Ethyl Sulfide Research Articles

A Pillar[5]arene-Containing Metal-Organic Framework for Rapid and Highly Capable Adsorption of a Mustard Gas Simulant.

Mustard gas causes irreversible damage upon inhalation or contact with the human body. Consequently, the development of adsorbents for effective interception of mustard gas at low concentrations and high flow rates is an urgent necessity. Here we report a stable porous pillar[5]arene-containing metal-organic framework (MOF) based on zirconium (EtP5-Zr-scu), demonstrating that embedding pillar[5]arene units in MOFs can provide specific binding sites for efficient adsorption of a mustard gas simulant, 2-chloroethyl ethyl sulfide (CEES). EtP5-Zr-scu achieves a higher capacity and more rapid adsorption compared to its counterpart without embedded pillar[5]arene units (H4tcpt-Zr-scu) and perethylated pillar[5]arene (EtP5) alone. Single crystal X-ray diffraction and solid-state nuclear magnetic resonance reveal that the enhanced performance of EtP5-Zr-scu is derived from the host-guest complexation between CEES and pillar[5]arene moieties. Moreover, breakthrough experiments confirmed that the interception performance of EtP5-Zr-scu against CEES (800 ppm, 120 mL/min) was significantly improved (566 min/g) compared with H4tcpt-Zr-scu (353 min/g) and EtP5 (0.873 min/g), attributed to the integration of open channels with specific recognition sites. This work marks a significant advancement in the development of macrocycle-incorporated crystalline framework materials with recognition sites for the efficient capture of guest molecules.

Synergistic Effects of Glutamine Deprivation and Metformin in Acute Myeloid Leukemia.

The metabolic reprogramming of acute myeloid leukemia (AML) cells is a compensatory adaptation to meet energy requirements for rapid proliferation. This study aimed to examine the synergistic effects of glutamine deprivation and metformin exposure on AML cells. SKM-1 cells (an AML cell line) were subjected to glutamine deprivation and/or treatment with metformin or bis-2-(5-phenylacetamido-1,2,4-thiadiazol-2-yl) ethyl sulfide (BPTES, a glutaminase inhibitor) or cytarabine. Cell viability was detected by Cell Counting Kit-8 (CCK-8) assay, and cell apoptosis and reactive oxygen species (ROS) by flow cytometry. Western blotting was conducted to examine the levels of apoptotic proteins, including cleaved caspase-3 and poly(ADP-ribose) polymerase (PARP). Moreover, the human long noncoding RNA (lncRNA) microarray was used to analyze gene expression after glutamine deprivation, and results were confirmed with quantitative RT-PCR (qRT-PCR). The expression of metallothionein 2A (MT2A) was suppressed using siRNA. Cell growth and apoptosis were further detected by CCK-8 assay and flow cytometry, respectively, in cells with MT2A knockdown. Glutamine deprivation or treatment with BPTES inhibited cell growth and induced apoptosis in SKM-1 cells. The lncRNA microarray result showed that the expression of MT family genes was significantly upregulated after glutamine deprivation. MT2A knockdown increased apoptosis, while proliferation was not affected in SKM-1 cells. In addition, metformin inhibited cell growth and induced apoptosis in SKM-1 cells. Both glutamine deprivation and metformin enhanced the sensitivity of SKM-1 cells to cytarabine. Furthermore, the combination of glutamine deprivation with metformin exhibited synergistic antileukemia effects on SKM-1 cells. Targeting glutamine metabolism in combination with metformin is a promising new therapeutic strategy for AML.

Bacterial microcompartment-mimicking Pickering emulsion droplets for detoxification of chemical threats under sweet conditions

Chemical warfare agents represent a severe threat to mankind and their efficient decontamination is a global necessity. However, traditional disposal strategies have limitations, including high energy consumption, use of aggressive reagents and generation of toxic byproducts. Here, inspired by the compartmentalized architecture and detoxification mechanism of bacterial micro-compartments, we constructed oil-in-water Pickering emulsion droplets stabilized by hydrogen-bonded organic framework immobilized cascade enzymes for decontaminating mustard gas simulant (2-chloroethyl ethyl sulfide, CEES) under sweet conditions. Two exemplified droplet systems were developed with two-enzyme (glucose oxidase/chloroperoxidase) and three-enzyme (invertase/glucose oxidase/chloroperoxidase) cascades, both achieving over 6-fold enhancement in decontamination efficiency compared with free enzymes and >99% selectivity towards non-toxic sulfoxide. We found that the favored mass transfer of sugars and CEES from their respective phases to approach the cascade enzymes located at the droplet surface and the facilitated substrate channeling between proximally immobilized enzymes were key factors in augmenting the decontamination efficacy. More importantly, the robustness of immobilized enzymes enabled easy reproduction of both the droplet formation and detoxification performance over 10 cycles, following long-term storage and in far-field locations.

