifluoromethyl sulfonyl)imide, 1-methyl-1-propylpyrrolidinium bis(trifluoromethyl sulfonyl)imide, 1-butyl-1-methylpyrrolidinium bis(trifluoromethyl sulfonyl)imide, and methyl trioctyl ammonium bis(trifluoromethyl sulfonyl)imide. The objective was to determine the influence of the chemical nature of the compounds, exposed surface area, sample volume, agitation, and temperature. For this purpose, we exposed the samples to abrupt increases in relative humidity from 15 to 100% for days in an atmosphere chamber and then proceeded with the reverse process in a gentle manner. The results show that the sorption of water from the atmosphere depends on the nature of the IL, especially the anion, with the chloride anion being of particular importance (chloride ≫ alkyl sulfates~bromide > tosylate ≫ tetrafluoroborate). It has also been proven for the EMIM-ES and EMIM-BF4 samples that the mechanism of moisture capture is both absorption and adsorption, and that the smaller the exposed surface area, the higher the ratio of the mass of water per unit area.

In vitro induction and investigation of salinity tolerance in the callus of Vigna spp. (L)

Cowpeas can be employed for rotational grazing or generating high-quality food when paired with crops such as maize. Cowpea seeds provide a substantial amount of protein and other essential elements. The purpose of this work was to use a mutagen and a high salt concentration to extract a salt tolerance gene from the callus. The callus was induced by adding 2,4-Dichlorophenoxyacetic acid 2,4- D at mg/l and was then subjected to various concentrations of a combination of salts consisting of sodium chloride NaCl and Calcium Chloride.CaCl2, in addition to Magnesium chloride MgCl2, with a rate of 2:2:1 and potion 0, 50, 100, 150, 200, and 250 mM of the salt mixture added to the culture medium. Various levels of di ethyl sulfate (DES) mutagenic solution at a concentration of 0.1 mM were used to soak the callus for 30 minutes. The results showed that when using quantitative polymerase chain reaction q-PCR, they showed two genes of vigna, the first gene in this research. Aldehyde dehydrogenase family 3 (ADF3) demonstrated the explanation of the genes at doses of DES+200, 200, and 250 mM; however, the most elevated level of gene expression at DES+200mM is CT 30.47, with an upregulation of 2.479. The second gene, Protein S2, demonstrated that the gene is highly expressed at DES+200mM, cycle threshold (CT) 31.68, and DES+250mM concentrations and is upregulated at DES+150mM was 128.

Imaging a solvent‐swollen polymer gel network by open liquid transmission electron microscopy

AbstractVisualizing the network of a solvent‐swollen polymer gel remains problematic. To address this challenge, open transmission electron microscopy (TEM) was applied to thin gel films permeated by a nonvolatile ionic liquid. The targeted physical gels were prepared by cooling concentrated solutions of poly(ethylene glycol) in 1‐ethyl‐3‐methyl imidazolium ethyl sulfate [EMIM][EtSO4]. During the cooling, gelation occurred by a frustrated crystallization of the dissolved polymer, leading to a percolated, solvent‐permeated semicrystalline network in which nanoscale polymer crystals acted as crosslinks. Crystalline features ranging from ~5 to ~200 nm were observed, with the visible network strands dominantly consisting of long curvilinear crystallites of ~15–20 nm diameter. Nascent spherulites irregularly decorated the network, creating a complex structural hierarchy that complicated analyses. Lacking diffraction contrast, TEM did not visualize the many disordered, fully solvated PEG chains present in the voids between crystals. Recognizing that a network's three dimensionality is ambiguous when assessed through two‐dimensional microscopy projections, a small gel region was studied by TEM tomography, revealing a nearly isotropic three‐dimensional arrangement of the curvilinear crystallites, which displayed remarkably uniform cylindrical cross sections.