Phenyl Phosphate Research Articles

Novel Aryl Phosphate for Improving Fire Safety and Mechanical Properties of Epoxy Resins.

Epoxy resins (EPs) are highly flammable, and traditional flame retardant modifications often lead to a significant reduction in their mechanical performance, limiting their applications in aerospace and electrical and electronic fields. In this study, a novel flame retardant, bis(4-(((diphenylphosphoryl)oxy)methyl)phenyl)phenyl phosphate (DMP), was successfully prepared and introduced into the EP matrix. When the addition of DMP was 9 wt%, the EP/9 wt% DMP thermosets passed the UL-94 V-0 rating, and their LOI was increased from 24.5% of EP to 35.0%. With the introduction of DMP, the phosphoric acid compounds from the decomposition of DMP promoted the dehydration and charring of the EP matrix, and the compact, dense char layer effectively exerted the shielding effect in the condensed phase. Meanwhile, the produced phosphorus-containing radicals played a quenching effect in the gas phase. As a result, the peak heat release rate (PHRR) and total heat release (THR) of EP/9 wt% DMP were reduced by 68.9% and 18.1% compared to pure EP. In addition, the polyaromatic structure of DMP had good compatibility with the EP matrix, and the tensile strength, flexural strength and impact strength of EP/9 wt% DMP were enhanced by 116.38%, 17.84% and 59.11% in comparison with that of pure EP. This study is valuable for expanding the application of flame-retardant EP/DMP thermosets in emerging fields.

Occurrence of legacy and emerging organophosphate flame retardants (OPFRs) on silicone wristbands: Comparison within couples

Novel organophosphate flame retardants (OPFRs) are recently identified and highly detected in indoor dusts, but their personal exposure was not clear. Here, wristband was used to estimate non-dietary exposure to emerging OPFRs in comparison with legacy OPFRs in 93 adults in Beijing, China. Comparison of studies in wristband monitoring data showed a clear difference in profiles of legacy OPFRs between China and United States, where tris(1,3-dichloro-2-propyl) phosphate (TDCIPP) was usually the dominant OPFR in the United States, but triphenyl phosphate has the highest contribution to total OPFRs in China. Five emerging OPFRs, including diethylene glycol bis(bis(2-chloroisopropyl) phosphate) (DEGBBCPP) and bis(2-ethylhexyl) phenyl phosphate (BEHPP), were detected in above 45 % of wristbands. The median concentration of DEGBBCPP (2.2 ng/g) was about three times higher than TDCIPP (0.76 ng/g), a legacy chloro-OPFR. Both emerging and legacy OPFRs were significantly correlated within 40 pairs of couples, suggesting major exposure in their homes. Wristbands from husbands had significantly higher tris(2-butoxyethyl) phosphate (TBOEP) and DEGBBCPP, while 2-ethylhexyl diphenyl phosphate (EHDPP) was significantly higher in wives' bands, suggesting gender-related exposure sources for these OPFRs.

Exposure levels and maternal transfer of emerging organophosphate flame retardants (OPFRs) in pregnant women: Comparison with traditional OPFRs

Prenatal exposure to organophosphorus flame retardants (OPFRs) has been linked with adverse effects on reproductive health, and new OPFRs are continually emerging. In this study, emerging OPFRs, such as bis(2-ethylhexyl) phenyl phosphate (BEHPP), triamyl phosphate (TAP), tris(4-tert-butylphenyl) phosphate (T4tBPPP), oxydi-2,1-ethanediyl phosphoric acid tetrakis(2 chloro-1-methylethyl) ester (RDT905), cresyl diphenyl phosphate (CDP), and 2-isopropylphenyl diphenyl phosphate (2IPPDPP), were detected in 84 %, 100 %, 100 %, 52 %, 40 %, and 40 % of 25 decidua samples with average concentrations of 2.36, 6.21, 1.5, 2.6, 1.07, and 0.09 ng/g of dry weight (dw), respectively. Six of the aforementioned emerging OPFRs (BEHPP, T4tBPPP, RDT905, 2IPPDPP, CDP, and TAP) were simultaneously detected in paired chorionic villus samples, and their average concentrations were 11.3, 1.77, 3.64, 0.11, 0.58, and 3.34 ng/g, which were significantly higher than and positively correlated with those in decidua samples. The geometric mean concentration ratios between chorionic villus and decidua samples for BEHPP, T4tBPPP, RDT905, 2IPPDPP, CDP, and TAP were 4.02, 1.61, 1.73, 1.48, 0.82, and 0.69, respectively, consistent with transthyretin binding-dependent behavior. Prenatal exposure to such emerging OPFRs, especially for BEHPP with relatively high concentration and maternal transfer, is of high concern from the view of women’s reproductive health.

