Ethyl Sulfide Research Articles

Bifunctional Fluorescent Probes for the Detection of Mustard Gas and Phosgene

Mustard gas [sulfur mustard (SM)] and phosgene are the most frequently used chemical warfare agents (CWAs), which pose a serious threat to human health and national security, and their rapid and accurate detection is essential to respond to terrorist attacks and industrial accidents. Herein, we developed a fluorescent probe with o-hydroxythioketone as two sensing sites, AQso, which can detect and distinguish mustard gas and phosgene. The dual-sensing-site probe AQso reacts with mustard gas to form a cyclic product with high sensitivity [limit of detection (LOD) = 70 nM] and is highly selective to SM over phosgene, SM analogues, active alkylhalides, acylhalides, and nerve agent mimics, in ethanol solutions. When encountering phosgene, AQso rapidly converts to cyclic carbonate, which is sensitive (LOD = 14 nM) and highly selective. Their sensing mechanisms of AQso to mustard gas and phosgene were well demonstrated by separation and characterization of the sensing products. Furthermore, a facile test strip with the probe was prepared to distinguish 2-chloroethyl ethyl sulfide (CEES) and phosgene in the gas phase by different fluorescence colors and response rates. Not using the complicated instrument, the qualitative and quantitative detection of CEES or phosgene can be achieved only by measuring the red-green-blue (RGB) channel intensity of the test strip after being exposed to CEES or phosgene gas by the smartphone with an RGB color application.

A zinc-containing porphyrin aluminum MOF in sorption of diethyl sulfide vapor: mechanistic experimental and computational study.

We report a mechanistic study of the interactions in the sorption of volatile organic sulfur compound (VOSC) diethyl sulfide (DES) by zinc porphyrin aluminum MOF (actAl-MOF-TCPPZn) compound 3. First, interactions were studied under dynamic conditions with the vapor of DES in flowing air, using in situ time-dependent ATR-FTIR spectroscopy in a controlled atmosphere with a new facile spectroscopic mini-chamber. The first binding site includes μ(O-H) and COO- groups as detected by characteristic peak shifts. Control experiments with a model compound, which lacks porosity and these groups, show no peak shifts. An additional insight was obtained by DFT computations using small clusters. The kinetics of sorption of DES by compound 3 is of the Langmuir adsorption model and pseudo-first order with rate constant robs = 0.442 ± 0.056 min-1. Sorption of DES under static conditions in saturated vapor results in stoichiometric adsorption complex [Al-MOF-TCPPZn]1(DES)4 characterized by spectroscopic, structural and gravimetric methods; the adsorbed amount is very high (381 mg g-1 sorbent). The repetitive sorption and desorption of DES are conducted, with facile regeneration. Finally, the mechanistic details were determined by Raman and photoluminescence (PL) spectroscopy using a confocal Raman microscope. Photoexcitation of compound 3 at 405 nm into the Soret band of the metalloporphyrin linker shows the characteristic PL peaks of Q-bands: the purely electronic Q(0-0) and first vibronic Q(0-1) bands. Upon interaction with DES, preferential quenching of PL from the Q(0-0) band occurs with a significant increase of the signal of the vibronic Q(0-1) band, reflecting bonding to the metalloporphyrin ring. Compound 3 is of interest to mechanistic studies of VOSCs, their removal from air, and optical chemo-sensing.

A fluorescent probe generating in situ the reactive species for rapid and selective detection of mustard gas.

Sulfur mustard (SM) is an important chemical warfare agent (CWA) and has been used frequently in various conflicts. It is important to develop a facile, rapid, sensitive and selective detection method for SM. In this work, we constructed a novel fluorescent probe PCS capable of generating active sensing species for rapid and selective detection of SM and its simulant CEES (2-chloroethyl ethyl sulfide). PCS exhibits excellent chemical and photostability and can generate reactive species in situ for rapid (within 90 s, at 60 °C) and selective detection of SM and CEES in solution with high sensitivity (∼nM level). Moreover, PCS could enable the detection of mustards in situ. A test strip with PCS and KOH was prepared and realized the sensitive and selective detection of CEES in the gas phase. In addition, the PCS probe can realize facile and rapid detection of CEES-contaminated surfaces by spraying its sensing system (ethanol solution containing PCS and KOH). The sensing mechanism was well demonstrated through the separation and characterization of the sensing product.

