Triethyl Phosphate Research Articles

Monitoring of OPFRs in WWTPs: Unveiling environmental insights with high resolution mass spectrometry

Exploring the occurrence pattern of organophosphate flame retardants (OPFRs) in environmental samples has attracted increasing attention lately. In the conventional wastewater treatment plants (WWTPs), OPFRs are not sufficiently removed and therefore are discharged to the aquatic environment. However, concerns arise from their release regarding the potential risk posed to organisms. Consequently, closely monitoring this group of emerging contaminants, along with the evaluation of the associated ecological risk are matters of utmost importance. Given the aforementioned information, influents and effluents from two WWTPs (WWTP-A and WWTP-S) in Thessaloniki were gathered during a 36-month sampling initiative spanning from 2020 to 2023 in order to evaluate the occurrence and concentration levels of OPFRs. The collected samples underwent solid-phase extraction and then preceded to analysis with a Q Exactive Focus Orbitrap mass analyzer. In the present study, except for the implementation of the target analysis approach, removal efficiencies and mass loads were further calculated. TBEP (tris-2-butoxyethylphosphate) and TEP (triethyl phosphate) were detected in all influent samples (%DF = 100 %) in WWTP-A while in WWTP-S only TCPP (tris-1-chloro-2-propyl phosphate) was omnipresent. In effluents of both WWTPs, only TEP maintained the same detection frequency (%DF = 100 %). The highest mean concentration levels in WWTP-S influents were calculated for TEP (327 ng/L) followed by TCPP (277 ng/L) while in WWTP-A the highest mean concentrations in influents were detected for TCPP (405 ng/L) and TDCP (Tris(1,3-dichloro-2-propyl)phosphate) (124 ng/L). In effluents, the highest mean concentration was reported for TCPP, in both WWTPs, reaching 295 ng/L and 240 ng/L in WWTP-S and WWTP-A respectively. Generally, OPFRs exhibited low to moderate average removal efficiencies. Positive and negative removal efficiencies were also noticed during the monitoring campaign. The average mass load in WWTP-S was as high as 10.1 mg/day/1000 inhabitants and in WWTP-A, 11 mg/day/1000 inhabitants in effluents. Finally, different mathematical tools were employed for the assessment of the risk posed to algae, invertebrates and fish. For the toxicity assessment in these three trophic levels the worst-case scenario was taken into consideration. Generally, all the target analytes presented low or medium values in all trophic levels for acute and chronic toxicity.

Interfacial Decomposition Behaviour of Triethyl Phosphate‐Based Electrolytes for Lithium‐Ion Batteries

Triethyl phosphate (TEP) is a cheap, environmentally benign, and non‐flammable electrolyte solvent, whose implementation in lithium‐ion batteries is held back by its co‐intercalation into graphite anodes, resulting in exfoliation of the graphite structure. In this work, the electrode‐electrolyte interface behaviour of electrolytes containing up to 100% TEP was investigated and correlated to electrochemical performance. High capacity and stable cycling are maintained with up to 30% TEP in carbonate ester‐based electrolytes, but above this threshold the reversibility of Li+ intercalation into graphite drops sharply to almost zero. This represents a potential route to improved battery safety, while TEP can also improve safety indirectly by enabling the use of lithium bis(oxalato borate), a fluorine‐free salt with limited solubility in traditional electrolytes. To understand the poor performance at TEP concentrations of >30%, its solvation behaviour and interfacial reaction chemistry were studied. Nuclear magnetic resonance spectroscopy data confirms changes in the Li+ solvation shell above 30% TEP, while operando gas analysis indicates extensive gas evolution from TEP decomposition at the electrode above the threshold concentration, which is almost entirely absent below it. X‐ray photoelectron spectroscopy depth profiling of electrodes demonstrates poor passivation by the solid electrolyte interphase above 30% TEP and significant graphite exfoliation.

Do phosphorus amendments enhance biodegradation activity in stalled petroleum hydrocarbon-contaminated soil?