Chemical and non-chemical stressors in a postpartum cohort through wristband and self report data: Links between increased chemical burden, economic, and racial stress

Multiple external stressors are known to have adverse impacts on health and development. Certain groups are more vulnerable and/or more likely to be exposed toenvironmental, psychological, and social stressors simultaneously. Yet, few studies have examined combined exposure to environmental toxicants and psychosocial stress. Here, we integrated environmental chemical exposure data collected using silicone wristbands and self-report social stressor data within the Brain and Early Experience (BEE) perinatal cohort to understand co-exposure to environmental chemicals and social stress. Silicone wristbands were worn for one week by mothers throughout central North Carolina who were 6 months postpartum (n = 97). Exposure to 110 environmental chemicals across eight chemical classes was quantified on silicone wristbands using gas chromatography mass spectrometry. Social stress was evaluated using eight established self-report questionnaires (e.g., Brief Symptom Inventory, Perceived Stress Scale), quantifying experiences such as race-related stress, economic strain, and relationship conflict. Hair cortisol levels were measured as an additional metric of stress. The chemical exposure landscape and associations among chemical exposure, demographic characteristics, and social stress were characterized through individual variable analyses, cluster and data reduction, and compiled scoring approaches to comprehensively evaluate chemical and social stress burdens. We found that chemicals contain co-occurring patterns largely based on chemical class, with phthalates representing the chemical class with highest exposure and polychlorinated biphenyls the lowest. Chemicals showed differential exposure across racial groups, with diethyl phthalate, triphenyl phosphate, and tris(3,5-dimethyl phenyl) phosphate at higher levels in Black participants compared with White participants. Integrating social stressor profiling with chemical exposure data identified one particularly vulnerable subset of participants in which high chemical exposure burden coincided with high experiences of racism and economic stress. These findings demonstrate co-occurring chemical and social stress, warranting further investigation to better understand how these combined stressors may contribute to disparities in maternal and child health.

Developmental toxicity of an emerging organophosphate ester Bis-(2-ethylhexyl)-phenyl phosphate on embryonic zebrafish: Comparison to 2-ethylhexyl diphenyl phosphate

Bis-(2-ethylhexyl)-phenyl phosphate (BEHPP) and its structural analog, 2-ethylhexyl diphenyl phosphate (EHDPP), are widely present in the environment. However, their toxic effects, particularly developmental toxicity, remain poorly understood. In this study, we evaluated the impacts of BEHPP and EHDPP on multiple developmental endpoints in zebrafish. BEHPP did not lead to mortality and malformations of embryos within the test concentration range (0.5–4.0 μM). In contrast, EHDPP had significant lethal effects, with an LC50 of 2.44 μM, and induced malformations, notably pericardial edema (PE), with an EC50 of 1.77 μM. In addition, BEHPP induced cardiac dysfunctions in embryos to a similar degree as EHDPP. Both stroke volume and cardiac output were significantly increased at BEHPP concentrations of 1.8 nM and above and at EHDPP concentrations of 4.3 nM and above. Transcriptomic analysis further corroborated the similar disturbance at the molecular level for both substances and revealed the Key Events (KEs) in the cardiac toxic regulation, including the focal adhesions, ECM-receptor interaction, cardiac muscle contraction, and the adrenergic signaling in cardiomyocytes. Taken together, the present study provided novel insights into the adverse effects of these emerging organophosphate esters and highlighted their potential risks to embryonic development in both ecosystems and humans.

Effect of Phosphate-Bridged Monomer on Thermal Oxidative Behavior of Phthalonitrile Thermosets.

