Alkyl Phosphates Research Articles

Regio- and Stereoselective (SN2) N-, O-, C- and S-Alkylation Using Trialkyl Phosphates

AbstractBimolecular nucleophilic substitution (SN2) is one of the most well-known fundamental reactions in organic chemistry to generate new molecules from two molecules. In principle, a nucleophile attacks from the back side of an alkylating agent having a suitable leaving group, most commonly a halide. However, alkyl halides are expensive, very harmful, toxic and not so stable, which makes them problematic for laboratory use. In contrast, trialkyl phosphates are inexpensive, readily accessible and stable at room temperature, under air, and are easy to handle, but rarely used as alkylating agents in organic synthesis. Here, we describe a mild, straightforward and powerful method for nucleophilic alkylation of various N-, O-, C- and S-nucleophiles using readily available trialkyl phosphates. The reaction proceeds smoothly in excellent yield, and quantitative yield in many cases, and covers a wide range of substrates. Further, the rare stereoselective transfer of secondary alkyl groups has been achieved with inversion of configuration of chiral centers (up to 98% ee).

Urinary Metabolites of Organophosphate Pesticides among Pregnant Women Participating in the Japan Environment and Children's Study (JECS).

Organophosphate pesticides (OPPs) exhibit neurodevelopmental toxicity. To evaluate the effect of prenatal exposure to OPPs in the Japan Environment and Children’s Study, a nationally representative birth cohort study, 4575 maternal urine samples were analysed for six OPP metabolites, i.e., dialkylphosphates (DAPs). This study aimed to investigate predictors of urinary DAPs using machine learning approaches and to assess the cumulative risk based on relative potency factors among Japanese pregnant women. The median creatinine-normalised urinary concentrations (interquartile ranges) of dimethylphosphate, dimethylthiophosphate and diethylphosphate, which had a detection rate of 50% or higher, were 3.53 (1.91–6.78), 4.09 (1.66–10.8) and 3.28 (1.88–5.98) µg/g-creatinine, respectively. Possible predictors of urinary DAP concentrations were the month of urine sampling, consumption of apple and maternal body mass index. When fenitrothion was used as an index chemical for cumulative risk assessment, 0.36% of participants exceeded the lower 95% confidence limit of the benchmark dose10.

Triazophos and its metabolite diethyl phosphate have different effects on endocrine hormones and gut health in rats

Organophosphorus pesticide (OP) residues present in food can be metabolized into diethylphosphate (DEP) in vivo. Epidemiological studies of OPs have usually focused on these metabolites, while animal studies mainly assessed the OPs. Here, we compared the health risks of a frequently detected OP, triazophos (TAP), and its major metabolite, DEP, in rats. Levels of serum lipids and, sex hormones were measured using immunoassay kits. Gut hormones and inflammatory cytokines were assessed using a multiplexing kit, and the gut microbiota was evaluated by 16S rRNA gene sequencing. After a 24-week exposure period, both TAP and DEP significantly decreased serum levels of triglycerides, cholesterol, low-density lipoprotein cholesterol, and IL-6 (p < 0.05). However, DEP exposure had a stronger effect on serum estradiol (p < 0.05) than TAP, whereas only TAP inhibited the secretion of gut hormones. Both TAP and DEP enriched the pathogenic genera Oscillibacter, Peptococcus and Paraprevotella in the gut, and TAP also enriched enteritis-related genera Roseburia and Oscillibacter, which may affect the secretion of gut hormones. These findings indicate that the use of dialkyl phosphates as markers of OPs to examine the correlations of OP exposure with diseases may only provide partial information, especially for diseases related to gut health and the endocrine system.

Exposure to Organophosphate and Neonicotinoid Insecticides and Its Association with Steroid Hormones among Male Reproductive-Age Farmworkers in Northern Thailand.

