Trimethyl Phosphate Research Articles

Enhancing the high temperature resistance of nanocomposite materials through dimethyl methyl phosphate impregnation‐coating treatment

AbstractIn order to enhance the thermal stability of polyvinyl alcohol (PVA), a modification scheme involving a dimethyl methyl phosphate (DMMP) impregnation‐coating treatment was adopted in this article. Initially, the interfacial compatibility of DMMP with PVA was characterized using scanning electron microscopy (SEM), inductively coupled plasma spectroscopy, elemental analysis and Fourier transform infrared spectroscopy (FTIR). Subsequently, the pyrolysis and combustion properties of DMMP‐coated PVA were evaluated via non‐isothermal thermogravimetric experiments and cone calorimeter tests. The pyrolysis products were then analyzed using a combination of thermogravimetric infrared chromatography and pyrolysis gas chromatography/mass spectrometry (Py‐GC/MS). Finally, a reaction model function closer to the actual co‐pyrolysis mechanism at high temperatures was established through thermal kinetics. The results indicated that the impregnation‐coating treatment could effectively distribute the DMMP molecules on the surfaces of PVA particles. Meanwhile, the DMMP coating could clearly slow the peak degradation rate of PVA grains and inhibit the combustion of PVA under fire conditions. Furthermore, the pyrolysis of DMMP‐coated PVA resulted in the formation of over 40 distinct compounds. The kinetic analysis revealed that the reaction model function established in this article could better characterize the actual reaction mechanism of the co‐pyrolysis of DMMP and PVA.

Effects of fluorine and phosphorus-based flame retardants addition on the lower flammability limit of dimethyl carbonate

This study initially examines the alteration pattern of the lower flammable limit (LFL) of dimethyl carbonate (DMC), a typical electrolyte component in lithium batteries, under the influence of inhibitors, namely di(2,2,2trifluoroethyl) carbonate (DtFEC), perfluorohexanone (C6F12O), and trimethylphosphate (TMP), through experimental investigation. Additionally, the critical inhibitory concentration required for complete inhibition is investigated. Subsequently, numerical simulations and chemical kinetic path analyses reveal how these inhibitors control combustion. Results show that C6F12O and DtFEC initially decrease and then increase the LFL of DMC, while TMP causes a monotonic increase. This is due to the competition between reaction-thermal and reaction-radical effects. Reaction kinetic analysis reveal that when small amounts of C6F12O and DtFEC are added, the fluorine-containing components decomposed by the reaction undergo oxidation, thereby promoting combustion. However, with increased amounts, these components combine with H and OH radicals to form stable substances like HF, inhibiting the combustion process. In the case of TMP, the phosphorus-containing intermediate components produced by cleavage catalyze the recombination of H and OH radicals, thereby inhibiting DMC combustion. The research findings offer a theoretical foundation for the development of safer lithium batteries and provide crucial data references for enhancing battery safety and prevention measures.

Ultralow Concentration Nonflammable Electrolytes Mediated by Intermolecular Interactions for Safer Potassium‐Ion Sulfur Batteries

AbstractDesigning electrolytes that are compatible with graphite anodes and possess flame‐retardant features is strongly demanded in potassium‐ion batteries (PIBs) to inhibit solvent co‐insertion and graphite exfoliation, and also stabilize the highly active potassium‐based species (e.g., KC8). Herein, a nonflammable electrolyte is designed by introducing the fluoroethers to stabilize graphite anodes, particularly at an ultralow concentration (<0.43 m) that is rarely reported before. It is discovered that intermolecular interactions can form between the 1,1,2,2‐tetrafluoroethyl‐2,2,3,3‐tetrafluoropropyl ether (i.e., HFE) diluent and trimethyl phosphate (TMP) flame‐retardant by electronegative fluorine (δ−F) and electropositive hydrogen (δ+H). The intermolecular interactions can change the potassium ion (K+) solvation structure (e.g., weakening the K+‐TMP interaction), and then determine the properties of the K+‐solvent‐anion complex at the electrode interface. a molecular interfacial model is presented with a new coordination mechanism involving the diluent to elucidate the relationship between the intermolecular interactions and electrode performance (i.e., K+‐solvent co‐insertion, or reversible K+ (de)intercalation) at the molecular scale, facilitating the design of high safety and high energy density potassium‐ion sulfur batteries. This study sheds light on the importance of intermolecular interactions to tune electrolyte properties and also opens new avenues for designing electrolytes for safe and practical PIBs.