Phthalonitrile thermosets are known for their excellent mechanical, physico-chemical, and fire-retardant properties, making them attractive for aerospace and mechanical engineering applications. When producing and applying phthalonitrile-based structural parts, it is essential to consider aspects such as processability and the long-term stability of the material's properties at high temperatures. In our previous studies, we demonstrated that resins containing phosphate-bridged bisphthalonitrile monomers are easily processable due to their low melting temperature and wide processing window. In this study, we investigated the impact of bis(3-(3,4-dicyanophenoxy)phenyl)phenyl phosphate (PPhPN) monomer content on physico-chemical and mechanical properties, thermal stability, and thermal oxidative stability. This research highlights the importance of conducting long-term thermal oxidative aging studies in addition to thermogravimetric analysis to properly assess the stability of thermosets. The findings indicate that adding less than 15% of PPhPN results in the formation of a crystalline phase, which impairs the resin's processability. Conversely, a high PPhPN content reduces the material's thermal oxidative stability. Therefore, based on mechanical and physico-chemical tests after thermal oxidative aging, it can be concluded that a 10-15% concentration of the phosphate-containing monomer enables easy processability of the phthalonitrile resin and provides excellent long-term thermal oxidative stability at temperatures up to 300 °C, while maintaining a flexural strength exceeding 120 MPa and an elasticity modulus of 4.3 GPa.

Divalent metal ion in the active site of purple acid phosphatase modulates substrate binding: Kinetic and thermodynamic properties

The purple acid phosphatase was purified from 5.9-fold to apparent homogeneity from Anagelis arvensis seeds using SP-Sephadex C-50 and Sephadex G-100 chromatography. The results of residual activity tests conducted using different temperature ranges (50–70 °C) were calculated as the activation energy (Ed = 72 kJ/mol), enthalpy (69.31 ≤ (ΔH° ≤ 69.10 kJ/mol), entropy (−122.48 ≤ ΔS° ≤ −121.13 J/mol·K), and Gibbs free energy (108.87 ≤ ΔG° ≤ 111.25 kJ/mol) of the enzyme irreversible denaturation. These thermodynamic parameters indicate that this novel PAP is highly thermostable and may be significant for use in industrial applications. However, it may be confirmed by stopped-flow measurements that this substitution produces a chromophoric Fe3+ site and a Pi-substrate interaction that is about ten times faster. Additionally, these data show that phenyl phosphate hydrolysis proceeds more rapidly in metal form of A. arvensis PAP than the creation of a μ-1,3 phosphate complex. The Fe3+ site in the native Fe3+-Mn2+ derivative interacts with it at a faster rate than in the Fe3+-Fe2+ form. This is most likely caused by a network of hydrogen bonds between the first and second coordination spheres. This suggests that the choice of metal ions plays a significant role in regulating the activity of this enzyme.

Diisodecyl phenyl phosphate promotes foam cell formation by antagonizing Liver X receptor alpha

While the cardiovascular system is a primary target of organophosphorus flame retardants (OPFRs), particularly aryl-OPFRs, it is still exclusive whether the diisodecyl phenyl phosphate (DIDPP), widely used and broadly present in the environment at high concentrations, elicits atherosclerosis effects. Liver X receptors (LXRs) play a direct role in regulating the formation of atherosclerotic lesions. This study was the first to demonstrate that DIDPP acts as an LXRα ligand and functions as an LXRα antagonist with a half-maximal inhibitory concentration of 16.2 μM. We showed that treatment of an in vitro macrophage model with 1 to 10 μM of DIDPP resulted in the downregulation of direct targets of LXRα, namely ABCA1, ABCG1 and SR-B1, thereby leading to a 7.9–13.2 % reduction in cholesterol efflux. This caused dose-dependent, 24.1–43.1 % increases in the staining intensity of foam cells in the macrophage model. This atherosclerotic effect of DIDPP was proposed to be due to its antagonism of LXRα activity, as DIDPP treatment did not alter cholesterol influx. In conclusion, the findings of this study demonstrate that exposure to DIDPP may be a risk factor for atherosclerosis due to the LXRα-antagonistic activity of DIDPP and its ubiquity in the environment.

Integrated Approach for Testing and Assessment for Developmental Neurotoxicity (DNT) to Prioritize Aromatic Organophosphorus Flame Retardants.