Several studies indicated organophosphate (OP) and neonicotinoid (NEO) insecticides are endocrine disruptors; however, data are scarce. This cross-sectional study recruited 143 male farmworkers aged 18–40 years in Fang district, Chiang Mai province, northern Thailand. OP exposure was assessed by measuring urinary dialkylphosphate (DAPs) using a gas-chromatography flame photometric detector. Urinary NEOs, their metabolites (NEO/m) and serum steroid hormones were measured using liquid chromatography–tandem mass spectrometry. Characteristics of participants were determined by face-to-face interviews. DAPs and five NEO/m were detected in more than 60% of samples. The concentration of diethylphosphate was highest among DAP metabolites (geometric mean concentration (GM: 23.9 ng/mL) and the concentration of imidacloprid (IMI) was highest among NEO/m (GM: 17.4 ng/mL). Linear regression models showed that the IMI level was positively associated with testosterone, dehydrocorticosterone (DHC) and dehydroepiandrosterone (DHEA) levels. Imidacloprid-olefin and DHEA levels were positively associated. Thiamethoxam (THX) were inversely associated with DHC and deoxycorticosterone levels. Clothianidin (CLO), THX and N-desmethyl-acetamiprid levels were positively associated with the androstenedione level. CLO and THX levels were inversely associated with the cortisone level. In conclusion, the association between NEO insecticides exposure and adrenal androgens, glucocorticoids and mineralocorticoids, suggest potential steroidogenesis activities. Our findings warrant further investigation.

Cytotoxicity of Ionic Liquids on Normal Human Dermal Fibroblasts in the Context of Their Present and Future Applications

The skin is the part of the body that is the most exposed to toxic substances; therefore, the impact of chemicals on the skin should be thoroughly studied prior to their implementation in any industrial-scale application. Herein, we examined and analyzed the influence of the structure of both the cation and anion of 31 different ionic liquids (ILs) on their cytotoxicity against normal human dermal fibroblasts in the context of their present and future potential applications. We found that imidazolium-based ILs combined with dialkyl phosphate anions or with the ethyl sulfate anion are the least cytotoxic. Notably, 1,3-diethylimidazolium ethyl sulfate can be potentially used as a hydraulic fluid similar to the commercially available hydraulic medium based on 1-ethyl-3-methylimidazolium ethyl sulfate. Moreover, the dialkyl phosphate-based ILs are considered as an efficient solvent for the utilization of lignocellulose-based biomass and as an extractant in eco-friendly and cost-effective processes for the extraction of bioplastic. Pyrrolidinium-based and cyano-based ILs, often used as heat transfer media and base fluids for ionanofluids, were also identified herein as good candidates based on their relatively low toxicity compared to other ILs.

Organophosphorus pesticide exposure biomarkers in a Mexican population.

The organophosphate (OP) pesticides are neurotoxic compounds widely used around the world. Evaluation of OP exposure in human studies is important for enabling adequate data analyses and drawing accurate conclusions. The aim of this study was to analyze OP exposure biomarkers and their relationships in a Mexican population with different exposure levels. Dialkylphosphates (DAP) were determined through gas chromatography-mass spectrometry (GC-MSD); acetylcholinesterase (AChE), butyrylcholinesterase (BuChE), arylesterase (AREase), basal paraoxonase 1 (PONase), and β-glucuronidase activities were detected using spectrophotometric methods. The albumin content was determined in a certified clinical laboratory. The DMTP metabolite was found in the highest concentration, and a negative and significant correlation between DAP and cholinesterase activity was observed. Our results suggested that BuChE is a considerably more sensitive biomarker than AChE. In addition, β-glucuronidase was positively correlated with albumin, BuChE, and PONase. In conclusion, our data strongly support the use of two or more biomarkers of exposure in human monitoring and the application of a strong and validated questionnaire.

Organophosphate pesticides and progression of chronic kidney disease among children: A prospective cohort study