PEG-based co-solvent aqueous electrolytes enabling high-energy rechargeable aqueous magnesium-ion batteries

In contrast to organic electrolyte systems, rechargeable aqueous magnesium-ion batteries (RAMIBs) offer unparalleled advantages, particularly in environmental sustainability, safety, cost-effectiveness, and their potential for large-scale energy storage. However, the practical implementation of RAMIBs has been hindered by the limited electrochemical stability of aqueous electrolytes. Although polyethylene glycol (PEG)-based aqueous electrolytes provide a wide electrochemical window, the poor ionic conductivity has restricted their widespread adoption. In this study, we address this challenge by employing trimethyl phosphate (TMP) and PEG400 as the co-solvent of aqueous magnesium-ion electrolytes. This combination significantly enhances the ionic conductivity to 4.44 mS cm−1 and increases the electrochemical stability window of the aqueous electrolyte by mitigating the activity of H2O. In addition, we underscore the role of TMP as a potent co-solvent in modulating the solvation structures of Mg2+ ions and modifying the electrochemical behavior of the electrolytes. Leveraging this advancement, in conjunction with a V2O5 cathode and a 3,4,9,10-perylenetetracarboxylic diimide (PTCDI) anode, the resulting RAMIBs demonstrate a remarkable discharge capacity of 227.6 mAh g−1, a large energy density of 157 Wh kg−1 and a high power density of 70 W kg−1. Our findings represent a significant stride toward exploiting the full potential of RAMIBs for future energy storage applications.

Structure-Dependent Distribution, Metabolism, and Toxicity Effects of Alkyl Organophosphate Esters in Lettuce (Lactuca sativa L.).

This study provides a comprehensive investigation into the structure-dependent uptake, distribution, biotransformation, and potential toxicity effects of alkyl organophosphate esters (OPEs) in hydroponic lettuce (Lactuca sativa L.). Trimethyl, triethyl, and tripropyl phosphates were readily absorbed and acropetally translocated, while tributyl, tripentyl, and trihexyl phosphates accumulated mainly in lateral roots. The acropetal translocation potential was negatively associated with log Kow values. Trimethyl and triethyl phosphates are less prone to biotransformation, while a total of 14 novel hydrolysis, hydroxylated, and conjugated metabolites were identified for other OPEs using nontarget analysis. The extent of hydroxylation decreases from tripropyl phosphate to trihexyl phosphate, but multiple hydroxylations occurred more frequently on longer chain OPEs. Further comparative toxicity test revealed that hydrolyzed and hydroxylated metabolites have stronger toxic effects on Ca2+-dependent protein kinases (CDPK) than their parent OPEs. Dibutyl 3-hydroxybutyl phosphate particularly induces upregulation of CDPK in lateral roots of lettuce, probably associated with adenine reduction that may play an important role in the self-defense and detoxification processes. This study contributes to understanding the uptake and transformation behaviors of alkyl OPEs as well as their associations with a toxic effect on lettuce. This emphasizes the necessary evaluation of the environmental risk of the use of OPEs, particularly focusing on their hydroxylated metabolites.

Value-Added Products Derived from Poly(ethylene terephthalate) Glycolysis.