Organophosphorus flame retardants (OPFRs) are abundant and persistent in the environment but have limited toxicity information. Their similarity in structure to organophosphate pesticides presents great concern for developmental neurotoxicity (DNT). However, current in vivo testing is not suitable to provide DNT information on the amount of OPFRs that lack data. Over the past decade, an in vitro battery was developed to enhance DNT assessment, consisting of assays that evaluate cellular processes in neurodevelopment and function. In this study, behavioral data of small model organisms were also included. To assess if these assays provide sufficient mechanistic coverage to prioritize chemicals for further testing and/or identify hazards, an integrated approach to testing and assessment (IATA) was developed with additional information from the Integrated Chemical Environment (ICE) and the literature. Human biomonitoring and exposure data were identified and physiologically-based toxicokinetic models were applied to relate in vitro toxicity data to human exposure based on maximum plasma concentration. Eight OPFRs were evaluated, including aromatic OPFRs (triphenyl phosphate (TPHP), isopropylated phenyl phosphate (IPP), 2-ethylhexyl diphenyl phosphate (EHDP), tricresyl phosphate (TMPP), isodecyl diphenyl phosphate (IDDP), tert-butylphenyl diphenyl phosphate (BPDP)) and halogenated FRs ((Tris(1,3-dichloro-2-propyl) phosphate (TDCIPP), tris(2-chloroethyl) phosphate (TCEP)). Two representative brominated flame retardants (BFRs) (2,2'4,4'-tetrabromodiphenyl ether (BDE-47) and 3,3',5,5'-tetrabromobisphenol A (TBBPA)) with known DNT potential were selected for toxicity benchmarking. Data from the DNT battery indicate that the aromatic OPFRs have activity at similar concentrations as the BFRs and should therefore be evaluated further. However, these assays provide limited information on the mechanism of the compounds. By integrating information from ICE and the literature, endocrine disruption was identified as a potential mechanism. This IATA case study indicates that human exposure to some OPFRs could lead to a plasma concentration similar to those exerting in vitro activities, indicating potential concern for human health.

Quantification of Irgafos P-168 and Degradative Profile in Samples of a Polypropylene/Polyethylene Composite Using Microwave, Ultrasound and Soxhlet Extraction Techniques

In polypropylene/polyethylene composite (C-PP/PE) production, stabilizing additives such as Irgafos P-168 are essential as antioxidant agents. In this study, an investigation was carried out that covers different solid–liquid extraction methods (Soxhlet, ultrasound, and microwaves); various variables were evaluated, such as temperature, extraction time, the choice of solvents, and the type of C-PP/PE used, and the gas chromatography coupled to mass spectrometry (GC-MS) technique was used to quantify the presence of Irgafos P-168 in the C-PP/PE samples. The results revealed that microwave extraction was the most effective in recovering Irgafos P-168. A recovery of 96.7% was achieved when using dichloromethane as a solvent, and 92.83% was achieved when using limonene as a solvent. The ultrasound technique recovered 91.74% using dichloromethane and 89.71% using limonene. The Soxhlet extraction method showed the lowest recovery percentages of 57.39% using dichloromethane as a solvent and 55.76% with limonene, especially when the C-PP/PE was in the form of pellets. The degradation products that obtained the highest degradation percentages were Bis (di-test-butyl phenyl) phosphate and Mono (di-test-butyl phenyl) phosphate using the microwave method with dichloromethane as a solvent and PP in film. Finally, the possible mechanisms for forming the degradation compounds of Irgafos P-168 were postulated.

Isolation and biochemical characterization of novel acid phosphatase and zinc-dependent acid phosphatase from the chicken's brain

The AcPase exhibits a specific activity of 31.32 U/mg of protein with a 728-fold purification, and the yield of the enzyme is raised to 3.15 %. The Zn2+-dependent AcPase showed a purification factor of 1.34 specific activity of 14 U/mg of proteins and a total recovery of 5.14. The SDS-PAGE showed a single band corresponding to a molecular weight of 18 kDa of AcPase and 29 kDa of Zn2+-dependent AcPase. The AcPase enzyme has shown a wide range of substrate specificity for p-NPP, phenyl phosphate and FMN, while in the case of ZnAcPase α and β-Naphthyl phosphate and p-NPP were proved to be superior substrates. The divalent metal ions like Mg2+, Mn2+, and Ca2+ increased the activity, while other substrates decreased the enzyme activity. The Km (0.14 mM) and Vmax (21 μmol/min/mg) values of AcPase were higher than those of Zn2+-AcPase (Km = 0.5 mM; Vmax = 9.7 μmol/min/mg). The Zn2+ ions activate the Zn2+-AcPase while Fe3+, Al3+, Pb2+, and Hg2+ showed inhibition on enzyme activity. Molybdate, vanadate and phosphate were found to be competitive inhibitors of AcPase with Ki values 316 μM, 185 μM, and 1.6 mM, while in Zn2+-AcPase tartrate and phosphate also showed competitive inhibition with Ki values 3 mM and 0.5 mM respectively.

