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The detection of highly toxic chemicals such as phosgene is crucial for addressing the severe threats to human health and public safety posed by terrorist attacks and industrial mishaps. However, timely and precise monitoring of phosgene at a low cost remains a significant challenge. This work is the first to report a novel fluorescent system based on the Intramolecular Charge Transfer (ICT) effect, which can rapidly detect phosgene in both solution and gas phases with high sensitivity by integrating a benzo[1,2-b:6,5-b']dithiophene-4,5-diamine (BDTA) probe. Among existing detecting methods, this fluorescent system stands out as it can respond to phosgene within a mere 30 s and has a detection limit as low as 0.16 μM in solution. Furthermore, the sensing mechanism was rigorously validated through high-resolution mass spectrometry (HRMS) and density functional theory (DFT) calculations. As a result, this fluorescent probing system for phosgene can be effectively adapted for real-time, high-sensitivity sensing and used as a test strip for visual monitoring without the need for specific equipment, which will also provide a new strategy for the fluorescent detection of other toxic materials. [ABSTRACT FROM AUTHOR]

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A reaction model was recently been postulated to describe the phosgene synthesis process over an activated carbon catalyst. That body of work exclusively considered a single grade of activated carbon (Donau Supersorbon K40), raising the issue that the mechanistic insight gleaned could be restricted to the single substrate. Therefore, to evaluate the generality of the proposed sequence of elementary reactions that lead to phosgene production, this article concentrates on Norit RX3 Extra, a representative activated carbon that finds wide application in industrial applications. Several phosgene synthesis traits were associated with Donau Supersorbon K40 and are reproduced with Norit RX3 extra over the reaction conditions studied, such as exclusive phosgene selectivity and a degree of reagent retention. However, temperature‐programmed reaction studies show the reaction profile of the Norit RX3 extra to exhibit deviations from that observed for Donau Supersorbon K40. A modified reaction model is proposed to account for these differences. The revised reaction model is thought to represent a generic model for phosgene synthesis that can accommodate disparities in the surface chemistry of different activated carbon formulations. [ABSTRACT FROM AUTHOR]

The reactions of oxalyl chloride were investigated in the binary superacidic systems HF/SbF5 and DF/SbF5. O‐Monoprotonated oxalyl chloride was isolated and represents the first example of a protonated acyl chloride. Diprotonated oxalyl chloride is only stable in solution. Salts of the ClCO+ cation were synthesized from the reactions of oxalyl chloride or COClF with SbF5 in 1,1,1,2‐tetrafluoroethane (R‐134a, CF3CFH2). The colourless salts were characterized by low‐temperature vibrational spectroscopy, NMR spectroscopy and single‐crystal X‐ray diffraction. (1,2‐Dichloro‐2‐oxoethylidene)oxidanium hexafluoridoantimonate(V), [C2O(OH)Cl2][SbF6], crystallizes in the monoclinic space group P21 and carbonyl chloride hexadecafluoridotriarsenate(V) [ClCO][Sb3F16], in the trigonal space group P31, with two and three formula units per unit cell, respectively. Monoprotonated oxalyl chloride and the ClCO+ cation both display very short C—Cl bonds with a strong double‐bond character. [ABSTRACT FROM AUTHOR]

The degree of ease of use and the readily observable signals associated with the detection process are critical factors in determining the success of a detection strategy. Considering this perspective, we report the detection of phosgene by modulating the photophysical characteristics of a molecular probe, Xanth-NH2. The probe is non-emissive in nature, but the presence of phosgene facilitates the probe's radiative decay, which enables phosgene detection via fluorescence turn-on change. The fluorescence changes vary linearly with phosgene concentration, contributing to a nanomolar level detection limit for phosgene. Additionally, under a controlled set of conditions, the half-time for the reaction of Xanth-NH2 with phosgene is 68 s. To demonstrate the potential application of Xanth-NH2, probe-loaded paper strips or silica gel were developed as an economic tool for the detection of phosgene in vapor or solution phase. Phosgene detection has been accomplished with a portable UV light source and a smartphone to track minute changes during the detection event. [ABSTRACT FROM AUTHOR]

Fire deaths present several diagnostic challenges for the forensic examiner, the most significant of which is the identification of the cause of death and the evaluation of the morphological consequences of heat injuries in the ante-mortem and post-mortem periods. Here, we describe the case of two young lovers found dead inside a travelling carousel destroyed by a fire. Circumstantial evidence of disputes between families running the town fair raised the suspicion of intentional arson. Comparative analysis of crime scene investigation, radiological, autoptic, histological, and toxicological findings revealed signs of vitality (i.e., presence of soot deposits inside the respiratory and digestive tracts, heat damage to the respiratory mucosa) and identified fatal asphyxia from haemorrhagic pulmonary oedema as the cause of death. Since the experimental burning of plastic samples collected from a similar carousel demonstrated the significant production of phosgene, the death of the two lovers was attributed to the probable inhalation of this gas. The case presented here underlines the importance of a multidisciplinary approach of any fire-related death, providing an insight into circumstantial and forensic (autopsy, toxicological, and immunohistopathological) elements useful in raising suspicion of possible toxic gas inhalation. In the presence of high levels of PVC materials at the fire scene and pulmonary oedema at the autopsy, with no alternative causes of death, the forensic pathologist must suspect a fatal exposure to phosgene. [ABSTRACT FROM AUTHOR]