Phosphorus (P) fertilizers promote soil petroleum-hydrocarbon (PHC) bioremediation by correcting carbon-to-P ratio imbalances. While these inputs create conditions favorable to microbial growth, areas of a site or an entire site with low degradation rates (i.e., "stalled") occur for unknown reasons. We hypothesized that soil conditions limit P bioavailability, leading to stalls in PHC bioremediation, and adding the correct P amendment restarts microbial activity. Soils were collected and characterized from four cold calcareous PHC-impacted sites in Saskatchewan, Canada, undergoing bioremediation. A generalized linear mixed model identified that regions with lower degradation rates possessed a neutral pH with high magnetic and salinity values. In a subsequent laboratory experiment, the proportion of benzene degraded at greater rates within active (i.e., higher degradation rates) than stalled soils, thereby following model predictions (p-value=0.19, Kruskal-Wallis). The PHC degradation efficiency of different P amendments was tested by doping stalled soils (n=3) with one of five treatments: 0 (control), 0 (autoclaved control), or 50mg phosphate kg-1 soil as sodium diphosphate, triethyl phosphate, or tripolyphosphate. Tripolyphosphate accelerated benzene degradation (75.5±5.4%) in one stalled soil (Outlook 323) and increased degradation non-significantly (43.9±9.4%) in another (Allan 917). Alternatively, the final sample (Davidson 421) possessed the greatest benzene removal with no amendments. This implies that soil P bioavailability may not be the sole cause of decreased microbial activity. Accordingly, combining model outputs with mineralogy and microbiology investigations could enhance PHC biodegradation rates in these cold calcareous soils.

Aliphatic hyperbranched polyphosphate: a novel multicolor RTP material with AIE character.

Long-lived photoluminescent probes are emerging as significant luminogens for biological imaging. However, currently, most long-lived luminescent materials contain expensive rare elements or cytotoxic bulky aromatic or conjugated units. Herein, a novel hyperbranched polyphosphate (HBPPE) was synthesized using triethyl phosphate (TEP) and ethylene glycol (EG) through a transesterification polycondensation reaction. The obtained HBPPE P1 can emit bright blue photoluminescence under UV light and show significant AIE character. Interestingly, the average photoluminescence lifetime of P1 is 12.82 μs. This suggests the first phosphorescent material without rare elements or aromatic structures attributed to the covalent-crystal-like structure. Besides, P1 shows an obvious red-shift along with the excitation wavelength, which emits blue, cyan, green, yellow and red photoluminescence, covering nearly all the visible light region. This study not only enriches the species of nonconventional multicolor AIE luminogens but also provides a concise method for the synthesis of HBPPE and demonstrates the possibility for phosphorescent materials without rare elements or bulky aromatic units.

Self‐Extinguishing and Low‐Cost Quasi‐Solid Polymer Electrolyte for Room Temperature Lithium Metal Batteries

AbstractMost modification strategies of polyethylene oxide (PEO)‐based solid polymer electrolyte focus on improving the room temperature ionic conductivity, while disregarding its inherent flammability that poses substantial safety hazard. Herein, a self‐extinguishing quasi‐solid‐state polymer electrolyte (PTTF‐SPE), which combines excellent room temperature electrochemical properties and high safety, has been developed by introducing triethyl phosphate (TEP) as a low‐cost and highly effective flame retardant. The cross‐linking structure derived from −CH2−CH2−O− segments of tetramethylene glycol dimethyl ether (TEGDME) and PEO makes a contribution to a high amorphous state of polymer. A robust solid electrolyte interphase (SEI) formed by preferential decomposition of fluoroethylene carbonate (FEC) that acts as a film‐forming additive, which can prevent TEP from degradation at lithium metal anode. The optimized PTTF‐SPE exhibits high ionic conductivity (0.54×10−3 S/cm) and lithium transference number (0.71) at room temperature. The LiFePO4||Li battery demonstrates excellent cycle life over 500 cycles at 0.5 C with a high average discharge capacity of 131 mAh/g. A symmetric Li||Li battery that operating for 850 hours indicates a good compatibility of PTTF‐SPE towards lithium metal. This work provides a new idea for developing high‐energy‐density and high‐safety lithium‐metal batteries (LMBs) for room temperature.