Flow detoxification of a sulfur mustard simulant with organometallic compounds enabled by an optimization algorithm

The flow detoxification of the yperite simulant CEES with PhMgBr (>99.5%) was developed at a minimal experimental cost thanks to an optimization algorithm.

High-performance metal-oxide gas sensors based on hierarchical core-shell ZnFe2O4 microspheres for detecting 2-chloroethyl ethyl sulfide.

Mustard gas, an erosive chemical agent, is primarily used as a chemical weapon, which seriously threatens human life and health. Therefore, detecting mustard gas and its simulant, 2-chloroethyl ethyl sulfide (2-CEES), is a very important task. As a binary metal oxide with a spinel structure, ZnFe2O4 is widely used for fabricating gas sensors because of its stable chemical structure and abundant oxygen vacancies. In this study, gas-sensing ZnFe2O4 microspheres with a hierarchical core-shell nanosheet structure were prepared via a simple one-step solvothermal method. Scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, and N2 adsorption analyses were performed to characterize the morphology, structure, and chemical composition of these microspheres. A gas sensor was fabricated from the as-synthesized material, and its gas sensing performance was evaluated, using 2-CEES as a target gas. The obtained ZnFe2O4-based sensor exhibited a high sensitivity of 9.07 to 1 ppm 2-CEES at the optimal working temperature of 250 °C. The sensor response and recovery times were 18 and 546 s, respectively, and its detection sensitivity of 2.87 achieved at a 2-CEES concentration of 0.01 ppm was within an acceptable range. Additionally, the sensor demonstrated sufficiently high 2-CEES selectivity, repeatability, and long-term stability.

Defective MOF-74 with ancillary open metal sites for the enhanced adsorption of chemical warfare agent simulants.

The development of effective porous adsorbents plays a vital role in eliminating hazardous substances from the environment. Toxic chemicals, including chemical warfare agents (CWAs), pose significant risks to both humans and ecosystems, highlighting the urgency to create efficient porous adsorbents. Therefore, substantial attention has been directed towards advancing adsorption techniques for the successful eradication of CWAs from the environment. Herein, we demonstrate a rational approach for enhancing the adsorption capability of a porous metal-organic framework (MOF) by employing ancillary open metal sites within the MOF structure. To generate defective MOF-74 (D-MOF-74) with ancillary open metal sites, some of the 2,5-dihydroxy-1,4-bezenedicarboxylic acid (DHBDC) linkers originally present in the MOF-74 structure were replaced with 1,4-benzenedicarboxylic acid (BDC) linkers. The absence of hydroxyl groups in the BDC linkers compared to the original DHBDC linkers creates ancillary open metal sites, which enhance the adsorption ability of D-MOF-74 for CWA simulants such as dimethyl methyl phosphonate, 2-chloroethyl ethyl sulfide, and methyl salicylate by providing effective interaction sites for the targeted molecules. However, excessive creation of open metal sites causes the collapse of the originally well-developed MOF-74 structure, resulting in a substantial reduction in its empty space and a subsequent decline in adsorption efficiency. Thus, to produce a defective MOF with the best performance, it is necessary to replace an appropriate amount of organic linker and create suitable open metal sites. Moreover, D-MOF-74 displays excellent recyclability during consecutive adsorption cycles without losing its original structure and morphology, suggesting that D-MOF-74 is an effective and stable material for the removal of CWA simulants.