Biomimetic liposome amplifying mitochondrial damage to potential cancer radio-immunotherapy

Radiotherapy, despite its precision and non-invasiveness, often fails due to the resistance of cancer stem cells (CSCs), which are characterized by high self-renewal capabilities and superior DNA repair mechanisms. These cells can evade RT and lead to tumor recurrence and metastasis. To address this challenge, a novel delivery system named PB has been introduced. This system combines liposomes with platelet membranes to encapsulate Bis-2-(5-phenylacetamido-1,2,4-thiadiazol-2-yl) ethyl sulfide (BPTES), thus enhancing its delivery and release specifically at tumor sites. In addition, this system not only targets CSCs effectively but also increases the local concentration of BPTES upon X-ray irradiation, which reduces glutathione levels in tumor cells, thereby increasing oxidative stress and damaging mitochondria. PB-elicited mitochondrial damage as the STING signal initiator, which mediated significant upregulation in the expression of a cGAS-STING pathway-related protein thereby amplifying the STING signal. Systemic intravenous administration of PB remarkably promoted DC maturation and CD8+ T cell infiltration, thus eliciting strong antitumor effects. Overall, this PB system presents a potent method to overcome CSC-related resistance and offers a promising approach for future cancer treatment protocols.

Three-type precursors for low-temperature solution-processed void-and-crack-free copper(I) iodide films: comparison of electrical conductivities and optical transparency

Abstract Copper(I) iodide is a wide-bandgap (colorless) p-type semiconductor with a high Seebeck coefficient. Although copper(I) iodide is promising for fabricating transparent thermoelectric devices and hole-transfer layers of solar cells, the insolubility in common solvents due to 3-dimensional coordination networks has been a drawback to constructing low-temperature solution-processed thin films. Moreover, it is challenging to fabricate void-and-crack-free copper(I) iodide thin films through a convenient spin-coating process. In limited solvents of acetonitrile and diethyl sulfide, copper(I) iodide is dissolved by forming soluble copper(I) iodide complexes; however, void-and-crack-free copper(I) iodide thin films have never been prepared. In this study, we report that copper(I) iodide–alkanolamine complexes are soluble in alcohols and the spin-coated complexes undergo thermal decomposition to a copper(I) iodide thin film at moderately low temperatures until 150 °C. We discover that the copper(I) iodide–alkanolamines show different properties such as solubility and melting/decomposition temperatures depending on their structures. Specifically, by using 1-amino-2-propanol, we obtain void-and-crack-free and transparent copper(I) iodide thin films with controlled thicknesses of >50 nm. The conductivity, carrier density, mobility, and Seebeck coefficient of the copper(I) iodide thin film are 9.35 S·cm−1, 6.38 × 1019 cm−3, 0.96 cm2·V−1·S−1, and 192 µV·K−1, respectively.

Diethyl Sulfide Oxidation with Sodium Peroxoborate in Water–Acetonitrile System. Kinetics and Mechanism

In aqueous solutions of acetonitrile (1 vol%), the rate of oxidation of diethyl sulfide with sodium peroxoborate, Na2[B2(O2)2(OH)4]∙6H2O, in the pH range of 8.5–11 is significantly higher than the oxidation rate in water and exceeds the rate of reaction of Et2S with hydrogen peroxide in the H2O–MeCN system. The reaction order with respect to the substrate, which is close to zero, suggests that the limiting stage of the process is the reaction of peroxoborate anions with MeCN, leading to the formation of active boron peroxyimidates, which then react in a rapid stage with Et2S.