Designing network structure hydrogels derived from carrageenan- phosphated polymers by covalent and supramolecular interactions for potential biomedical applications

Recently, various efforts have been made to explore the potential of natural polysaccharides derived from sea weeds to promote sustainable development. Herein, carrageenan (CG), a polysaccharide extracted from red sea algae, was utilized to design network structures as hydrogels, aimed at significant applications in drug delivery (DD) systems. Hydrogels were designed by graft copolymerization reaction of poly(bis [2-methacryloyloxy] ethyl phosphate [poly(BMEP)] and poly(acrylic acid) [poly(AAc)] onto CG in the presence of a crosslinking agent. Hydrogels were developed by covalent linkage by graft copolymerization and supramolecular interactions, existing in the copolymers. Copolymers were characterized by Atomic force microscopy (AFM), Fourier transform infrared spectroscopy (FTIR), 13C-nuclear magnetic resonance (NMR), and X-ray diffraction (XRD) instrumentations. The drug diffusion exhibited a sustained pattern due to polymer-drug interactions. The drug release followed non-Fickian diffusion mechanism and the release profile was most accurately depicted by first order kinetic model. The biocompatible nature of the copolymer was demonstrated from the hemolytic index value signifying minimal adverse interactions with blood component upon exposure. A protein adsorption test was performed using bovine serum albumin (BSA), exhibiting 8.15 ± 0.26 % albumin adsorption. Polymers exhibited mucoadhesive character, evidenced by their requirement of a detachment force measuring 195 ± 4.72 mN for separation from the membrane during interactions with the mucosal surface. The hydrogels exhibited antioxidant properties, evidenced by 2, 2′-Diphenylpicrylhydrazyl (DPPH) assay, revealing copolymer capable of scavenging 58.21 ± 2.26 % of free radical. The hydrogel revealed antimicrobial activity against P. aeruginosa and S. aureus bacteria, a property further enhanced in hydrogels with the drug doxycycline. These findings suggest suitability of these hydrogels for biomedical applications, with a significant emphasis on drug delivery.

Tri-anions regulated solvation structure in intrinsically nonflammable phosphate-based electrolytes for stable lithium metal batteries

The cycling instability and unsafety blocked the application of lithium metal batteries (LMB). Nonflammable solvents are hoped to improve the security of LMB; however, employing these solvents will irreversibly damage the cycling stability owing to incompatibility with Li metal. Herein, we regulated solvation structures in triethyl phosphate (TEP) through a simple Tri-anions strategy to achieve cycling stability and safety of LMB. Molecular dynamic simulation demonstrates that the solvation structure is well adjusted which can induce a powerful inorganic-rich solid electrolyte interface (SEI) to circumvent parasitic reactions between TEP solvents and Li anode as well as promote uniformly Li deposition. As a result, Li/LiNi0.8Co0.1Mn0.1O2 (NCM 811) cell has a capacity retention of 98.6 % after 300 cycles and Li/LiFePO4 (LFP) cell retains 75 % after 700 cycles. The novel electrolyte is expected to offer a promising approach for improving high safety and high-electrochemical-performance LMB.

Enhancing the Performance of Tyndall-Powell Gate Ion Mobility Spectrometry by Combining Ion Enrichment, Discrimination Reduction, and Temporal Compression into a Single Gating Process.

The broad applications of ion mobility spectrometry (IMS) demand good sensitivity and resolving power for ion species with different reduced mobilities (K0). In this work, a new Tyndall-Powell gate (TPG) gating method for combining ion enrichment, mobility discrimination reduction, and temporal compression into a single gating process is proposed to improve IMS analysis performance. The two-parallel-grid structure and well-confined gate region of the TPG make it convenient to spatiotemporally vary the electric fields within and around the gate region. Under the new gating method, a potential wave is applied on TPG grid 1 to enrich ions within the ionization region adjacent to the TPG during the gate-closed state; meanwhile, a potential wave is applied on TPG grid 2 to enhance mobility discrimination reduction and temporal compression simultaneously during the gate-open state. For triethyl phosphate (TEP) and dimethyl methylphosphonate mixtures, product ion peaks within K0 of 1.9 to 1.1 cm2/V·s exhibit a 19-fold increase in ion current compared to the traditional TPG gating method, while maintaining a resolving power of 85. The estimated limit of detection for the TEP dimer is lowered from 8 ppb to 135 ppt. The new gating method can be applied to other TPG-based IMS systems to enhance their performance in analyzing complex samples.