Among polymer wastes, poly(ethylene terephthalate) (PET) is the most important commercial thermoplastic polyester. Less than 30% of total PET production is recycled into new products. Therefore, large amounts of waste PET need to be recycled. We describe a feasible approach for the direct application of the glycolysis products of PET (GP-PET), without further purification, for the synthesis of value-added products. It was established that GP-PET is valorized via phosphorylation with phenylphosphonic dichloride (PPD), as well as with trimethyl phosphate (TMP). When PPD is used, a condensation reaction takes place with the evolution of hydrogen chloride. During the interaction between GP-PET and TMP, the following reactions take place simultaneously: a transesterification with the participation of the hydroxyl group of GP-PET and the methoxy group of TMP and an exchange reaction between the ester group of GP-PET and the methyl ester group of TMP. The occurrence of the exchange reaction was confirmed by 1H, 31P, 13C NMR, and GPC analysis. Thermogravimetric analysis (TGA) revealed that the percentage of a carbon residual (CR) implies the possibility of using the end products as flame retardant (FR) additives, especially for polyurethanes as well as thermal stabilizers of polymer materials or Li-ion cells.

Apatite Formation on α-Tricalcium Phosphate Modified with Bioresponsive Ceramics in Simulated Body Fluid Containing Alkaline Phosphatase.

Bioresponsive ceramics, a new concept in ceramic biomaterials, respond to biological molecules or environments, as exemplified by salts composed of calcium ions and phosphate esters (SCPEs). SCPEs have been shown to form apatite in simulated body fluid (SBF) containing alkaline phosphatase (ALP). Thus, surface modification with SCPEs is expected to improve the apatite-forming ability of a material. In this study, we modified the surface of α-tricalcium phosphate (α-TCP) using methyl, butyl, or dodecyl phosphate to form SCPEs and investigated their apatite formation in SBF and SBF containing ALP. Although apatite did not form on the surface of the unmodified α-TCP in SBF, apatite formation was observed following surface modification with methyl or butyl phosphate. When ALP was present in SBF, apatite formation was especially remarkable on α-TCP modified with butyl phosphate. These SCPEs accelerated apatite formation by releasing calcium ions through dissolution and supplying inorganic phosphate ions, with the latter process only occurring in SBF containing ALP. Notably, no apatite formation occurred on α-TCP modified with dodecyl phosphate, likely because of the low solubility of the resulting calcium dodecyl phosphate/calcium phosphate composites. This new method of using SCPEs is anticipated to contribute to the development of novel ceramic biomaterials.

The Unimolecular Decomposition Mechanism of Trimethyl Phosphate.

Trimethyl phosphate (TMP), an organophosphorus compound (OPC), is a promising fire-retardant candidate for lithium-ion battery (LIB) electrolytes to mitigate fire spread. This study aims to understand the mechanism of TMP unimolecular thermal decomposition to support the integration of a TMP chemical kinetic model into a LIB electrolyte surrogate model. Reactive intermediates and products of TMP thermal decomposition were experimentally detected using vacuum ultraviolet (VUV) synchrotron radiation and double imaging photoelectron photoion coincidence (i2PEPICO) spectroscopy. Phosphorus-containing intermediates such as PO, HPO and HPO2 were identified. Sampling effects could successfully be obviated thanks to photoion imaging, which also showed evidence for isomerization reactions upon wall collisions in the ionization chamber. Quantum chemical calculations performed for the unimolecular decomposition of TMP revealed for the first time that isomerization channels via hydrogen and methyl transfer (barrier heights of 65.9 and 72.6 kcal/mol, respectively) are the lowest-energy primary steps of TMP decomposition followed by CH3OH/CH3/CH2O or dimethyl ether (DME) production, respectively. We found an analogous DME production channel in the unimolecular decomposition of dimethyl methylphosphonate (DMMP), another important OPC fire-retardant additive with a similar molecular structure to TMP, which are not included in currently available chemical kinetic models.

Nonwoven fabric supported flame-retarding quasi-solid electrolyte for wider-temperature safer Li-ion battery