L-[5-11C]Glutamine PET imaging noninvasively tracks dynamic responses of glutaminolysis in non-alcoholic steatohepatitis

Inhibiting glutamine metabolism has been proposed as a potential treatment strategy for improving non-alcoholic steatohepatitis (NASH). However, effective methods for assessing dynamic metabolic responses during interventions targeting glutaminolysis have not yet emerged. Here, we developed a positron emission tomography (PET) imaging platform using l-[5-11C]glutamine ([11C]Gln) and evaluated its efficacy in NASH mice undergoing metabolic therapy with bis-2-(5-phenylacetamido-1,3,4-thiadiazol-2-yl)ethyl sulfide (BPTES), a glutaminase 1 (GLS1) inhibitor that intervenes in the first and rate-limiting step of glutaminolysis. PET imaging with [11C]Gln effectively delineated the pharmacokinetics of l-glutamine, capturing its temporal-spatial pattern of action within the body. Furthermore, [11C]Gln PET imaging revealed a significant increase in hepatic uptake in methionine and choline deficient (MCD)-fed NASH mice, whereas systemic therapeutic interventions with BPTES reduced the hepatic avidity of [11C]Gln in MCD-fed mice. This reduction in [11C]Gln uptake correlated with a decrease in GLS1 burden and improvements in liver damage, indicating the efficacy of BPTES in mitigating NASH-related metabolic abnormalities. These results suggest that [11C]Gln PET imaging can serve as a noninvasive diagnostic platform for whole-body, real-time tracking of responses of glutaminolysis to GLS1 manipulation in NASH, and it may be a valuable tool for the clinical management of patients with NASH undergoing glutaminolysis-based metabolic therapy.

Confining polyoxometalates in porphyrin-based porous cationic polymer toward boosting visible-light-driven synthesis of sulfoxides and detoxification of mustard gas simulants

Visible-light-driven oxidation of sulfides has attracted the profound attention to synthesize sulfoxides and purify mustard gas simulant. In this work, a series of visible-light-responsive polyoxometalate-based porous cationic polymers, i.e. SiW12-PCP 1, PW12-PCP 2, SiW11-PCP 3, SiW10-PCP 4, SiW9-PCP 5 (PCP = porphyrin-based porous cationic polymer), were synthesized by ion exchange process. These POM-PCPs exhibit excellent ability of trapping visible light due to their built-in porphyrin units, which can rapidly oxidize sulfides and degrade 2-chloroethyl ethyl sulfide (CEES) in the presence of a 10 W white LED light and O2. Benefiting from the synergistic effect between [SiW12] and PCP, hybrid 1 has the highest photocatalytic efficiency, attaining 99 % conversion of sulfides within 16 min and 99 % CEES purification in 8 min, much higher than PCP precursor. The reaction mechanism reveals that both O2•− and 1O2 are involved in the photocatalytic process. What's more, hybrid 1 has remarkable applicability to numerous sulfides and robust six-round recycling with no reduction in catalytic efficiency.

Chromo-fluorogenic detection of Sarin, Tabun, and mustard gas mimics triggering the ring-opening reaction in a spirolactam-based probe

Nerve agents are becoming serious issues for the healthy and sustainable environment in modern civilization. Strategically, we have designed and introduced a Schiff base triggered dual chromo-fluorogenic probe BASO via condensation reaction between rhodamine B hydrazide and 3-formyl chromone, which can selectively recognize different toxic target analytes helping a reference to a healthy and sustainable environment. The BASO probe displays enhanced pink photoluminescence extraordinarily due to the introduction of sarin, tabun, and mustard gas mimics diethylchlorophosphate (DCP), diethylcyanophosphonate (DCNP), and 2-chloroethyl ethyl sulfide (2CEES), in a 1:1 water–dimethyl sulfoxide (DMSO) mixture while native one was non-fluorescent. The opening of the spirolactam ring owing to the addition of DCP, DCNP, and 2CEES shows a noticeable pink colorimetric and pink color fluorometric change, which is readily detectable by the naked eye in the µM range in neutral medium and found to be better than numerous available chemosensor (Table S1). We have also fabricated simple paper strip-based test kits as portable and displayable handy photonic tools for on-site detection without any expensive instrumental techniques. The probe BASO has also been employed for detecting the vapor phase and soil sample analysis as a practical applicability. The simple, rapid detection techniques make our probe unique and have significant utility for the recognition of DCP, DCNP, and vesicant or blistering agents mimicking 2CEES.