BackgroundGrowing evidence suggests that exposure to environmental chemicals, such as pesticides, impacts renal function and chronic kidney disease (CKD). However, it is not clear if pesticides may affect CKD progression and no studies exist in children. ObjectivesThe objective of this study was to examine associations between serially measured urinary OP pesticide metabolites and clinical and laboratory measures of kidney function over time among children with CKD. MethodsThis study used data on 618 participants enrolled in the CKD in Children study (CKiD), a cohort study of pediatric CKD patients from the US and Canada. Children were followed over an average of 3.0 years (standard deviation (SD) = 1.6) between 2005 and 2015. In serially collected urine samples over time, six nonspecific dialkyl phosphate (DAP) metabolites of OP pesticides were measured. Biomarkers of tubular injury (kidney injury molecule-1 (KIM-1) and neutrophil gelatinase-associated lipocalin (NGAL)) and oxidant stress (8-hydroxy-2′-deoxyguanosine (8-OHdG) and F2-isoprostane) were determined in the same specimens. Estimated glomerular filtration rate (eGFR), proteinuria, and blood pressure were assessed annually. ResultsDAPs were associated with increased KIM-1 and 8-OHdG throughout follow-up. A standard deviation increase in ∑diethyl metabolites was associated with increases of 11.9% (95% Confidence Interval (CI): 4.8%, 19.4%) and 13.2% (95% CI: 9.3%, 17.2%) in KIM-1 and 8-OHdG over time, respectively. DAPs were associated with lower eGFR at baseline and higher eGFR over subsequent years. ConclusionsThese findings provide preliminary evidence suggesting that urinary DAP metabolites are associated with subclinical kidney injury among children with CKD, which may signal the potential for clinical events to manifest in the future. The results from this study are significant from both a clinical and public health perspective, given that OP pesticide exposure is a modifiable risk factor.

Synthesis of alkyl phosphates and investigation of their surface-active properties in an alkaline surfactant polymer system for enhanced oil recovery

Chemical flooding is a technique of enhanced oil recovery (CEOR) using formulations containing alkaline components, surfactants and polymers (ASP technology). The development and synthesis of novel highly efficient industrial surfactants take this technology to a new level, allowing the chemical composition of reagents to be tailored to the reservoir conditions of fields in Western Siberia. Alkyl phosphates with various structures are one type of the surfactants that can be used in ASP technology. This work aimed to synthesize and examine the properties of commercial (semi-industrial) alkyl phosphates and alkoxylated alkyl phosphates of mixed composition that meet the requirements of an efficient surfactant component of an ASP-flooding formulation. The synthesis was carried out using industrial fatty alcohols by the phosphating reaction with phosphorus pentoxide. A mixture of monoand disubstituted phosphoric acid esters of a defined ratio can be obtained by target tailoring of the feedstock properties (structural changes, molecular weight distribution in alcohols) and the synthesis conditions. This mixture, requiring no addition of cosurfactants, is an effective multi-component surfactant for an ASP-system. In this work, three effective alkyl phosphates and alkoxylated alkyl phosphates blends were synthesized. The composition of the synthesized phosphoric esters was evaluated by high-resolution mass spectrometry (HRMS), infrared (IR) spectroscopy and potentiometric titration. At reservoir temperature, the obtained samples provided sufficient solubility in an oil-displacing aqueous solution in the technologically required salinity interval, compatibility with other components, low interfacial tension (IFT) values at the interface between ASP solution and oil from Western Siberia fields, and the formation of the sufficient volume of the emulsion phase in a phase experiment. The primary laboratory research data proved the efficiency of the synthesized surfactants in ASP technology in the fields of Western Siberia.

Organophosphate pesticide exposure during pregnancy and childhood and onset of juvenile delinquency by age 16 years: The CHAMACOS cohort

BackgroundThough prenatal organophosphate pesticide (OP) exposure has been associated with lower intellectual quotient and behavioral disorders in childhood, factors related to later delinquency, no research has directly evaluated the impact of OPs on delinquency. ObjectiveTo evaluate the association between prenatal and childhood OP exposure and juvenile delinquency in Mexican-American youth in the Center for Health Assessment of Mothers and Children of Salinas (CHAMACOS). MethodsWe measured dialkyl phosphate (DAPs) urinary metabolites of OPs in two prenatal maternal samples and in five child samples collected between six months and five years of age. Youth completed delinquency questionnaires at 16 years. We examined associations of prenatal and childhood DAPs with several delinquency outcomes (n = 313) using survival and generalized linear models. ResultsAlmost 60% of youth reported delinquent acts (mostly minor), and 8% reported a police arrest. We observed largely null results of prenatal or childhood DAP concentrations and delinquency outcomes, with some isolated associations. A ten-fold increase in maternal dimethylphosphate (DM) concentrations measured after 20 weeks gestation was associated with an earlier age of first delinquent act (Hazard Ratio = 1.38, 95% CI: 1.01, 1.88) and an increased Odds Ratio (OR) of having committed 1–3 or ≥4 delinquent acts, compared to the no delinquency reference group (OR = 1.77, 95% CI: 1.01–3.08 and 2.17, 95% CI: 1.13–4.17, respectively). Higher childhood diethylphosphate (DE) concentrations were associated with a later age of first delinquent act (HR: 0.67; 95% CI: 0.46–0.97). DiscussionWe did not find strong evidence of association between prenatal or childhood OP exposure and juvenile delinquency in the present cohort. There is an increasing literature that relates OP exposure to neurobehavioral impairments in childhood, and there is a need to understand long-term potential neurodevelopmental effects of early-life OP exposure.