Energy-dense lithium-ion battery (LIB) is in high demand for advanced portable electronics as well as electric vehicle EV applications. However, the flammability of conventional carbonate-based electrolytes makes the safety of the LIB questionable. Here, we demonstrate a nonflammable, thermally stable electrolyte for LIB application in the wide temperature range of −20 °C–50 °C. Specifically, we developed a non-woven fabric-supported quasi-solid flexible polymer electrolyte with a unique liquid electrolyte combination of methyl propionate (MP), trimethyl phosphate (TMP), fluoroethylene carbonate (FEC), and Poly (vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) polymer. The resulting composite electrolyte is compatible with Li metal, and in a half-cell (Li||LFP) performs superior to the commercial electrolyte over the wide temperature range. A full-cell with high-loading (cathode loading 13.2 mg/cm2) LFP combined with graphite demonstrated electrochemical performance. An initial discharge capacity of 115 mAh/g at a C/10 rate and capacity retention of 57 % was observed after 100 cycles. The thermal safety of the full cell was evaluated through multimodule calorimetry, where a low heat release of 37 J/g was observed, compared to 1.5 kJ/g with commercial electrolyte. This report aims to demonstrate the great potential of using flame-retardant quasi-solid polymer electrolytes for fabricating safer LIBs.

The Biopolymer Active Surface for Optical Fibre Sensors.

Optical fibre sensors have the potential to be overly sensitive and responsive, making them useful in various applications to detect the presence of pollutants in the environment, toxic gasses, or pesticides in soil. Deoxyribonucleic acid (DNA) as biopolymer active surfaces for fibre sensors can be designed to detect specific molecules or compounds accurately. In the article, we propose to use an optical fibre taper and DNA complex with surfactant-based sensors to offer a promising approach for gas detection, including ammonia solution, 1,4 thioxane, and trimethyl phosphate imitating hazardous agents. The presented results describe the influence of the adsorption of evaporation of measured agents to the DNA complex layer on a light leakage outside the structure of an optical fibre taper. The DNA layer with additional gas molecules becomes a new cladding of the taper structure, with the possibility to change its properties. The process of adsorption causes a change in the layer's optical properties surrounding a taper-like refractive index and increasing layer diameter, which changes the boundary condition of the structure and interacts with light in a wide spectral range of 600-1200 nm. The research's novelty is implementing a DNA complex active surface as the biodegradable biopolymer alignment for optical devices like in-line fibre sensors and those enabled for hazardous agent detection for substances appearing in the environment as industrial or even warfare toxic agents.

Unlocking 4.9 V Quasi-Solid-State Lithium Metal Battery via Solvent Screening and Interfacial Manipulation.

Parlous structure integrity of the cathode and erratic interfacial microdynamics under high potential take responsibility for the degradation of solid-state lithium metal batteries (LMBs). Here, high-voltage LMBs have been operated by modulating the polymer electrolyte intrinsic structure through an intermediate dielectric constant solvent and further inducing the gradient solid-state electrolyte interphase. Benefiting from the chemical adsorption between trimethyl phosphate (TMP) and the cathode, the gradient interphase rich in LiPFxOy and LiF is induced, thereby ensuring the structural integrity and interface compatibility of the commercial LiNi0.8Co0.1Mn0.1O2 (NCM811) cathode even at the 4.9 V cutoff voltage. Eventually, the specific capacity of NCM811|Li full cell based on TMP-modulated polymer electrolyte increased by 27.7% from 4.5 to 4.9 V. Such a universal screening method of electrolyte solvents and its derived electrode interfacial manipulation strategy opens fresh avenues for quasi-solid-state LMBs with high specific energy.

Realization of Long-Life Proton Battery by Layer Intercalatable Electrolyte.

Proton batteries have attracted increasing interests because of their potential for grid-scale energy storage with high safety and great low-temperature performances. However, their development is significantly retarded by electrolyte design due to free water corrosion. Herein, we report a layer intercalatable electrolyte (LIE) by introducing trimethyl phosphate (TMP) into traditional acidic electrolyte. Different from conventional role in batteries, the presence of TMP intriguingly achieves co-intercalation of solvent molecules into the interlayer of anode materials, enabling a new working mechanism for proton reactions. The electrode corrosion was also strongly retarded with expanded electrochemical stability window. The half-cell therefore showed an outstanding long-term cycling stability with 91.0 % capacity retention at 5 A g-1 after 5000 cycles. Furthermore, the assembled full batteries can even deliver an ultra-long lifetime with a capacity retention of 74.9 % for 2 months running at -20 °C. This work provides new opportunities for electrolyte design of aqueous batteries.