Enhancing the Cathode/Electrolyte interface in Ni-Rich Lithium-Ion batteries through homogeneous oxynitridation enabled by NO3− dominated clusters

To meet the demand for higher energy density in lithium-ion batteries, extensive research has focused on advanced cathodes and metallic lithium anodes. However, Ni-rich cathodes suffer from the inactive phase-transition and side reactions at the cathode-electrolyte interfaces (CEI). In this study, we propose a novel approach to enhance the solubility of LiNO3 in carbonate electrolyte systems using a local high-concentrated addition strategy with triethyl phosphate as a co-solvent. Rather than the traditional solvent-dominated solvation clusters, the NO3− dominated electrolyte is examined to elucidate unique complexation phenomena. Two distinct clusters in NO3− dominated electrolyte arising from as a consequence of intramolecular interactions intrinsic to the constituents. This promotes the formation of a homogeneous oxynitride interphase and facilitates more expeditious lithium ion diffusion kinetics. Hence, the less stress fragmentation and irreversible phase transformation occur on the cathode surface with the homogeneous oxynitridation interface. This innovative design enables efficient cycling of the Li || NCM811 cell, offering a promising strategy to improve lithium-ion batteries performance.

Sustainable fabrication of solvent resistant biodegradable cellulose membranes using green solvents

The paradigm of the polymer industry is confronting an inevitable transition from fossil-based to bio-derived sources. The membrane-based separation process, generally regarded as a sustainable technology, mostly employs fossil-based polymeric membranes. In order to become an entirely carbon–neutral technology, all of the materials and chemicals employed during membrane fabrication must be scrutinized from a sustainability perspective. In this work, we report a versatile strategy to fabricate solvent-resistant cellulose membranes using bio-derived green solvents. The thermodynamic and kinetic aspects of the membrane fabrication process were systematically investigated. It was found that well-known green solvents such as Cyrene and PolarClean were not suitable due to high dope viscosity, whereas bio-derived methyl lactate and triethyl phosphate exhibited desirable properties to yield excellent cellulose membranes. The membrane performance could be tailored from the ultrafiltration to nanofiltration range by controlling the fabrication parameters. Importantly, the thermal treatment step prior to the deacetylation reaction was necessary to improve the solute rejection profile. The cellulose membranes displayed adequate compression resistance against pressure. However, their shear resistance was insufficient compared to that of commercial membranes. Nevertheless, the prepared cellulose membranes exhibited excellent solvent resistance in strong aprotic solvents such as N-methylpyrrolidone and N,N-dimethylacetamide, potentially allowing them to enter niche membrane markets such as the organic solvent nanofiltration (OSN).

Dendrite‐Free Zn Metal Anodes with Boosted Stability Achieved by Four‐in‐One Functional Additive in Aqueous Rechargeable Zinc Batteries

AbstractZn interfacial issues involved dendrite evolution and undesired parasitic reactions are tough challenges to impede the progress of Zn ion battery. Herein, dendrite‐free Zn anode with boosted stability is achieved by four‐in‐one functional additive triethyl phosphate (TEP). Experiments and theoretical calculation reveal that TEP additive participates in the generation of compact inorganic interface to prevent Zn from corrosion. Meanwhile, the interfacial electrical double layer (EDL) is reconstructed with adsorbed TEP molecules in inner layer and weakened Zn2+ solvation structure in diffusion layer, which efficiently shields Zn from active H2O and moderate electrochemical kinetics, thereby preventing water‐related secondary reaction and Zn electroplating on tip region. Additionally, TEP additive manipulates zinc growth direction by adsorbing on the (002) facet, thus enabling long‐lasting dendrite‐free deposition. Accordingly, Zn||Zn symmetric cell demonstrates an ultralong lifespan over 5000 h (almost 7 months) at 1 mA cm−2, 1 mAh cm−2 and remarkable coulombic efficiency (CE) of ≈97.6% for 1500 cycles. For practical demonstration, Zn||LiFePO4 full cell demonstrates an improved rate capability and an elevated capacity of 116.0 mAh g−1. These findings highlight interface chemistry manipulated by multifunctional additives as an efficient approach to stabilize Zn anode, holding promise for top‐notch Zn‐based batteries with improved longevity.