Organophosphate pesticide exposure: Demographic and dietary predictors in an urban pregnancy cohort

Pregnant women are widely exposed to organophosphate (OP) pesticides, which are potentially neurotoxicant for the developing fetus. We aimed to identify principal demographic and dietary predictors of OP pesticide exposure among 450 pregnant women participating in the New York University Children’s Health and Environment Study (enrolled 2016–19). Urinary concentrations of six dialkyl phosphate (DAP) metabolites (3 dimethyl (DM) metabolites and 3 diethyl (DE) metabolites) of OP pesticides were determined at three time points across pregnancy. At mid-gestation, the Diet History Questionnaire II was used to assess women’s dietary intake over the past year. Demographic characteristics were obtained using questionnaires and/or electronic health records. We used linear mixed models to evaluate the associations of demographic and food groups with DAP metabolite levels, and partial-linear single-index (PLSI) models to analyze the contribution proportions of food groups to DAP metabolite concentrations and the dose-response relationships between them. We observed that pregnant women in NYC had lower levels of OP pesticide metabolites than pregnant populations in Europe, Asia, and other regions in the U.S. Having lower pre-pregnancy body mass index and being Asian, employed, and single were associated with higher DAP metabolite concentrations. Fruit and grain intakes were associated with higher ∑DM, ∑DE, and ∑DAP levels. ∑DE concentrations increased 9.0% (95% confidence interval (CI) = 1.2%, 17.4%) per two-fold increase in dairy consumption, whereas ∑DE concentrations decreased 1.8% (95%CI = −3.1%, −0.4%) per two-fold increase in seafood consumption. The PLSI model indicated that among the food mixture, fruit and grains were the main food groups contributed to higher levels of ∑DAP, while meat contributed to lower levels of ∑DAP. The contribution proportions of fruit, grains, and meat were 18.7%, 17.9%, and 39.3%, respectively. Our results suggest that fruit, grains, and meat are major dietary components associated with OP pesticide exposure in urban pregnant women.

An Attempt to Formulate Non‐Carbonate Electrolytes for Sodium‐Ion Batteries

AbstractNon‐aqueous carbonate solvents have been the main choice for the development of lithium‐ion batteries, and similarly most research on sodium‐ion batteries have been performed using carbonate‐based solvents. However, the differences between sodium and lithium batteries – in term chemistry/electrochemistry properties as well as electrode materials used – open up opportunities to have a new look at solvents that have attracted little attention as electrolyte solvent. This work investigates properties of a wide range of different solvent classes in the context of sodium‐ion battery electrolytes and compares them to the performance of propylene carbonate. The thirteen solvents studied here include one or several members of glymes, carbonates, lactones, esters, pyrrolidones, sulfones, and alkyl phosphates. Out of those, five outperforming solvents of γ‐butyrolactone (GBL), γ‐valerolactone (GVL), N‐methyl‐2‐pyrrolidone (NMP), propylene carbonate (PC), and trimethyl phosphate (TMP) were further investigated using additives of ethylene sulfite (ES), vinylene carbonate (VC), fluoroethylene carbonate (FEC), prop‐1‐ene‐1,3‐sultone (PES), sulfolane (TMS), tris(trimethylsilyl) phosphite (TTSPI), and sodium bis(oxalato)borate (NaBOB). The solvents TMS and tetraethylene glycol dimethyl ether (TEGDME) were tested in 1 : 1 mixtures by volume with the co‐solvents; NMP, dimethoxyethane (DME), and TMP. All electrolytes used NaPF6 as the salt. Primary evaluation relied on electrochemical cycling of full‐cell sodium‐ion batteries consisting of Prussian white cathodes and hard‐carbon anodes. Galvanostatic cycling was performed using both two‐ and three‐electrode cells, in addition, cyclic and linear sweep voltammetry was used to further evaluate the electrolyte formulations. Moreover, the resistance was measured on the anode and cathode, using Intermittent current interruption (ICI) technique.