Realization of Long‐Life Proton Battery by Layer Intercalatable Electrolyte

Proton batteries have attracted increasing interests because of their potential for grid‐scale energy storage with high safety and great low‐temperature performances. However, their development is significantly retarded by electrolyte design due to free water corrosion. Herein, we report a layer intercalatable electrolyte (LIE) by introducing trimethyl phosphate (TMP) into traditional acidic electrolyte. Different from conventional role in batteries, the presence of TMP intriguingly achieves co‐intercalation of solvent molecules into the interlayer of anode materials, enabling a new working mechanism for proton reactions. The electrode corrosion was also strongly retarded with expanded electrochemical stability window. The half‐cell therefore showed an outstanding long‐term cycling stability with 91.0% capacity retention at 5 A g−1 after 5000 cycles. Furthermore, the assembled full batteries can even deliver an ultra‐long lifetime with a capacity retention of 74.9% for 2 months running at ‐20 °C. This work provides new opportunities for electrolyte design of aqueous batteries.

Tetraethylphosphonium tetrafluoroborate electrolyte for paving the way to construct high-power and high-voltage supercapacitors

Phosphonium-containing electrolytes offer a new avenue for advancing high-performance supercapacitors. In this study, for the first time, we investigated the physical and electrochemical characteristics of a new phosphonium salt—tetraethylphosphonium tetrafluoroborate (TEPBF4) in various solvents including acetonitrile (AN), propionitrile (PN), propylene carbonate (PC), and trimethyl phosphate (TMP). Our investigations revealed that TEPBF4/AN electrolytes demonstrated high solubility (2.15 M), high ionic conductivity (52.2 mS cm−1), and wide electrochemical stability windows (≥4.7 V), suggesting that TEPBF4/AN emerges as a compelling alternative to conventional ammonium salts in AN for developing high-power and high-voltage supercapacitors. Our results also showed that supercapacitors based on 1 M TEPBF4/AN achieved the highest capacitance (24.7 F g−1), superior rate performance, highest energy (24.9 Wh kg−1) and power densities (6752 W kg−1) among the investigated electrolytes. Furthermore, it retained 75 % of its capacitance after 1000 h float test at a high working voltage of 3.2 V, which significantly outperformed other supercapacitors using conventional ammonium salts in AN.

Degradation of organophosphate esters by UV/persulfate: Kinetic, mechanistic and toxicity evaluation

With the ban of brominated flame retardants, organophosphate esters (OPEs) have been widely used. The ultraviolet combined sodium persulfate (UV/PS) process is a promising advanced oxidation process (AOPs), which effectively removes organic micropollutants by generating various reactive substances such as hydroxyl radical (•OH) and sulfate radical (SO• 4−). The degradation kinetics, influencing factors, degradation path, and toxicity of three organic phosphates, trimethyl phosphate (TMP), tris (2-chloroethyl) phosphate (TCEP) and triphenyl phosphine oxide (TPPO) were studied. The results showed that UV/PS could degrade OPEs efficiently, and 254 nm UV light was more conducive to the degradation of OPEs than 365 nm UV light, and the degradation of OPEs accelerated with the increase of PS concentration. Under acidic and neutral conditions, UV/PS was more conducive to the degradation of OPEs, and the concentration of NOM was inversely proportional to the degradation rate of OPEs, Cl− and SO42− had almost no effect on the degradation of OPEs, while HCO3− has an inhibitory effect on the degradation of OPEs. UV/PS also has a good effect on the degradation of OPEs in actual water. •OH and SO• 4−, as the main reactive radicals, participate in the degradation of OPEs. Hydroxylation, debenzene ring, demethylation, and ring opening reactions are the main reactions occurring in the process of OPEs degradation. The theoretical toxicity value of most intermediates is lower than that of the initial OPEs. This study reveals the transformation of OPEs in the UV/PS system and provides a new idea for wastewater treatment of OPEs.