Interface-regulated S-type core–shell PCN-224@TiO2 heterojunction for visible-light-driven generation of singlet oxygen for selective photooxidation of 2-chloroethyl ethyl sulfide

Selective oxidation of sulfur mustard gas (HD) to non-toxic sulfoxide by the visible-light-catalyzed generation of singlet oxygen (1O2) is a promising degradation strategy. Although PCN-224 can absorb visible light, it suffers from rapid electron-hole recombination and low redox capacity, which limits the performance of HD degradation. Titanium dioxide (TiO2) is an excellent photocatalyst but it lacks visible-light-activity in degrading HD. In this study, PCN-224@TiO2 heterojunction with S-type core–shell structure was synthesized by in-situ growth method to prolong the visible light absorption capacity of TiO2 and inhibit the rapid recombination of PCN-224. The interface formation and internal electric field were optimized by adjusting the Zr/Ti ratio to enhance the charge transfer, redox capacity, electron-hole separation, and visible light absorption. In this study, the formation of heterojunction composites based on Zr-O-Ti linkages is demonstrated by a series of characterization methods. It is demonstrated by experiments and theoretical calculations that PCN-224@TiO2 can generate nearly 100 % 1O2 under visible light conditions without a sacrificial agent, resulting in efficient and selective oxidation of 2-chloroethyl ethyl sulfide (CEES), a simulant of HD, to non-toxic sulfoxide form.

Ultrathin WO3 Nanosheets/Pd with Strong Metal-Support Interactions for Highly Sensitive and Selective Detection of Mustard-Gas Simulants.

Exposure to mustard gas can cause damage or death to human beings, depending on the concentration and duration. Thus, developing high-performance mustard-gas sensors is highly needed for early warning. Herein, ultrathin WO3 nanosheet-supported Pd nanoparticles hybrids (WO3 NSs/Pd) are prepared as chemiresistive sulfur mustard simulant (e.g., 2-chloroethyl ethyl sulfide, 2-CEES) gas sensors. As a result, the optimal WO3 NSs/Pd-2 (2 wt % of Pd)-based sensor exhibits a high response of 8.5 and a rapid response/recovery time of 9/92 s toward 700 ppb 2-CEES at 260 °C. The detection limit could be as low as 15 ppb with a response of 1.4. Moreover, WO3 NSs/Pd-2 shows good repeatability, 30-day operating stability, and good selectivity. In WO3 NSs/Pd-2, ultrathin WO3 NSs are rich in oxygen vacancies, offer more sites to adsorb oxygen species, and make their size close to or even within the thickness of the so-called electron depletion layer, thus inducing a large resistance change (response). Moreover, strong metal-support interactions (SMSIs) between WO3 NSs and Pd nanoparticles enhance the catalytic redox reaction performance, thereby achieving a superior sensing performance toward 2-CEES. These findings in this work provide a new approach to optimize the sensing performance of a chemiresistive sensor by constructing SMSIs in ultrathin metal oxides.

Measuring Mass Transfer of n-Hexane and 2-Chloroethyl Ethyl Sulfide in Sorbent/Polymer Fiber Composites Using a Volumetric Adsorption Apparatus.

The integration of metal-organic frameworks (MOFs) into composite systems serves as an effective strategy to increase the processability of these materials. Notably, MOF/fiber composites have shown much promise as protective equipment for the capture and remediation of chemical warfare agents. However, the practical application of these composites requires an understanding of their mass transport properties, as both mass transfer resistance at the surface and diffusion within the materials can impact the efficacy of these materials. In this work, we synthesized composite fibers of MOF-808 and amidoxime-functionalized polymers of intrinsic microporosity (PIM-1-AX) and measured the adsorption and mass transport behavior of n-hexane and 2-chloroethyl ethyl sulfide (CEES), a sulfur mustard simulant. We developed a new Fickian diffusion model for cylindrical shapes to fit the dynamic adsorption data obtained from a commercial volumetric adsorption apparatus and found that mass transport behavior in composite fibers closely resembled that in the pure PIM fibers, regardless of MOF loading. Moreover, we found that n-hexane adsorption mirrors that of CEES, indicating that it could be used as a structural mimic for future adsorption studies of the sulfur mustard simulant. These preliminary insights and the new model introduced in this work lay the groundwork for the design of next-generation composite materials for practical applications.