Relation between organophosphate pesticide metabolite concentrations with pesticide exposures, socio-economic factors and lifestyles: A cross-sectional study among school boys in the rural Western Cape, South Africa.

Evidence on the relationship between lifestyle, socio-economic factors and pesticide exposure and urinary concentrations of organophosphate (OP) pesticide metabolites among children is generally incomplete. This study investigated the relationship between socio-economic factors and reported pesticide exposures and the sum of three urinary concentrations of dialkyl phosphate metabolites (DAP) among boys living in the rural areas of the Western Cape, South Africa. Data was collected during a cross-sectional study of 183 boys from three agricultural intense areas. Measurements included a questionnaire on socio-economic and pesticide exposures and urinary DAP concentrations. Most boys (70%) lived on farms with a median age of 12 years (range: 5.0-19.5 years). Children aged >14 years had lower DAP urine concentrations (median=39.9ng/ml; β=-68.1ng/ml; 95% CI:-136.8, 0.6) than children aged 9 years and younger (median=107.0ng/ml). DAP concentrations also varied significantly with area, with concentrations in the grape farming area, Hex River Valley (median=61.8ng/ml; β=-52.1; 95% CI:-97.9,-6.3ng/ml) and the wheat farming area, Piketberg (median=72.4ng/ml; β=-54.2; 95% CI: 98.8,-9.7ng/ml) lower than those in the pome farming area, Grabouw (median=79.9ng/ml). Other weaker and non-significant associations with increased DAP levels were found with increased household income, member of household working with pesticides, living on a farm, drinking water from an open water source and eating crops from the vineyard and or garden. The study found younger age and living in and around apple and grape farms to be associated with increased urinary DAP concentrations. Additionally, there were other pesticide exposures and socio-economic and lifestyle factors that were weakly associated with elevated urinary DAP levels requiring further study. The study provided more evidence on factors associated to urinary DAP concentrations especially in developing country settings.

Non-linear model analysis of the relationship between cholinesterase activity in rats exposed to 2, 2-dichlorovinyl dimethylphosphate (dichlorvos) and its metabolite concentrations in urine

Urinary dialkylphosphates (DAPs) are measured to assess exposure to organophosphorus pesticides (OPs), but they are common metabolites of OPs and not specific indices for individual agents. Biomonitoring (BM) of urinary DAPs has been widely adopted as an assessment of individual exposure in general environments, however, guidance values for DAPs based on health effects have yet to be established. The present study aimed to clarify the relationship between the amount of urinary dimethylphosphate (DMP), a metabolite of dichlorvos (DDVP), and the inhibition of cholinesterase (ChE) activity in rats exposed to DDVP. The relationship was analyzed using a nonlinear model analysis, and the excretion level of urinary DMP equivalent to ChE 20 % inhibition (EL20) and the lower limit of the 95 % confidence interval of EL20 (ELL20) were estimated. EL20 and ELL20 (mg/24 h urine) of brain, erythrocyte, and plasma ChE activities after 10-day administration of DDVP were 0.21 and 0.15, 0.11 and 0.06, and 0.23 and 0.09, respectively. Extrapolating ELL20 of the brain ChE to humans, the range of 24 h urinary DMP concentration according to the 20 % inhibition of cholinesterase activity was estimated to be 20.5–30.8 mg/l. In conclusion, the amount of urinary DMP as ELL20 for DDVP exposure was identified and could probably be used as a novel index for the assessment of risk from OP exposure. Further studies are needed to clarify the ELL20 s derived from OPs other than DDVP, for informing efforts to establish guidance values of urinary OP metabolites that should prevent neurotoxicity.