Decagram-scale synthesis of heterometallic Ag/Ti cluster as sustainable catalyst for selective oxidation of sulfides

Atomically precise heterometallic clusters constitute a new family of model catalysts for understanding the fundamental catalysis process widely occurred in supported nanocatalysts, however, their syntheses and structure/composition modulations are nonetheless daunting challenges. Herein, three novel heterometallic Ag/Ti clusters with different Ag-doping ratios, Ag4Ti14, Ag4Ti6 and Ag4Ti2, have been readily synthesized in decagram-scale quantities through ligand engineering strategy. Thereinto, Ag4Ti2 can be efficiently prepared within 3 h in a quite high yield > 95 %. More remarkably, Ag4Ti2 shows unprecedented catalytic activity (>90 % conversion within 1 min) and selectivity (nearly 100 %) towards oxidation of thioethers with a wide substrate scope even including notorious 2-chloroethyl ethyl sulfide (CEES) at room temperature (turnover frequency = 11,880 h−1), which is mainly attributed to its full-surface-exposure-doping Ag atoms (affinity for binding of substrate) on TiO support and their cooperativity, whereas the other two are not the same case. Moreover, the Ag4Ti2 is highly robust in catalysis process and can be readily recovered and reused at least six cycles without observable loss of activity and selectivity, enabling this cluster hold great promise in industrial applications. This work not only establishes a general method to scale-up synthesis of Ag/Ti clusters but also provides an atom-precise model catalyst to understand the structure–property correlations of real-world conventional nanocatalysts such as silver doped-TiO2 nanoparticles.

Glutaminase inhibitors rejuvenate human skin via clearance of senescent cells: a study using a mouse/human chimeric model.

Skin aging caused by various endogenous and exogenous factors results in structural and functional changes to skin components. However, the role of senescent cells in skin aging has not been clarified. To elucidate the function of senescent cells in skin aging, we evaluated the effects of the glutaminase inhibitor BPTES (bis-2-(5-phenylacetamido-1, 3, 4-thiadiazol-2-yl)ethyl sulfide) on human senescent dermal fibroblasts and aged human skin. Here, primary human dermal fibroblasts (HDFs) were induced to senescence by long-term passaging, ionizing radiation, and treatment with doxorubicin, an anticancer drug. Cell viability of HDFs was assessed after BPTES treatment. A mouse/human chimeric model was created by subcutaneously transplanting whole skin grafts from aged humans into nude mice. The model was treated intraperitoneally with BPTES or vehicle for 30 days. Skin samples were collected and subjected to reverse transcription-quantitative polymerase chain reaction (RT-qPCR), western blotting, and histological analysis. BPTES selectively eliminated senescent dermal fibroblasts regardless of the method used to induce senescence; aged human skin grafts treated with BPTES exhibited increased collagen density, increased cell proliferation in the dermis, and decreased aging-related secretory phenotypes, such as matrix metalloprotease and interleukin. These effects were maintained in the grafts 1 month after termination of the treatment. In conclusion, selective removal of senescent dermal fibroblasts can improve the skin aging phenotype, indicating that BPTES may be an effective novel therapeutic agent for skin aging.

Enhanced Catalytic Performance of a Ce/V Oxo Cluster through Confinement in Mesoporous SBA-15.

To increase catalytic efficiency, mesoporous supports have been widely applied to immobilize well-defined metal oxide clusters due to their ability to stabilize highly dispersed clusters. Herein, a redox-active heterometallic Ce12V6-oxo cluster (CeV) was first presynthesized and then incorporated into mesoporous silica, SBA-15, via a straightforward impregnation method. Scanning transmission electron microscopy (STEM) and Fourier transform infrared spectroscopy (FTIR), in concert with scanning electron microscopy and energy-dispersive X-ray spectroscopy (SEM-EDS), verified the successful introduction of the CeV cluster inside the pore of SBA-15. The 51V magic angle spinning solid-state nuclear magnetic resonance (51V MAS NMR) spectroscopy and differential pair distribution function (dPDF) analysis confirmed the structural integrity of the CeV cluster inside the SBA-15. The composite was then benchmarked for liquid-phase oxidation of 2-chloroethyl ethyl sulfide (CEES) under mild conditions and gas-phase oxidative dehydrogenation (ODH) of propane under high temperatures (up to 550 °C). The catalytic reactivity results demonstrated 8- and 14-fold increase in turnover frequency (TOF) values of the composite (CeV@10SBA-2) than the bulk CeV cluster under the same conditions for CEES oxidation and ODH, respectively. These results highlight the improved reactivity of the catalytically active CeV cluster as attributed to the higher dispersion of the discrete cluster upon immobilization within the SBA-15 support.