Electrografting of Phenyl Phosphate Layers onto Glassy Carbon for Tuning Catalytic Activity toward the Hydrogen Evolution Reaction.

In this study, we explored the surface modification of a glassy carbon electrode through the electrografting of 4-Aminophenyl phosphate, which features heteroatoms and ionic properties. The electrochemical grafting process involves reducing in situ-generated diazonium derivatives. The primary objective of this research was to immobilize organic layers and assess their electrochemical and surface properties. Subsequently, the generated surface serves as a template for the electrochemical growth of Pd and Co nanoparticles on functionalized electrodes. The electrocatalytic performances of these hybrid electrodes in driving the hydrogen evolution reaction were investigated. The obtained results indicate an enhancement in the electrocatalytic activity of the modified electrodes, where lower overpotential and higher stability were observed when the catalyst was electrodeposited onto the attached ionic layer. These findings highlight the synergistic effect between the attached phenyl phosphate moieties and electrocatalysts.

Dual-readout colorimetric immunoassay based on halogenated indophenol for rapid detection of aflatoxin B1

Aflatoxin B1 (AFB1) is one of the most toxic mycotoxins. In view of the great harm of AFB1, it has attracted much attention to explore a super-sensitive and low-cost rapid detection method for aflatoxin B1. Herein, a dual-readout colorimetric immunoassay was established for the detection of AFB1. Under the catalysis of alkaline phosphatase (ALP), phenyl phosphate (PP) can produce phenol by dephosphorylation. Then phenol can react with 2,6-dibromoquinone-4-chloroimide (DBQC) under alkaline conditions to produce blue halogenated indophenol (HIP). Through this reaction, the color of the solution became blue, which can be observed by the naked eye. In addition, this color signal can be converted into digital signal via smartphone, enabling quantitative detection of AFB1. Under the optimal condition, the detection limit of this colorimetric immunoassay was 0.70 ng/mL by naked eye and 0.013 ng/mL by smartphone. The application results showed that the proposed daul-readout colorimetric immunoassay was feasible and real-time for AFB1 detection in actual samples.

Study on the Preparation of a Polydiethylene Phenyl Phosphate Resin and its Adsorption of Cu2+ in Wastewater

In view of the problems and imperfections in the synthesis of phosphoric acid resins by existing techniques, we prepared a different phosphoric acid resin and used it to adsorb Cu2+ in wastewater. When phosphoric acid resin is prepared using cross-linked polydiethylbenzene resin as a matrix, the experimental raw material can be more selective and the experimental process is safe and non-toxic. The particle size of the synthesized resin is uniform, most of which are distributed in 100-300 μm, and the functional group content can be as high as 2.4 mmol/g. The static/dynamic adsorption on Cu2+ is excellent, with a static adsorption capacity of 51.2 mg/g. When hydrochloric acid is used as an eluant, the resin has favorable reproducibility, which provides a reference value for the preparation and application of phosphate resins.

Self-Assembled Integrated Nanozyme Cascade Biosensor with Dual Catalytic Activity for Portable Urease Analysis.

In this work, a novel nanozyme (Cu@Zr) with all-in-one dual enzyme and fluorescence properties is designed by simple self-assembly. A nanozyme cascade sensor with disodium phenyl phosphate (PPDS) as substrate was first established by exploiting the dual enzymatic activities of phosphatase and laccase. Specifically, phosphatase cleaves the P-O bond of PPDS to produce colorless phenol, which is then oxidized by laccase and complexed with the chromogenic agent 4-aminoantipyrine (4-AP) to produce red quinoneimine (QI). Strikingly, the NH3 produced by the urease hydrolysis of urea can interact with Cu@Zr, accelerating the electron transfer rate and ultimately leading to a significantly improved performance of the cascade reaction. Moreover, the fluorescence at 440 nm of Cu@Zr is further quenched by the inner filter effect (IFE) of QI. Thus, the colorimetric and fluorescence dual-mode strategy for sensitive urease analysis with LODs of 3.56 and 1.83 U/L was established by the proposed cascade sensor. Notably, a portable swab loaded with Cu@Zr was also prepared for in situ urease detection with the aid of a smartphone RGB readout. It also provides a potentially viable analytical avenue for environmental and biological analysis.