Assessment of Organophosphate Pesticides Exposure in Men with Idiopathic Abnormal Semen Analysis: A Cross-Sectional Pilot Study.

Background:Because of the widespread use of organophosphate (OP) pesticides in agriculture, they are major environmental contaminants in developing countries. OP pesticides decrease sperm concentration and affect its quality, viability, and motility. Studies have demonstrated the association between abnormal semen analysis and OP pesticides exposure among the high-risk population. As there is limited data on the percentage of OP pesticides exposure, the study aimed to determine the OP pesticides exposure in Southern Indian men with idiopathic abnormal semen analysis and find the possible source of their OP pesticides exposure.Materials and Methods:In this cross-sectional pilot study, fifty men with idiopathic abnormal semen analysis as cases and fifty men with normal semen analysis as controls were recruited. Detailed history was taken and general and systemic examinations were carried out. OP pesticides exposure was determined by assessment of pseudocholinesterase and acetylcholinesterase levels and urinary OP pesticides metabolites dialkyl phosphate (DAP) consisting of dimethyl phosphate (DMP), diethyl thiophosphate (DETP), and diethyl dithiophosphate (DEDTP).Results:Cases had statistically significantly lower levels of pseudocholinesterase (5792.07 ± 1969.89 vs. 10267.01 ± 3258.58 IU/L) (P=0.006) and acetylcholinesterase [102.90 (45.88-262.74) vs. 570.31 (200.24-975.30) IU/L] (P=0.001) as compared to controls. Cases had a statistically significantly higher percentage of urinary DAP positivity as compared to controls (80 vs. 38%, P<0.0001). Hence, cases had a significantly higher percentage of OP pesticides exposure as compared to controls (20 vs. 4%, P=0.015). OP-exposed cases had significantly higher urinary DETP and DEDTP levels as compared to OP non-exposed cases. Also, urinary DETP and DEDTP levels were significantly negatively associated with sperm concentration, motility, and normal morphology among OP-exposed cases.Conclusion: Southern Indian men with idiopathic abnormal semen analysis had a significantly higher percentage of OP pesticides exposure as compared to men with a normal semen analysis.

Competitive extraction of Li, Na, K, Mg and Ca ions from acidified aqueous solutions into chloroform layer containing diluted alkyl phosphates

Alkyl phosphates were extensively used in liquid–liquid extraction of lanthanides and actinides, but to a lesser extent for alkali and alkaline earth metals. The high amount of alkyl phosphate, which is usually used in the organic layer (>40 wt%), is not favoured due to its corrosive effect and toxicity. In the present work, diluted chloroform solutions (20.0 mM) of tri-n-butyl phosphate (TBP), tris(2-ethylhexyl) phosphates (TRIS) and bis(2-ethylhexyl) phosphate (BIS) were investigated for their extraction of Li, Na, K, Mg and Ca ions. The extraction experiments were conducted on 7.0 M HNO3 aqueous solutions containing 60.0 mM of metal ions in binary (Li+ and Mg2+), ternary (Li+, Na+ and K+) and quinary (Li+, Na+, K+, Mg2+ and Ca2+) mixtures. The Li+ selectivity over Mg2+ was very high in the binary system. Remarkably, increasing HNO3 concentration in the aqueous layer had opposing effect on the extraction of Li+ (positive) and Mg2+ (negative). However, the selectivity for Li+ became less dramatic in the case of ternary and quinary system, though the selectivity varied with initial metal concentrations. The amounts of water and NO3– transferred into the organic layer demonstrated their synergistic effect on extracting metal ions. In the ternary and quinary systems, the total concentrations of metal ions in the organic layer (ranged from 49 to 85 mM) were higher than the concentration of ligand in the organic layer (20.0 mM), suggesting that metal ions may be extracted into water/ligand/NO3– aggregates in the organic layer. TBP, TRIS and BIS do not have significant difference in their extraction behaviour. The FTIR results indicated formation of P+-O-M+/M2+ in the solid TBP/metal complex.