Highly Reactive Heterogeneous Nanofibers Catalyst based on [Mo154] Clusters for Green Aerobic Oxidation of Sulfur Mustard Analogues under Ambient Conditions.

Due to the increasing chemical and biological threats posed by terrorist attacks, there is a need to design and prepare nanofibers (NFs) with the ability to neutralize CWAs. For this purpose polyacrylonitrile NFs and polyoxomolybdate [Mo154] (abbreviated as PAN NFs/[Mo154]) as a heterogeneous catalyst was prepared by electrospinning method with a diameter of about 100nm. The PAN NFs/[Mo154] catalyze the selective aerobic oxidation of sulfur mustard stimulants, such as 2-chloroethyl ethyl sulfide (2-CEES) and 2-chloroethyl phenyl sulfide (2-CEPS) under green and "ambient" conditions (25 °C, 1atm O2) in the presence of ethanol with high efficiency and selectivity. 2-CEES was selected as a model reaction to optimize the parameters of the reaction. The progress of the reaction was evaluated after different times using GC-FID, GCMS and TLC. The reaction product was also confirmed by 1H-NMR spectroscopy. The aerobic oxidation results of 2-CEES showed that PAN NFs/[Mo154] have a conversion of 98% to produce only a nontoxic product, 2-CEESO with the selectivity of 100% after 45min. The results were performed using [Mo154] without any PAN NFs for comparison whereas [Mo154] converts only 52% of 2-CEES under identical conditions. Heterogeneous PAN NFs/[Mo154] catalyst was reused after washing with solvent up to 5 steps without leaching of [Mo154] from PAN NFs and without any loss in efficiency due to the morphology of NFs. In addition to the recovery of PAN NFs/[Mo154] in different cycles, the use of FT-IR, UV-Vis and TEM techniques confirms the stability and morphology of PAN NFs/[Mo154] after the fifth cycle, 2-CEES oxidation. According to our information, this report is the first use of PAN NFs enriched with [Mo154] for aerobic oxidation of sulfur mustard simulants.

Evaluation of the effects of dexamethasone in modulating breathing pattern decomplexification in rats with 2-chloroethyl ethyl sulfide-induced lung injury

"Background and Objectives: Sulfur mustard is a functional alkylating chemical warfare agent that gives rise to appalling lung injury. In people with pulmonary diseases, including asthma, the complication of respirational dynamics is reduced. However, the complexity of breathing patterns in lung injury caused by chemical agents is not clear. In the current study, the outcome of 2-chloroethyl ethyl sulfide (CEES), and mustard analogue, upon breathing pattern of rats without or with treatment were reviewed. Methods: The interbeat interval (IBI) and respiratory volume (RV) data have been acquired from spontaneous respiration rats with lung injury by CEES using a whole-body plethysmograph. We calculated mean and coefficient of variation, alpha exponent derived from detrended fluctuation analysis (DFA), and sample entropy of IBI and RV. Finding: Entropy examination of respiratory variation displayed reduced inconsistency (less complication) in the breathing pattern of this rat model of lung injury. The mustard analogue also led to increased lung inflammation in damaged rats. However, treatment by NAC and dexamethasone had a compelling impact on the complication of the breathing rhythm and lung inflammation of rats with lung injury. Conclusion: Our findings show that inflammation could be the possible origin of respiratory dynamics shifting apart from the normal variation in CEES-induced lung injury"

Detection of hazardous chemical using dual-wavelength Raman spectroscopy in the ultraviolet region

This study proposes a stand-off Raman spectroscopy system using dual-wavelength in the ultraviolet (UV) region to detect hazardous chemicals. The Raman spectrum generated by the UV excitation source avoids solar background noise during daytime for chemical detection as the spectrum is in the solar blind range. Wavelengths of 213 and 266 nm by 5th and 4th harmonics are generated from Nd:YAG laser. However, Raman spectra of chemicals exhibit different signal-to-noise ratios for both the excitation wavelengths; therefore, to detect such chemicals, Raman spectra by two sources are required. Raman spectra were acquired using a dual-wavelength laser and spectrometer with a single grating and detector at the wavelengths of 213 and 266 nm simultaneously. The Raman spectra of sulfuric acid, 2-chloroethyl ethyl sulfide, and dimethyl methylphosphonate were acquired and analyzed, thus highlighting the application of dual-wavelength Raman spectroscopy. For efficient chemical detection in the field, we have ensured that the system developed in this study is robust.