Post‐Synthetic Modification of Mixed‐Metal UiO‐66 Framework for Rapid Neutralization of Chemical Warfare Agent Simulants

AbstractMetal‐organic frameworks (MOFs) are a promising class of materials for catalysis, offering unique opportunities for designing efficient and selective catalysts. In this study, we have focused on the synthesis and catalytic activity of a novel mixed metal MOF, Ce/Zr−UiO‐66@LiOtBu, designed for the rapid hydrolysis of chemical warfare agents simulants: dimethyl 4‐nitrophenyl phosphate (DMNP) and 2‐chloroethyl ethyl sulfide (CEES). This MOF was thoroughly characterized using powder X‐ray diffraction (PXRD), BET surface area, and inductively coupled plasma optical emission spectrometry (ICP‐OES). The catalytic performance of Ce/Zr−UiO‐66@LiOtBu was monitored in the hydrolysis of DMNP and CEES by using 31P NMR and GC‐MS respectively. Remarkably, the MOF demonstrated rapid and efficient catalytic activity, breaking the P−O bond in DMNP with 2 min and the hydrolysis of CEES was observed in less than 45 min The results suggest the potential application of Ce/Zr−UiO‐66@LiOtBu as a robust catalyst in the detoxification of chemical warfare agent simulants. Our findings highlight the novelty of Ce/Zr−UiO‐66@LiOtBu as a catalytically active MOF, showcasing the successful integration of cerium ions and lithium tert‐butoxide to enhance basicity.

Necroptosis-Mediated Synergistic Photodynamic and Glutamine-Metabolic Therapy Enabled by a Biomimetic Targeting Nanosystem for Cholangiocarcinoma.

Targeted delivery of glutamine metabolism inhibitors holds promise for cholangiocarcinoma therapy, yet effective delivery vehicles remain a challenge. This study reports the development of a biomimetic nanosystem, termed R-CM@MSN@BC, integrating mesoporous organosilicon nanoparticles with reactive oxygen species-responsive diselenide bonds for controlled release of the glutamine metabolism inhibitor bis-2-(5-phenylacetamido-1,3,4-thiadiazol-2-yl) ethyl sulfide (BPTES) and the photosensitizer Ce6. Erythrocyte membrane coating, engineered with Arg-Gly-Asp (RGD) peptides, not only enhanced biocompatibility but also improved tumor targeting and tissue penetration. Upon laser irradiation, R-CM@MSN@BC executed both photodynamic and glutamine-metabolic therapies, inducing necroptosis in tumor cells and triggering significant immunogenic cell death. Time-of-flight mass cytometry analysis revealed that R-CM@MSN@BC can remodel the immunosuppressive tumor microenvironment by polarizing M1-type macrophages, reducing infiltration of M2-type and CX3CR1+ macrophages, and decreasing T cell exhaustion, thereby increasing the effectiveness of anti-programmed cell death ligand 1 immunotherapy. This strategy proposed in this study presents a viable and promising approach for the treatment of cholangiocarcinoma.

UV-Cured Highly Crosslinked Polyurethane Acrylate to Serve as a Barrier against Chemical Warfare Agent Simulants.

Ultraviolet (UV) curing is an efficient and environmentally friendly curing method. In this paper, UV-cured polyurethane acrylates (PUAs) were investigated as potential military coatings to serve as barriers against chemical warfare agents (CWAs). Seven UV-cured PUA coatings were formulated utilizing hydroxyethyl methacrylate-capped hexamethylene diisocyanate trimer (HEMA-Htri) and trimethylolpropane triacrylate-capped polycarbonate prepolymer (PETA-PCDL) as the PUA monomers. Isobornyl acrylate (IBOA) and triethyleneglycol divinyl ether (DVE-3) were employed as reactive diluents. Gas chromatography was utilized to investigate the constitutive relationships between the structures of the PUA coatings and their protective properties against simulant agents for CWAs, including dimethyl methylphosphonate (DMMP), a nerve agent simulant, and 2-chloroethyl ethyl sulfide (CEES), a mustard simulant. The glass transition temperature (Tg) and crosslinking density (υe) of PUAs were found to be crucial factors affecting their ability to serve as barriers against CWAs. The incorporation of IBOA units led to enhanced Tg and barrier performance of the PUAs, resulting in a DMMP retention of less than 0.5% and nearly 0 retention of CEES. However, an excessive introduction of polycarbonate chains decreased the υe and barrier performance of the PUAs. These findings may offer valuable insights for enhancing the protection of UV-cured PU coatings against CWAs.