Harnessing melt processing for the preparation of mechanically robust thermoplastic vulcanizate electrolytes

We report a new type of polymer blend electrolyte based on the principle of thermoplastic vulcanizates (TPV). TPV materials have been extensively used in the automotive and manufacturing sectors. However, to the best of our knowledge, TPV-based electrolytes have yet to be produced. These electrolytes, obtained via melt-processing, combine the high ionic conductivity and processibility of a thermoplastic phase with the improved mechanical strength of a crosslinked elastomeric phase. TPV electrolytes prepared with poly(caprolactone) (PCL) (thermoplastic phase) and hydrogenated nitrile butadiene rubber (HNBR) (elastomeric phase) are presented in this work. These materials deliver promising results in terms of ionic conductivity, electrochemical stability and mechanical strength. Further improvements in ionic conductivity are obtained by doping the TPV electrolyte with a flame-retardant solvent, triethyl phosphate. The crosslinked nature of the TPV allows both mechanical strength and electrochemical stability to be conserved upon doping which is not possible in non-crosslinked polymer blend electrolytes prepared with PCL and HNBR.

OPFR removal by white rot fungi: screening of removers and approach to the removal mechanism.

The persistent presence of organophosphate flame retardants (OPFRs) in wastewater (WW) effluents raises significant environmental and health concerns, highlighting the limitations of conventional treatments for their remotion. Fungi, especially white rot fungi (WRF), offer a promising alternative for OPFR removal. This study sought to identify fungal candidates (from a selection of four WRF and two Ascomycota fungi) capable of effectively removing five frequently detected OPFRs in WW: tributyl phosphate (TnBP), tributoxy ethyl phosphate (TBEP), trichloroethyl phosphate (TCEP), trichloro propyl phosphate (TCPP) and triethyl phosphate (TEP). The objective was to develop a co-culture approach for WW treatment, while also addressing the utilization of less assimilable carbon sources present in WW. Research was conducted on carbon source uptake and OPFR removal by all fungal candidates, while the top degraders were analyzed for biomass sorption contribution. Additionally, the enzymatic systems involved in OPFR degradation were identified, along with toxicity of samples after fungal contact. Acetate (1.4 g·L-1), simulating less assimilable organic matter in the carbon source uptake study, was eliminated by all tested fungi in 4 days. However, during the initial screening where the removal of four OPFRs (excluding TCPP) was tested, WRF outperformed Ascomycota fungi. Ganoderma lucidum and Trametes versicolor removed over 90% of TnBP and TBEP within 4 days, with Pleorotus ostreatus and Pycnoporus sanguineus also displaying effective removal. TCEP removal was challenging, with only G. lucidum achieving partial removal (47%). A subsequent screening with selected WRF and the addition of TCPP revealed TCPP's greater susceptibility to degradation compared to TCEP, with T. versicolor exhibiting the highest removal efficiency (77%). This observation, plus the poor degradation of TEP by all fungal candidates suggests that polarity of an OPFR inversely correlates with its susceptibility to fungal degradation. Sorption studies confirmed the ability of top-performing fungi of each selected OPFR to predominantly degrade them. Enzymatic system tests identified the CYP450 intracellular system responsible for OPFR degradation, so reactions of hydroxylation, dealkylation and dehalogenation are possibly involved in the degradation pathway. Finally, toxicity tests revealed transformation products obtained by fungal degradation to be more toxic than the parent compounds, emphasizing the need to identify them and their toxicity contributions. Overall, this study provides valuable insights into OPFR degradation by WRF, with implications for future WW treatment using mixed consortia, emphasizing the importance of reducing generated toxicity.