Cooperative Catalysis between Dual Copper Centers in a Metal-Organic Framework for Efficient Detoxification of Chemical Warfare Agent Simulants.

Chemical warfare agents (CWAs) are among the most lethal chemicals known to humans. Thus, developing multifunctional catalysts for highly efficient detoxification of various CWAs is of great importance. In this work, we developed a robust copper tetrazolate metal-organic framework (MOF) catalyst containing a dicopper unit similar to the coordination geometry of the active sites of natural phosphatase and tyrosinase enzymes. This catalyst aided in phosphate ester bond hydrolysis and hydrogen peroxide decomposition, ultimately achieving high detoxification efficiency against both a nerve agent simulant (diethoxy-phosphoryl cyanide (DECP)) with a half-life of 3.5 min and a sulfur mustard simulant (2-chloroethyl ethyl sulfide (CEES)) with a half-life of 4.5 min, making it competitive with other reported materials. The dicopper sites in ZZU-282 provide versatile binding modes with the substrates, thereby promoting the activation of substrates and enhancing the catalytic efficiency. A combination of postmodified metal exchange control experiments, density functional theory calculations, and catalytic evaluations confirmed that dual Cu sites are the active centers promoting the catalytic reaction. This study offers a new design perspective to achieve advanced catalysts for CWA detoxification.

MIP-202 catalyst-integrated solid-contact potentiometric chloride sensor for versatile multiphasic detection of a sulfur mustard simulant

Existing sensor devices for sulfur mustard (HD) detection are commonly bulky, sluggish in response, or not sensitive enough to detect HD contamination owing to its low aqueous solubility. Herein, we describe the development of a miniaturized catalytic electrochemical sensor, in both portable and wearable configurations, for the real-time, remote/on-site wireless detection of low micromolar levels of the HD simulant, 2-chloroethyl ethyl sulfide (CEES). The screen-printed CEES potentiometric sensor relies on coating a new solid-contact chloride ion-selective electrode (Cl-ISE) with a biomimetic zirconium metal-organic framework (Zr-MOF), MIP-202-based reagent layer for catalytic CEES hydrolysis and electrochemical detection of the liberated Cl anion. We describe and characterize the use of the green MIP-202 Zr-MOF towards such CEES hydrolysis, and demonstrate its superior catalytic performance versus the established MOF catalysts UiO-66 and HKUST-1 using proton nuclear magnetic resonance (1H NMR) analysis. The attractive analytical performance of the resulting strip and textile-based sensors has been demonstrated for the detection of CEES contamination in multiphasic samples ranging from aqueous buffered solutions, drinking water to aqueous buffered aerosols.

Tumor-targeted dual-starvation therapy based on redox-responsive micelle nanosystem with co-loaded LND and BPTES.

The starvation therapy mediated by the lonidamine (LND) was limited by the low drug delivery efficiency, off-target effect and compensative glutamine metabolism. Herein, a hyaluronic acid (HA)-modified reduction-responsive micellar nanosystem co-loaded with glycolysis and glutamine metabolism inhibitor (LND and bis-2-(5-phenylacetmido-1,2,4-thiadiazol-2-yl)ethyl sulfide, BPTES) was constructed for tumor-targeted dual-starvation therapy. The in vitro and in vivo results collectively suggested that the fabricated nanosystem could effectively endocytosed by tumor cells via HA receptor-ligand recognition, and rapidly release starvation-inducers LND and BPTES in response to the GSH-rich intratumoral cytoplasm. Furthermore, the released LND and BPTES were capable of inducing glycolysis and glutamine metabolism suppression, and accompanied by significant mitochondrial damage, cell cycle arrest and tumor cells apoptosis, eventually devoting to the blockade of the energy and substance supply and tumor killing with high efficiency. In summary, HPPPH@L@B nanosystem significantly inhibited the compensatory glycolysis and glutamine metabolism via the dual-starvation therapy strategy, blocked the indispensable energy and substance supply of tumors, consequently leading to the desired tumor starvation and effective tumor killing with reliable biosafety.