Efficient phenyl phosphate ester extractant synthesis and solvent extraction performance evaluation for transition metals

The extraction performance of traditional acidic phosphate ester extractants (P204 and P507) will decrease sharply as the aqueous-phaseacidity increases. Although saponification pretreatment can maintain the stability of aqueous-phase acidity during solvent extraction, allowing for the efficient extraction of target metals, it also generates a large amount of salt-contaminated wastewater. Thus, an acid-resistant phenyl phosphate ester extractant was synthesized based on the conjugated effect of the benzene ring, and the impact of synthesis temperature on its structural composition and extraction performance was studied. The molecular structures of the synthesized products were determined as [(CH3)3CCH2C(CH3)2C6H4O]2P(=O)OH (phosphate di-ester, DAP) and (CH3)3CCH2C(CH3)2C6H4OP(=O)(OH)2 (phosphate mono-ester, MAP) through FT-IR, NMR, and HRMS characterization. The extraction rates of Ni2+, Co2+, and Mn2+ by DAP/MAP synthesized at 75 °C were 57.58 %, 69.42 %, and 75.70 %, respectively, without saponification pretreatment. Under the same conditions, the extraction rates of Ni2+, Co2+, and Mn2+ by P204 were 21.16 %, 16.11 %, and 19.31 %, while those by P507 were 22.79 %, 9.05 %, and 11.31 %, respectively. The density functional theory (DFT) calculations indicate that P = O and P-OH groups are the active centers of the DAP/MAP coordination reaction with metal ions. The Gibbs free energy changes during extraction reveal the performance difference between DAP and MAP (sequence: DAP > MAP). The order of coordination ability of the three transition metal ions with DAP and MAP is Mn2+ > Co2+ > Ni2+, consistent with the experimental data.

Mechanism of interaction between ascorbic acid and soil iron-containing minerals for peroxydisulfate activation and organophosphorus flame retardant degradation

Soil constituents may play an important role in peroxydisulfate (PDS)-based oxidation of organic contaminants in soil. Iron-containing minerals (Fe-minerals) have been found to promote PDS activation for organics degradation. Our study found that ascorbic acid (H2A) could enhance PDS activation by soil Fe-minerals for triphenyl phosphate (TPHP) degradation. Determination and characterization analyses of Fe fractions showed that H2A could induce the reductive dissolution of solid Fe-minerals and the increasing of oxygen vacancies/hydroxyl groups content on Fe-minerals surface. The increasing of divalent Fe (Fe(II)) accelerated PDS activation to generate reactive oxygen species (ROS). Electron paramagnetic resonance (EPR) and quenching studies showed that sulfate radicals (SO4•−) and hydroxyl radicals (HO•) contributed significantly to TPHP degradation. The composition and content of Fe-minerals and soil organic matter (SOM) markedly influenced ROS transformations. Surface-bond and structural Fe played the main role in the production of Fe(II) in reaction system. The high-concentration SOM could result in ROS consumption and degradation inhibition. Density functional theory (DFT) studies revealed that H2A is preferentially adsorbed at α-Fe2O3(012) surface through Fe–O–C bridges rather than hydrogen bonds. After absorption, H atoms on H2A may further be migrated to adjacent O atoms on the α-Fe2O3(012) surface. With the transformation of H atoms to the α-Fe2O3(012) surface, the Fe–O–C bridge is broken and one electron is transferred from the O to Fe atom, inducing the reduction of trivalent Fe (Fe(III)) atom. MS/MS2 analysis, HPLC analysis, and toxicity assessment demonstrated that TPHP was transformed to less toxic 4-hydroxyphenyl diphenyl phosphate (OH-TPHP), diphenyl hydrogen phosphate (DPHP), and phenyl phosphate (PHP) through phenol-cleavage and hydroxylation processes, and even be mineralized in reaction system.