Coordination structure regulation in non-flammable electrolyte enabling high voltage lithium electrochemistry

High-voltage battery systems bring significant increases in energy density but are also accompanied by fast degradation of electrochemical performance and serious safety issues. Herein, Li+ coordination structure regulation was conducted to formulate a non-flammable electrolyte, which consists of 1.5 M lithium bis (fluor sulfonyl) imide (LiFSI) in triethyl phosphate and methyl 2,2,2-trifluoromethyl carbonate (FEMC). The renamed TEP-FEMC-FEC (TFF) electrolyte exhibits an FSI−-dominated solvation structure contributed by the weakly-solvating ability of FEMC. The generated inorganic-rich interfacial layers are conducive to stabilizing the phase transition of high-voltage cathodes while suppressing the dendritic growth on lithium metal or co-intercalation behavior in graphite anode. This TFF electrolyte enables LiCoO2 || Li batteries to achieve capacity maintenance over 79% after 400 cycles with high-rate of 5 C at an ultra-high voltage of 4.6 V, and an outstanding capacity exceeding 100 mA h g−1 even at a super-high current density of 20 C. Additionally, the Ah-level LiCoO2 || graphite pouch cells also exhibit high capacity retention and satisfactory safety performance even under fast charging. This work provides a novel research direction for the pursuit of high energy density non-flammable electrolytes.

Air-Stable and Low-Cost High-Voltage Hydrated Eutectic Electrolyte for High-Performance Aqueous Aluminum-Ion Rechargeable Battery with Wide-Temperature Range.

Aqueous aluminum-ion batteries (AAIBs) are considered as a promising alternative to lithium-ion batteries due to their large theoretical capacity, high safety, and low cost. However, the uneven deposition, hydrogen evolution reaction (HER), and corrosion during cycling impede the development of AAIBs, especially under a harsh environment. Here, a hydrated eutectic electrolyte (AATH40) composed of Al(OTf)3, acetonitrile (AN), triethyl phosphate (TEP), and H2O was designed to improve the electrochemical performance of AAIBs in a wide temperature range. The combination of molecular dynamics simulations and spectroscopy analysis reveals that AATH40 has a less-water-solvated structure [Al(AN)2(TEP)(OTf)2(H2O)]3+, which effectively inhibits side reactions, decreases the freezing point, and extends the electrochemical window of the electrolyte. Furthermore, the formation of a solid electrolyte interface, which effectively inhibits HER and corrosion, has been demonstrated by X-ray photoelectron spectroscopy, X-ray diffraction tests, and in situ differential electrochemical mass spectrometry. Additionally, operando synchrotron Fourier transform infrared spectroscopy and electrochemical quartz crystal microbalance with dissipation monitoring reveal a three-electron storage mechanism for the Al//polyaniline full cells. Consequently, AAIBs with this electrolyte exhibit improved cycling stability within the temperature range of -10-50 °C. This present study introduces a promising methodology for designing electrolytes suitable for low-cost, safe, and stable AAIBs over a wide temperature range.

Micro-shear bond strength of a novel resin-modified glass ionomer luting cement (eRMGIC) functionalized with organophosphorus monomer to different dental substrates

ObjectivesThis study aims to assess and compare the micro-shear bond strength (μSBS) of a novel resin-modified glass-ionomer luting cement functionalized with a methacrylate co-monomer containing a phosphoric acid group, 30 wt% 2-(methacryloxy) ethyl phosphate (2-MEP), with different substrates (dentin, enamel, zirconia, and base metal alloy). This assessment is conducted in comparison with conventional resin-modified glass ionomer cement and self-adhesive resin cement. Materials and methodsIn this in vitro study, ninety-six specimens were prepared and categorized into four groups: enamel (A), dentin (B), zirconia (C), and base metal alloys (D). Enamel (E) and dentin (D) specimens were obtained from 30 human maxillary first premolars extracted during orthodontic treatment. For zirconia and metal alloys, 48 disks were manufactured using IPS e.max ZirCAD through dry milling and Co–Cr powder alloy by selective laser milling. Each group was further subdivided into three subgroups (n = 8) according to the luting cement used: (1) Fuji PLUS resin-modified glass ionomer luting cement (FP) as a control cement, (2) modified control cement (eRMGIC), and (3) RelyX U 200 (RU 200) self-adhesive resin cement. The two-way analysis of variance and Tukey's HSD were used to assess the data obtained from measuring the μSBS of the samples. ResultsThe results of this study showed that the mean μSBS values of eRMGIC were statistically higher compared to FP in all tested groups (p < 0.001). The mean μSBS results of eRMGIC were non-significantly different from those recorded by RU 200 for all substrates except for the dentin substrate, where the RU200 cement produced significantly higher strength (p < 0.001). The failure modes were limited to a combination of mixed and adhesive failures without pure cohesive failure. SignificanceThe functionalization of FP with an organophosphorus co-monomer (2-MEP) directly affects the adhesion performance of the functionalized cement, which may be utilized to develop a new type of acid-base cement. It exhibited a performance comparable to that of resin-based cement and should serve well under different clinical conditions.