Highly Stable and Efficient Lead Halide Perovskite Nanocrystals for Light-Emitting Diodes Displays

All inorganic lead halide perovskite nanocrystals (NCs), CsPbX3 (X=Cl, Br, I), have been attracting increasing attention because of their excellent optical properties, such as tunable emission wavelength, high photoluminescence quantum yield (PLQY), narrow full width at half maximum (fwhm), and high defect tolerance. Therefore, the NCs have great potential application in light-emitting diodes for display. However, the NCs suffer from poor stability due to the hydrolytic degradation and fluorescence quenching in the solid agglomerations state. To improve the photoluminescence (PL) stability of the NCs, the ammonium bromide, alkyl phosphate, microscale Cs4PbX6, and super hydrophobic porous organic polymers (SHOP) were used as frameworks to from the composites with NCs. Specially, the CsPbBr3-super hydrophobic polymers composites not only preserve a high PLQY (60%) and narrow band emission (fwhm~16nm) but also inherit the outstanding water-resistant property of SHOP to protect the NCs from hydrolytic degradation. The PLQY of the composites was maintained at 91% of the initial one after being immersed in water for 31 days. Even after being immersed in water for six months, the composites still retain bright green emission. A white light-emitting diode (WLEDs) device was prepared by combining green-emitting composites and red-emitting K2SiF6:Mn4+ phosphors with a blue LED chip. The device exhibits a high luminous efficiency of 50 lm/W and a wide color gamut (127% of the National Television System Committee and 95% Rec. 2020). This work provides an alternative approach to solve the challenging stability issue of perovskite QDs; therefore, it has a positive implication for their practical application in liquid crystal display backlights.

Aerobic degradation of nonhalogenated organophosphate flame esters (OPEs) by enriched cultures from sludge: Kinetics, pathways, bacterial community evolution, and toxicity evaluation

The degradation by bacteria has been considered the main process for eliminating nonhalogenated organophosphate esters (OPEs) from wastewater treatment plants (WWTPs), but limited research has reported the biodegradation processes and clarified the microbial-mediated mechanisms for nonhalogenated OPE degradation in WWTPs. The aim of this study was to monitor the biodegradation of the most common nonhalogenated OPEs, namely, tris(2-butoxyethyl) phosphate (TBOEP), tris (n-butyl) phosphate (TNBP) and trisphenyl phosphate (TPHP), under aerobic conditions by sludge cultures from a conventional sewage plant. The microbial cultures were enriched separately with each OPE from activated sludge cultures, and the presence of glucose significantly enhanced degradation of the OPEs during the enrichment. The removal ratios for the three OPEs reached 29.3–89.9% after 5 cycles (25 days) of cultivation, and the first-order degradation kinetics followed the order of TPHP > TBOEP > TNBP, with their half-lives ranging between 12.8 and 99.0 h. Pathways of hydrolysis, hydroxylation, methoxylation, and substitution were confirmed for the aerobic biodegradation of these nonhalogenated OPEs, but only di-alkyl phosphates (DAPs) largely accumulated in culture medium as the most predominant transformation products. Phylotypes in Klebsiella were significantly more abundant during OPE biodegradation than in the initial sludge, which indicated that these microorganisms are associated with the biodegradation of nonhalogenated OPEs in sludge culture. Biodegradation of all investigated nonhalogenated OPEs was associated with a significant reduction in the residual toxicity to Vibrio fischeri, indicating a rather positive ecotoxicological outcome of the aerobic biotransformation processes achieved by the enriched sludge culture.

Organophosphate pesticide dose estimation from spot and 24-hr urine samples collected from children in an agricultural community