Efficient removal of 2-chloroethyl ethyl sulfide in solution under solar light by magnesium oxide-decorated polymeric carbon nitride photocatalysts and mechanism investigation

• CN/MgO heterostructure was prepared by thermal exfoliation followed by precipitation. • Rich N defects and O dopants boosted photo-activity of CN/MgO with high surface area. • A built-in electric field at the interface spatially separated electron-hole pairs. • CN/MgO degraded 99% CEES within 120 min under visible light and ambient conditions. • CN/MgO detoxified CEES with good selectivity to non-toxic sulfoxide in solution. Removing hazardous chemicals such as chemical warfare agents is crucial for the environment, defense, and public security. Herein, magnesium oxide-decorated carbon nitride photocatalysts (CN/MgO) were fabricated for detoxification of 2-chloroethyl ethyl sulfide (CEES) in solutions under the irradiation of a solar simulator. CN/MgO samples were prepared via thermal exfoliation followed by precipitation. The surface enhancements of as-prepared photocatalyst, such as high specific surface area, rich-nitrogen defects, and oxygen dopants, improved adsorption capacity, reaction active sites, and localized charge distribution. CN/MgO catalyst showed high performance of detoxification of CEES in solutions (99% of 200 parts per million volume (ppmv) hydroxylethyl ethyl sulfide, a hydrolysis product of CEES, within 120 min). In addition, the detoxification in chloroform solution was conducted to elucidate the hydrolysis effect in the solution phase. Density functional theory calculations revealed that a built-in electric field at the heterostructure interface could facilitate spatial separation of photo-excited electron-hole pairs. Scavenger tests proved that superoxide radicals contributed to good photo-oxidation reactivity. The reaction mechanism was suggested using the results with GC-MS, XPS, FTIR, and XRD. The as-prepared photocatalyst could function under ambient conditions without adding any base or acid. The detoxification exhibited good selectivity to transfer CEES to sulfoxide, avoiding over-oxidation to generate toxic sulfone.

Study of metal-Co/Zn-doped CuSCN contacts for efficient hole transport in perovskite solar cells

Developing innovative ways to revolutionize perovskite solar cell (PSC) technology requires overcoming many challenges, which has motivated extensive research on this field in the last decade. Compared to Spiro-OMETAD, CuSCN, a p-type wide bandgap semiconductor, possesses higher hole mobility, more extended stability, more suitable energy levels, and a cost-competitive hole transport layer (HTL) in the PSCs. CuSCN is insoluble in most typical solvents; consequently, its processing is still under investigation, except for sulfur-based solvents, which are among the most effective and widely studied solvents. In this work, the best morphology of CuSCN layer was obtained at its 0.3 Molar concentration in Diethyl Sulfide (DES), the most excellent polar Sulfur-based solvent, and applying Acetonitrile as the co-solvent in volume ratio of 1:1.5 (DES:Acetonitrile). Moreover, choosing the proper metal as the back contact of the CuSCN to achieve a high-quality metal contact is also considered important in this study. Because of its high conductivity, which is recommended by examining the resistivity of various metal contacts, Titanium is considered as the most suitable option to be in contact with CuSCN. Furthermore, it is found that the addition of substitution additives such as Co and Zn (0.1 M) improves the uniformity, conductivity, and solubility of CuSCN.

Fe-Doped MoS2 Nanozyme for Antibacterial Activity and Detoxification of Mustard Gas Simulant.