Establishment of a Mouse Model of Mycoplasma pneumoniae-Induced Plastic Bronchitis.

Plastic bronchitis (PB) constitutes a life-threatening pulmonary disorder, predominantly attributed to Mycoplasma pneumoniae (MP) infection. The pathogenic mechanisms involved remain largely unexplored, leading to the absence of reliable approaches for early diagnosis and clear treatment. Thus, the present investigation aimed to develop an MP-induced mouse model of PB, thereby enhancing our understanding of this complex condition. In the first stage, healthy BALB/c mice were utilized to investigate the optimal methods for establishing PB. This involved the application of nebulization (15-20 min) and intratracheal administration (6-50 μL) with 2-chloroethyl ethyl sulfide (CEES) concentrations ranging from 4.5% to 7.5%. Subsequently, the MP model was induced by administering an MP solution (2 mL/kg/day, 108 CFU/50 μL) via the intranasal route for a duration of five consecutive days. Ultimately, suitable techniques were employed to induce plastic bronchitis in the MP model. Pathological changes in lung tissue were analyzed, and immunohistochemistry was employed to ascertain the expression levels of vascular endothelial growth factor receptor 3 (VEGFR-3) and the PI3K/AKT/mTOR signaling pathway. The administration of 4.5% CEES via a 6 µL trachea was the optimal approach to establishing a PB model. This method primarily induced neutrophilic inflammation and fibrinous exudate. The MP-infected group manifested symptoms indicative of respiratory infection, including erect hair, oral and nasal secretions, and a decrease in body weight. Furthermore, the pathological score of the MP+CEES group surpassed that of the groups treated with MP or CEES independently. Notably, the MP+CEES group demonstrated significant activation of the VEGFR-3 and PI3K/AKT/mTOR signaling pathways, implying a substantial involvement of lymphatic vessel impairment in this pathology. This study successfully established a mouse model of PB induced by MP using a two-step method. Lymphatic vessel impairment is a pivotal element in the pathogenetic mechanisms underlying this disease entity. This accomplishment will aid in further research into treatment methods for patients with PB caused by MP.

{SeO2(OH)} Bridging Lanthanide-Containing Antimono-Seleno-Tungstates.

A series of new trigonal pyramidal {SeO2(OH)} bridging lanthanide-containing antimono-seleno-tungstates [H2N(CH3)2]8Na8Cs4H9[Ln2SeW4O11(OH)(H2O)4(SbW9O33)(SeW9O33)(Se1/2Sb1/2W9O33)]2·32H2O [Ln = Tb (1), Dy (2), Ho (3), Er (4)] have been prepared by the synthetic strategy of simultaneously using the antimonotungstate precursor and simple material in an acidic aqueous solution and structurally characterized by single-crystal X-ray diffraction, powder X-ray diffraction, IR spectrometry, and thermogravimetric analysis. Their molecular structures contain an unprecedented hexameric polyoxoanion [Ln2SeW4O11(OH)(H2O)4(SbW9O33)(SeW9O33)(Se1/2Sb1/2W9O33)]229- constituted by two equivalent trimeric subunits Ln2W4O9(H2O)4(SbW9O33)(SeW9O33)(Se1/2Sb1/2W9O33) bridged via two μ2-{SeO2(OH)} linkers. Furthermore, the catalytic oxidation of various aromatic sulfides and sulfur mustard simulant 2-chloroethyl ethyl sulfide (CEES) by compound 3 as the heterogeneous catalyst has been investigated, exhibiting high conversion and selectivity as well as good stability and recyclability.

One-pot synthesis of a porphyrin functionalized metal-organic frameworks as a recyclable visible-light-driven photosensitizer for efficient detoxification of a sulfur mustard simulant in air