BackgroundSpot urine samples are often used to assess exposure to organophosphate (OP) pesticides in place of “gold standard” 24-hr samples, which are cumbersome to collect. Assessment of non-persistent chemicals using spot urine samples may result in exposure misclassification that could bias epidemiological analyses towards the null. Few studies have examined the validity of measurements of urinary metabolites in spot samples to estimate daily OP dose or the potential implications of reliance on spot samples for risk assessments. ObjectiveExamine the validity of using first morning void (FMV) and random non-FMV urine samples to estimate cumulative 24-hr OP pesticide dose among children living in an agricultural region. MethodsWe collected urine samples over 7 consecutive days, including two 24-hr samples, from 25 children living in an agricultural community. We used measurements of urinary dialkylphosphate (DAP) metabolites, data on nearby agricultural pesticide applications, and daily dietary intake data to estimate internal dose from exposure to a mixture of OP pesticides according to the U.S. Environmental Protection Agency Cumulative Risk Assessment guidelines. Dose estimates from volume- and creatinine-adjusted same-day FMV and non-FMV spot urine samples were compared to the “gold standard” estimates from 24-hr samples. ResultsNon-FMV samples had relatively weak ability to predict 24-hr dose (R2 = 0.09–0.38 for total DAPs) and tended to underestimate the percentage of samples exceeding regulatory guidelines. Models with FMV samples or the average of an FMV and non-FMV sample were similarly predictive of 24-hr estimates (R2 for DAPs = 0.40–0.68 and 0.40–0.80, respectively, depending on volume adjustment method). ConclusionReliance on non-FMV samples for risk assessments may underestimate daily OP dose and the percentage of children with dose estimates exceeding regulatory guidelines. If 24-hr urine sample collection is infeasible, we recommend future studies prioritize the collection of FMV samples to most accurately characterize OP dose in children.

Association between Organophosphate Pesticide Exposure and Insulin Resistance in Pesticide Sprayers and Nonfarmworkers.

Insulin resistance is a risk factor for various diseases. Chronic organophosphate exposure has been reported to be a cause of insulin resistance in animal models. This cross-sectional study aimed to evaluate the association between organophosphate exposure and insulin resistance in pesticide sprayers and nonfarmworkers. Participants aged 40–60 years, consisting of 150 pesticide sprayers and 150 nonfarmworkers, were interviewed and assessed for their homeostatic model assessment of insulin resistance (HOMA-IR) level. Organophosphate (OP) exposure was measured in 37 sprayers and 46 nonfarmworkers by first morning urinary dialkyl phosphate (DAP) metabolites. The DAP metabolite levels were not different in either group except for diethylthiophosphate (DETP; p = 0.03), which was higher in sprayers. No significant association was observed between DAP metabolite levels and HOMA-IR. Wearing a mask while handling pesticides was associated with lower dimethyl metabolites (95% CI = −11.10, −0.17). Work practices of reading pesticide labels (95% CI = −81.47, −14.99) and washing hands after mixing pesticide (95% CI = −39.97, −3.35) correlated with lower diethyl alkylphosphate level. Overall, we did not observe any association between OP exposure and insulin resistance in pesticide sprayers and the general population. However, personal protective equipment (PPE) utilization and work practice were associated with OP exposure level in sprayers.

ALTERACIONES DEL CICLO MENSTRUAL DE ADOLESCENTES EXPUESTAS NO OCUPACIONALMENTE A UNA MEZCLA DE PLAGUICIDAS DE UNA ZONA AGRÍCOLA DE SAN LUIS POTOSÍ, MÉXICO. ESTUDIO PILOTO

Persistent organic pollutants are a group of chemical compounds of global concern due to the health damages caused by the exposure to them. Their capacity as endocrine disrupters is one of their main characteristics, being women in reproductive age the most vulnerable population. The aim of the present study was to evaluate the effect of exposure to a mixture of pesticides in the menstrual cycle of a sample of 29 teenagers between the ages of 12 and 17 years old from El Refugio, San Luis Potosi, Mexico, a community whose predominant activity is agriculture. The participants were trained to record in a diary/logbook all the events related to their menstrual cycle. Serum levels of sex hormones were measured by chemiluminescence, and plasma concentrations of organochlorine (OC) pesticides and the level of dialkyl phosphates metabolites (DAPs) of organophosphorus agrochemicals presented in urine were measured through gas chromatography-mass spectrometry. Around 41.6 % of the participants presented some alteration in their hormonal levels, mainly of follicle-stimulating hormone and progesterone. Of these, OC pesticides in plasma were detected in 62 % (ΣOC = 1651.25 ng/g of lipid), and 66 % had detectable levels of DAPs (ΣDAP = 153.82 mg/g of creatinine). Together, these results suggest damage to the endocrine system that could be generated by exposure to a mixture of OC and organophosphorus pesticides could generate.