Gum karaya polymer-based biodegradable silver nanocomposite hydrogel through green approach for photocatalytic dye degradation and antimicrobial activity

The rise in industrialization and population growth has elevated water pollution to a critical environmental concern. This study introduces a novel polymer-mediated silver nanocomposite hydrogel for antibacterial activity and photocatalytic dye degradation for environmental remediation. In this study, silver nanocomposite hydrogels were developed using Karaya gum (KG), acrylamide, N-isopropyl acrylamide (NI), and 2-Bismethacryloyloxy ethyl phosphate (BMEP) as a crosslinker through a radical polymerization process. These hydrogels were utilized as templates for the eco-friendly synthesis of silver nanoparticles by employing an aqueous Canthium leaf extract as a reducing and stabilizing agent. Various analytical methods, including FTIR, UV–Vis, XPS, FESEM, EDX, XRD, AFM, and HRTEM, are characterized by the green synthesized KG-NIB-Ag nanocomposite hydrogel. Evaluation of the KG-NIB-Ag hydrogel involved examining its chemical composition, morphology, size, crystallinity, surface properties, bandgap, and chemical purity. TEM analysis validated an average crystallite size 33.2 nm. Moreover, the photocatalytic performance of the green-synthesized KG-NIB-Ag nanocomposite hydrogel was utilized to examine the degradation of Congo red dye under visible light irradiation. The findings of this study demonstrate that the degradation efficiency of CR reached approximately 73.25 % within 90 min, with a corresponding kinetic rate constant of 0.032 min−1. Furthermore, the antibacterial efficacy of the Ag nanocomposite hydrogel was evaluated against both Staphylococcus aureus and Escherichia coli. The disc diffusion method was employed to assess its antibacterial activity, and the diameter of the inhibition zones was measured. This study introduces an innovative and influential strategy for environmental remediation, emphasizing the potential of KG-NIB-Ag nanocomposite hydrogel in tackling ecological challenges associated with wastewater treatment across various industries.

Investigation of Urinary Metabolites of Organophosphate Esters in Hanoi, Vietnam: Assessment Exposure and Estimated Daily Intake.

In recent years, organophosphate esters (OPEs) have become one of the most common additives in various consumer products worldwide, therefore the exposure and impact of OPEs on human health are drawing a lot of attention. In this study, three metabolites of OPEs including bis(1,3-dichloro-2-propyl) phosphate (BDCIPP), diphenyl phosphate (DPhP) and diethyl phosphate (DEP) were investigated in first-morning void urine samples taken from a population (age range: 3-76years old) in Hanoi, Vietnam. The most dominant urinary OPE metabolite was DEP with the geometric mean of specific gravity adjust (SG-adjusted) concentration were 1960ngmL-1 and detected frequency (DF) of 98%. Followed by DPhP (8.01ngmL-1, DF: 100%) and BDCIPP (2.18ngmL-1, DF: 51%). The results indicated that gender and age might have associations with the OPE metabolites variation in urine samples. The levels of OPE metabolites in urine samples from females were slightly higher than in males. An increase in age seems to have an association with a decrease in DPhP levels in urine. Exposure doses of parent OPEs were evaluated from the unadjusted urinary concentration of corresponding OPE metabolite. The estimated exposure doses of triethyl phosphate (TEP) (mean: 534,000ngkg-1d-1) were significantly higher than its corresponding reference dose, suggesting the high potential risk from the current exposure doses of TEP to human health. The results of this work provided the initial information on the occurrence of three OPE metabolites in urine from Hanoi, Vietnam and estimated exposure dose of corresponding parent OPEs.