The peroxidase-like catalytic activity of various nanozymes was extensively applied in various fields. In this study, we have demonstrated the preparation of Fe-doped MoS2 (Fe@MoS2) nanomaterials with enhanced peroxidase-like activity of MoS2 in a co-catalytic pathway. In view of Fenton reaction, the peroxidase-like Fe@MoS2 nanozyme prompted the decomposition of hydrogen peroxide (H2O2) to a reactive hydroxyl radical (·OH). The efficient decomposition of H2O2 in the presence of Fe@MoS2 has been employed toward the antibacterial activity and detoxification of mustard gas simulant. The combined effect of Fe@MoS2 and H2O2 showed remarkable antibacterial activity against the drug-resistant bacterial strain methicillin-resistant Staphylococcus aureus and Escherichia coli with the use of minimal concentration of H2O2. Fe@MoS2 was further applied for the detoxification of the chemical warfare agent sulfur mustard simulant, 2-chloroethyl ethyl sulfide, by selective conversion to the nontoxic sulfoxide. This work demonstrates the development of a hybrid nanozyme and its environmental remediation from harmful chemicals to microbes.

Experimental and Theoretical Kinetic Studies of the Ozonolysis of Selected Allyl Sulfides (H2C═CHCH2SR, R = CH3, CH3CH2): The Effect of Nascent OH Radicals.

Rate coefficients of the O3-initiated oxidation of allyl methyl sulfide (H2C═CHCH2SCH3, AMS) and allyl ethyl sulfide (H2C═CHCH2SCH2CH3, AES) were determined at atmospheric conditions by "in situ" FTIR. The relative kinetic experiments were performed using methylcyclohexane (McH) and carbon monoxide (CO) as nascent OH radical scavengers and in the absence of any scavenger, to determine the impact that the formation of OH radicals has on the rate coefficients. In the absence of scavengers, values of kAMS+O3 = (5.23 ± 3.57) × 10-18 and kAES+O3 = (5.76 ± 1.80) × 10-18 cm3 molecule-1 s-1 were obtained. In the presence of the scavengers, however, the rates decreased to kAMS+O3+McH = (3.92 ± 1.92) × 10-18 and kAMS+O3+CO = (2.63 ± 0.47) × 10-18 cm3 molecule-1 s-1 for AMS, and kAES+O3+McH = (4.78 ± 1.38) × 10-18 and kAES+O3+CO = (3.50 ± 0.27) × 10-18 cm3 molecule-1 s-1 for AES. On the basis of these results, we have decided to recommend the values obtained using CO as scavenger as those best representing the rate coefficient for the reactions of O3 with AMS and AES. The reaction mechanism was explored using DFT and post-Hartree-Fock computational methods. It is shown that the barrier for the common cyclization to primary ozonide (-3.7 ± 0.1 kcal mol-1) followed by other reactions, as well as that for the reaction with the sulfur atom (-5.1 ± 0.1 kcal mol-1), is small and quite close, meaning that both reaction paths should contribute significantly to the global reaction rate.

Sulfur mustard analog 2-chloroethyl ethyl sulfide increases triglycerides by activating DGAT1-dependent biogenesis and inhibiting PGC1ɑ-dependent fat catabolism in immortalized human bronchial epithelial cells

Using sulfur mustard analog 2-chloroethyl ethyl sulfide (CEES), we established an in vitro model by poisoning cultured immortalized human bronchial epithelial cells. Nile Red staining revealed lipids accumulated 24 h after a toxic dose of CEES (0.9 mM). Lipidomics analysis showed most of the increased lipids were triglycerides (TGs), and the increase in TGs was further confirmed using a Triglyceride-Glo™ Assay kit. Protein and mRNA levels of DGAT1, an important TG biogenesis enzyme, were increased following 0.4 mM CEES exposure. Under higher dose CEES (0.9 mM) exposure, protein and mRNA levels of PPARγ coactivator-1ɑ (PGC-1ɑ), a well-known transcription factor that regulates fatty acid oxidation, were decreased. Finally, application with DGAT1 inhibitor A 922500 or PGC1ɑ agonist ZLN005 was able to block the CEES-induced TGs increase. Overall, our dissection of CEES-induced TGs accumulation provides new insight into energy metabolism dysfunction upon vesicant exposure. HIGHLIGHTS In CEES (0.9 mM)-injured cells: Triglycerides (TGs) were abundant in the accumulated lipids. Expression of DGAT1, not DGAT2, was increased. Expression of PGC1ɑ, not PGC1β, was reduced. DGAT1 inhibitor or PGC1ɑ agonist blocked the CEES-mediated increase in TGs.