Biodegradation of monocrotophos by Stenotrophomonas maltophilia and its potential in vitro plant growth promoting activities

Extensive field application of monocrotophos (MCP), an organophosphate pesticide to protect agricultural crops and yields, imposes severe environmental issues due to its long-term persistence in soil and water. Indigenous bacterial strain CAB5 was isolated from a severely monocrotophos-contaminated agricultural field in Mysuru, Karnataka. The strain was assessed for its ability to biodegrade monocrotophos and plant-growth promoting factors. CAB5, identified as Stenotrophomonas maltophilia (OQ861256). It exhibited monocrotophos tolerance up to 1000 ppm by utilizing it as sole carbon source for metabolism and growth. S. maltophilia can produce several plant growth-promoting (PGP) traits, including ammonia, cellulase, IAA, catalase, and phosphate solubilization. The optimal condition for CAB5 growth observed as pH 8, 37 ℃ temperature, and 96 h of incubation time, respectively. Biodegradation was analyzed by combining hyphenated techniques like UV spectroscopy and TLC, and the intermediate metabolites were analyzed by FT-IR and LC-MS. Dimethyl-phosphate, Trimethyl phosphate, and Cyclohexanone, 2-cyclohexylidene were the intermediate metabolites formed from biodegradation. It is concluded that S. maltophilia CAB5 could be an advantageous with the consortium-based formulated prototype for the refinement of polluted sites for toxic pollutants along with plant growth promotion.

Distribution, traceability, and risk assessment of organophosphate flame retardants in agricultural soils along the Yangtze River Delta in China.

Severe pollution threatens the ecosystem and human health in the Yangtze River Delta (YRD) in China because of the rapid development of industry in this area. This study examines the types, distribution, concentration, and origin of fourteen typical organophosphate flame retardants (OPFRs) in agricultural soils within the YRD region to offer insights for pollutant control and policy-making. The total concentration of OPFRs (ΣOPFRs) varied between 79.19 and 699.58 μg/kg dry weight (dw), averaging at 209.61 μg/kg dw. Among the OPFRs detected, tributoxyethyl phosphate (TBEP) was identified as the main congener, followed by tri-n-butyl phosphate (TnBP), tris(2-chloroisopropyl) phosphate (TCPP), and trimethyl phosphate (TMP). Source analysis, conducted through correlation coefficients and PCA, indicated that OPFRs in agricultural soils within the YRD region mainly originate from emissions related to plastic products and transportation. The health risk exposure to ΣOPFRs in agricultural soil was considered negligible for farmers, with values below 1.24 × 10-2 and 1.76 × 10-9 for noncarcinogenic and carcinogenic risks, respectively. However, the ecological risk of ΣOPFRs in all the samples ranged from 0.08-1.08, indicating a medium to high risk level. The results offer a comprehensive understanding of OPFR pollution in agricultural soils in the YRD region and can be useful for pollution control that mitigates ecological and health risks in this region.

Unraveling the role of ubiquitin C-terminal hydrolase L1 in high grade serous ovarian cancer pathogenesis.