Nontarget Identification of Novel Organophosphorus Flame Retardants and Plasticizers in Indoor Air and Dust from Multiple Microenvironments in China.

The indoor environment is a typical source for organophosphorus flame retardants and plasticizers (OPFRs), yet the source characteristics of OPFRs in different microenvironments remain less clear. This study collected 109 indoor air samples and 34 paired indoor dust samples from 4 typical microenvironments within a university in Tianjin, China, including the dormitory, office, library, and information center. 29 target OPFRs were analyzed, and novel organophosphorus compounds (NOPs) were identified by fragment-based nontarget analysis. Target OPFRs exhibited the highest air and dust concentrations of 46.2-234 ng/m3 and 20.4-76.0 μg/g, respectively, in the information center, where chlorinated OPFRs were dominant. Triphenyl phosphate (TPHP) was the primary OPFR in office air, while tris(2-chloroethyl) phosphate dominated in the dust. TPHP was predominant in the library. Triethyl phosphate (TEP) was ubiquitous in the dormitory, and tris(2-butoxyethyl) phosphate was particularly high in the dust. 9 of 25 NOPs were identified for the first time, mainly from the information center and office, such as bis(chloropropyl) 2,3-dichloropropyl phosphate. Diphenyl phosphinic acid, two hydroxylated and methylated metabolites of tris(2,4-ditert-butylphenyl) phosphite (AO168), and a dimer phosphate were newly reported in the indoor environment. NOPs were widely associated with target OPFRs, and their human exposure risk and environmental behaviors warrant further study.

A convenient method for the relative and absolute quantification of lipid components in liposomes by 1H- and 31P NMR-spectroscopy

ObjectiveLiposomes are promising delivery systems for pharmaceutical applications and have been used in medicine in the recent past. Preparation of liposomes requires reliable characterization and quantification of the phospholipid components for which the traditional cumbersome molybdate method is used frequently. The objective was to improve relative and absolute quantification of lipid components from liposomes. MethodsA reliable method for quantification of lipid composition in liposome formulations in the 1–10 μmol range with 1H- and 31P NMR spectroscopy at 600 MHz has been developed. The method is based on three crystalline small-molecule standards (Ph3PO4, (Tol)3PO4, and Ph3PO) in CDCl3. ResultsExcellent calibration linearity and chemical stability of the standards was observed. The method was tested in blind fashion on liposomes containing POPC, PEG-ceramide and a pH-sensitive trans-aminocyclohexanol-based amphiphile (TACH).11Et3PO4 Triethyl phosphate, Ph3PO4 triphenyl phosphate, (Tol)3PO4 tritolyl phosphate, Ph3PO triphenylphosphine oxide, POPC 1-palmitoyl-2-oleyl-sn-glycero-3-phosphocholine, DPPC 1,2-dipalmitoyl-sn-glycero-3-phosphocholine, DOPC 1,2-dioleyl-sn-glycero-3-phosphocholine, DOPE 1,2-dioleoyl-sn-glycero-3-phosphoethanolamine, POPE 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphoethanolamine, PEG-ceramide N-palmitoyl-sphingosine-1-(succinyl[methoxy(polyethylene glycol)2000]), COSY correlation spectroscopy, TOCSY total correlation spectroscopy, HMBC heteronuclear multiple-bond correlation, TACH trans-aminocyclohexanol, ANTS 8-aminonaphthalene-1,3,6-trisulfonic acid, disodium salt, DPX p-xylene-bis-pyridinium bromide, HEPES 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanesulfonic acid, pfg pulse-field gradient. Relative quantification (percentage of components) as well as determination of absolute lipid amount was possible with excellent reproducibility with an average error of 5%. Quantification (triplicate) was accomplished in 15 min based on 1H NMR and in 1 h based on 31P NMR. Very little change in mixture composition was observed over multiple preparative steps. ConclusionLiposome preparations containing POPC, POPE, DOPC, DPPC, TACH, and PEG-ceramide can be reliably characterized and quantified by 1H NMR and 31P NMR spectroscopy at 600 MHz in the μmol range.