Herein, we report a facile one-pot in situ self-assembly approach that enables a porphyrin photosensitizer, [5,10,15,20-tetrakis(4-methoxycarbonylphenyl)porphyrin]-Zn(II) (ZnTPP), to be enshrouded by a zeolitic imidazolate framework-8 (ZIF-8) to afford a novel visible-light-driven heterogeneous photosensitizer, ZnTPP@ZIF-8 composite. The ZnTTP photosensitizer was well dispersed and fully confined within the ZIF-8 crystals and the framework intactness and porosity were well maintained. The as-prepared ZnTPP@ZIF-8 composite integrates the advantages of ZIF-8 MOFs and ZnTTP photosensitizer. It not only can effectively produce both singlet oxygen (1O2) and superoxide ion (∙O2−) under visible light irradiation, but also exhibit high surface area and excellent stability. The structure characterization of ZnTPP@ZIF-8 composite was first carried out, and then this material can be used as a heterogeneous photosensitizer for the rapid and highly selective detoxification of a sulfur mustard simulant (2-chloroethyl ethyl sulfide) into the corresponding much less toxic sulfoxide product with a half-life of only 1.5 min under visible light irradiation at room temperature in air atmosphere. This catalyst can be readily recycled and reused at least six times without obvious loss of catalytic activity. This study will provide us a new strategy for the facile, rapid and environmentally friendly preparation of photosensitizer@MOFs composites and the rapid detoxification of sulfur mustard under ambient conditions in the future.

Au- ZnFe2O4 hollow microspheres based gas sensor for detecting the mustard gas simulant 2-chloroethyl ethyl sulfide

Mustard gas, a representative of blister agents, poses a severe threat to human health. Although the structure of 2-chloroethyl ethyl sulfide (2-CEES) is similar to mustard gas, 2-CEES is non-toxic, rendering it a commonly employed simulant in related research. ZnFe2O4-based semiconductor gas sensors exhibit numerous advantages, including structural stability, high sensitivities, and easy miniaturization. However, they exhibit insufficient sensitivity at low concentrations and require high operating temperatures. Owing to the effect of electronic and chemical sensitization, the gas-sensing performance of a sensor may be remarkably enhanced via the sensitization method of noble metal loading. In this study, based on the morphologies of ZnFe2O4 hollow microspheres, a solvothermal method was adopted to realize different levels of Au loading. Toward 1 ppm of 2-CEES, the gas sensor based on 2 wt.% Au-loaded ZnFe2O4 hollow microspheres exhibited a response sensitivity twice that of the gas sensor based on pure ZnFe2O4; furthermore, the response/recovery times decreased. Additionally, the sensor displayed excellent linear response to low concentrations of 2-CEES, outstanding selectivity in the presence of several common volatile organic compounds, and good repeatability, as well as long-term stability. The Au-loaded ZnFe2O4-based sensor has considerable potential for use in detecting toxic chemical agents and their simulants.Graphical abstract

Glutamate rescues heat stress-induced apoptosis of Sertoli cells by enhancing the activity of antioxidant enzymes and activating the Trx1-Akt pathway in vitro

Heat stress reduces the number of Sertoli cells, which is closely related to an imbalanced redox status. Glutamate functions to maintain the equilibrium of redox homeostasis. However, the role of glutamate in heat treated Sertoli cells remains unclear. Herein, Sertoli cells from 3-week-old piglets were treated at 44 °C for 30 min (heat stress). Glutamate levels increased significantly following heat stress treatment, followed by a gradual decrease during recovery, while glutathione (GSH) showed a gradual increase. The addition of exogenous glutamate (700 μM) to Sertoli cells before heat stress significantly reduced the heat stress-induced apoptosis rate, mediated by enhanced levels of antioxidant substances (superoxide dismutase (SOD), total antioxidant capacity (TAC), and GSH) and reduced levels of oxidative substances (reactive oxygen species (ROS) and malondialdehyde (MDA)). Glutamate addition to Sertoli cells before heat stress upregulated the levels of glutamate-cysteine ligase, modifier subunit (Gclm), glutathione synthetase (Gss), thioredoxin (Trx1) and B-cell leukemia/lymphoma 2 (Bcl-2), and the ratio of phosphorylated Akt (protein kinase B)/total Akt. However, it decreased the levels of Bcl2-associated X protein (Bax) and cleaved-caspase 3. Addition of the inhibitor of glutaminase (Gls1), Bptes (Bis-2-(5-phenylacetamido-1,3,4-thiadiazol-2-yl)ethyl sulfide, 30 μM)to Sertoli cells before heat stress reversed these effects. These results inferred that glutamate rescued heat stress-induced apoptosis in Sertoli cells by enhancing activity of antioxidant enzymes and activating the Trx1-Akt pathway. Thus, glutamate supplementation might represent a novel strategy to alleviate the negative effect of heat stress.