e15078 Background: High grade serous ovarian cancer (HGSOC) is the most lethal of all gynecologic malignancies, due to the fact that the majority of patients are diagnosed at an advanced stage and eventually develop chemoresistant disease 12-18 months following completion of frontline therapy. Therefore, novel targeted therapies are urgently needed to combat chemoresistance and improve patient clinical outcomes. Ubiquitin C-terminal hydrolase L1 (UCHL1) is a deubiquitinating enzyme that plays a vital role in protein homeostasis and is highly overexpressed in HGSOC. It was previously uncovered that targeting UCHL1 with small molecule inhibition reduced cell viability in a chemoresistant ovarian cancer cell line. Methods: Comparative-label free proteomic analysis was used to uncover significant changes in HGSOC cell line OVCAR8WT following treatment with UCHL1 small molecule inhibitor, LDN-5744 or corresponding DMSO control. Significant pathway changes were determined by KEGG analysis. Matched chemosensitive and resistant HGSOC cells PEA1 and PEA2 were treated in combination with LDN-5744 and carboplatin, with cell viability was determined by an MTS assay. Furthermore, western blot analysis was employed to compare common cell growth pathway changes as a result of UCHL1 inhibition in HGSOC cells. Results: Proteomic analysis revealed a significant (p<0.05) upregulation in methyl phosphate capping enzyme (MEPCE) (4.9-fold), asparagine synthetase (ASNS) (2.5-fold), Phosphoserine aminotransferase 1 (PSAT1) (1.7-fold), and downregulation in centrosomal protein 55 (CEP55) (-7.2-fold), These identified proteomic changes were confirmed by western blot. KEGG pathways analysis using all significantly (p<0.05) differentially expressed proteins showcased significant (p<0.05) enrichment in amino acid biosynthesis, and metabolism, and chemical carcinogenesis-reactive oxygen species. Chemoresistant PEA2 cells treated in combination with LDN-5744 and carboplatin demonstrated a 59% reduction in cell viability, significantly (p<0.001) lower than the 13% and 22%, that was observed from UCHL1 and carboplatin treatment alone, respectively. Conversely, PEA1, the chemosensitive counterpart to PEA2 demonstrated a significant (p<0.001) 37% increase in cell viability upon combinatorial treatment compared with carboplatin alone, indicating that UCHL1 inhibition rescues the cells from chemotherapy induced cell death. Finally, LDN-5744 treatment in PEA2 led to a reduction in levels of phospho-(p-)AKT, p-STAT3, and p-ERK, while conversely in PEA1 cells levels of these proteins were increase or unchanged. Conclusions: Our findings demonstrate that targeting UCHL1 results in prominent metabolic changes in HGSOC cells and that the efficacy of UCHL1 inhibition is heavily dependent upon platinum status. Overall, this study highlights UCHL1’s novel therapeutic role in the recurrent HGSOC.

Fiber-optic Michelson interferometric trace dimethyl methyl phosphate sensor based on MnO2/ZnO composites film

A dimethyl-methyl phosphonate (DMMP) sensor based on MnO2/ZnO composite film integrated fiber-optic Michelson interference structure is proposed. The sensing structure is formed by a thick taper between a single-mode fiber (SMF) and a four-core fiber (FCF), and then the no-core fiber (NCF) is spliced at the other end of the FCF. To enhance reflection, the silver film was deposited on the end of the NCF, and the fiber optic Michelson interference structure is formed. MnO2/ZnO composite sensing film was deposited on the FCF surface, and the structure, morphology, and properties of the sensing material were analyzed by x-ray diffraction, Scanning electron microscopy, Fourier-transform infrared spectroscopy, x-ray photoelectron spectroscopy, etc. The sensitivity and the response time of the sensor are 0.3478 dB/ppm and 180 s, respectively. The sensor has good selectivity and stability, and it has a good application prospect in trace DMMP detection with high sensitivity.

Efficient conversion of hemoglobin to a non-vasoactive oxygen carrier by site-specific cross-linking with azido acyl methyl phosphates followed by bio-orthogonal CuAAC with a bis-alkyne

While cross-linked hemoglobin tetramers are functional acellular oxygen carriers, their ability to scavenge endogenous nitric oxide (NO) by endothelial pore penetration results in adverse cardiovascular effects. Animal studies established that cross-linked human hemoglobins, chemically joined into a double protein, avoid NO scavenging, presumably due to their larger size preventing penetration into endothelial regions that produce NO. In the present report, we utilize azide-containing acyl phosphate reagents to form cross-linked hemoglobins then bio-orthogonally click-couple them with a bis-alkyne (CuAAC). The production of these larger oxygen-carrying hemoglobin conjugates is obtained in high yields through subunit-specific cross-linking between each βLys82 ε-amino group. The methyl phosphate leaving groups provide electrostatically induced β-subunit site-selectivity, producing azido-cross-linked hemoglobin that undergoes highly efficient CuAAC compared with previous cross-linkers. The acyl phosphates also efficiently cross-link both T-state and R-state hemoglobin. The resulting bis- and tris-tetrameric hemoglobin conjugates exhibit oxygen affinity and cooperativity that are comparable to those of the native protein. The hemoglobin derivatives from the process we describe can function as sources of oxygen in biomedical applications, such as in ex-vivo donor organ perfusion.