Nontargeted Analysis Reveals a Broad Range of Bioactive Pollutants in Drinking Water by Estrogen Receptor Affinity-Mass Spectrometry.

Exposure to environmental endocrine-disrupting chemicals (EDCs) can cause extensive health issues. However, specific EDCs remain elusive. This work aimed at performing nontargeted identification of estrogen receptor α (ERα)-active compounds using an ERα protein affinity assay combined with high-resolution mass spectrometry in the source and drinking water sampled from major rivers in China. Fifty-one potential ERα-active compounds across 13 categories were identified. For the first time, diisodecyl phenyl phosphate was found to have antiestrogenic activity, and three chemicals (galaxolidone, bensulfuron methyl, and UV234) were plausible ERα ligands. Among the 51 identified compounds, 12 were detected in the aquatic environment for the first time, and the concentration of N-phenyl-2-naphthylamine, a widely used antioxidant in rubber products, was up to 1469 and 1190 ng/L in source and drinking water, respectively. This study demonstrated the widespread presence of known and unknown ERα estrogenic and antiestrogenic pollutants in the major rivers that serve as key sources of drinking water in China and the low removal efficiency of these chemicals in drinking water treatment plants.

Simple dual-readout immunosensor based on phosphate-triggered and potassium permanganate for visual detection of fenitrothion

Multicolor-based visual immunosensor is a promising tool for rapid analysis without the use of bulky instruments. Herein, an anti-fenitrothion nanobody-alkaline phosphatase fusion protein (VHHjd8-ALP) was employed to develop a multicolor visual immunosensor (MVIS) and a ratiometric fluorescence MVIS (RFMVIS, respectively). After one-step competitive immunoassay, the VHHjd8-ALP bound to microplate catalyzed phenyl phosphate disodium salt (ArP) into phenol. Under high alkaline condition (pH 12), the phenol reduced KMnO4 to intermediate (K2MnO4) and further to MnO2 in alkaline condition (pH 12), accompanied by a visible color transition of purple-green-yellow, which can be used for semiquantitative visual analysis or qualitative detection by measuring RGB value. RFMVIS was proposed on the basis of MVIS to further improve sensitivity. The CdTe quantum dot and fluorescein were used as signal probes to develop the fluorescent immunosensor. The CdTe dots with red emission (644 nm) was quenched by oxidation of KMnO4, whereas the fluorescein with green emission (520 nm) remained constant, accompanied by a fluorescent color transition of green-yellow-red. By measuring the ratio of the fluorescence intensity (I644/I520), the ratiometric fluorescence immunosensor was developed for qualitative analysis. The two visual immunosensors were sensitive and simple, and they showed good accuracy and practicability in the recovery test, thus are ideal tools for rapid screening.

Organophosphate ester (OPE) exposure among waste recycling and administrative workers in Denmark using silicone wristbands

In a recent estimate, 96 million tons of hazardous waste were produced in the European Union, most of which were handled among the member states. Organophosphate esters (OPEs) are applied as flame retardants and plasticizers and are present in many products, e.g., electronics, which end up in the hazardous waste stream upon disposal. Given the growing body of information suggesting potential adverse health effects of OPEs, waste recycling workers who handle hazardous waste could potentially be at risk of elevated exposure to these chemicals. Using silicone wristbands, we evaluated OPE exposure among waste recycling workers who handled hazardous waste and compared their exposure to that of administrative workers from the same waste companies. Wristbands were extracted and analyzed for six OPEs, which were all detected in >75% of wristbands. Overall, the sum of tris(2-chloroisopropyl) phosphate (∑TCIPP) isomers was the most abundant OPE across all wristbands collected within the study. In general, the sum of tri(methyl phenyl) phosphate isomers (∑TMPP) was elevated for all waste workers (10β = 7.9), whereas tri-n-butyl phosphate (TnBP), tris(1,3-dichloroisopropyl) phosphate (TDCIPP), and ∑TMPP were 3–12 times higher among those specifically handling electronic and hazardous waste compared to the administrative workers (p < 0.05). Repeated wristband measurements from the same worker had fair to good consistency in OPE concentrations (intraclass correlation coefficients = 0.54–0.77), except for the two most volatile chlorinated OPEs. Taken together, our results suggest that waste recycling workers who handle electronic and hazardous waste have significantly elevated exposure to OPEs, and efforts to reduce these exposures should be considered.