Chemical warfare agents (CWAs) are very toxic and dangerous to all forms of life. With the purpose of protecting environment and human health, it is essential to identify and eliminate these threats quickly and effectively. B38 nanocage as a sensor is rarely discussed therefore the detection of harmful CWAs (phosgene and thiophosgene) by using the B38 nanocage has been examined using density functional theory (DFT) parameters. Optimized geometries, adsorption energies, NCI, NBO, FMO and QTAIM studies have been used to analyze the interactions between CWAs and the B38 nanocage. The adsorption energy values indicate that CWAs are adsorbed on the B38 nanocage in a stable manner and the reaction is exothermic. The complex T-S@B38-B have the greatest conductivity, lowest stability and maximum sensitivity due to its narrow energy gap of 1.9648 eV while complex T-S@B38-6r, with the highest energy gap of 1.9988 eV is the most stable. The global reactivity parameters indicate that the complex T-S@B38-B has the highest electrophilicity index, the lowest chemical hardness and the highest chemical softness and resultantly leads to highest sensitivity. Van der Waals forces are present between the B38 nanocage and CWAs as shown by NCI and QTAIM studies. The formation of new energy level in PDOS of B38 results into the interaction of CWAs with the surface of B38. Nanocage sensing capacity is evaluated by measuring Eg value, sensitivity and recovery time of the complex. B38 has the highest sensitivity and shortest recovery time for T-S@B38-B and P-Cl@B38-B complex with 5.90 × 10−3 and 2.78259 × 10−12 s values which results the B38 nanocage is more effective sensor for detecting CWAs. Consequently, B38 nanocage is recommended as fine future sensor for the sensing of phosgene and thiophosgene. [ABSTRACT FROM AUTHOR]

The Ni‐catalyzed enantioselective addition reaction of aryl halides to aldehydes was studied with cyanobis(oxazoline) as chiral ligands and Mn as reductant. Aryl and heteroaryl bromides reacted with phenyl aldehyde at room temperature to produce dibenzyl alcohols in 16–99 % yields with 53–92 % ees. Moreover, the coupling of phenyl chloride with a variety of aryl, heteroaryl and alkyl aldehydes was demonstrated in the presence of cyanobis(oxazoline)/Ni(II) at 60 °C in generally high yields with moderate enantioselectivities. [ABSTRACT FROM AUTHOR]

The crystal and molecular structures of the complex [99TcCl(CO)3(C5H8O2)]2 (C5H8O2 = Hacac = acetylacetone) formed in the course of prolonged standing of a [99Tc(acac)(CO)4] solution in ССl4/CDCl3 and of its analog containing no organic ligand, [99TcCl(CO)4]2, were determined. Both complexes contain a [Tc2(μ-Cl)2] four-membered ring. The remaining sites in the coordination sphere of the Tc atom are occupied by carbonyl ligands, and in the case of [99TcCl(CO)3(Hacac)]2, also by the neutral acetylacetone molecule in the enol form. The Hacac molecules in the binuclear complex are in the cis position to the Cl atoms in the octahedral surrounding of the Тс atoms and in the trans position to each other relative to the [Tc2(μ-Cl)2] ring. A comparative analysis of the geometries of the complexes and their known analogs was performed. [ABSTRACT FROM AUTHOR]

The crystal and molecular structures of the complex [99TcCl(CO)3(C5H8O2)]2 (C5H8O2 = Hacac = acetylacetone) formed in the course of prolonged standing of a [99Tc(acac)(CO)4] solution in ССl4/CDCl3 and of its analog containing no organic ligand, [99TcCl(CO)4]2, were determined. Both complexes contain a [Tc2(μ-Cl)2] four-membered ring. The remaining sites in the coordination sphere of the Tc atom are occupied by carbonyl ligands, and in the case of [99TcCl(CO)3(Hacac)]2, also by the neutral acetylacetone molecule in the enol form. The Hacac molecules in the binuclear complex are in the cis position to the Cl atoms in the octahedral surrounding of the Тс atoms and in the trans position to each other relative to the [Tc2(μ-Cl)2] ring. A comparative analysis of the geometries of the complexes and their known analogs was performed. [ABSTRACT FROM AUTHOR]

The theoretical examination of the interaction among formaldehyde, phosgene, and thiophosgene molecules on both pristine Zn12O12 nanocage and TM-decorated (Cu, Ni, Ti, and Cr) Zn12O12 nanocage is conducted using density functional theory (DFT). The Zn12O12 nanocage by doping of Cu, Ni, Ti, and Cr atoms remarks in altering the electronic properties and actively reassuring the adsorption of these toxic gases. The finding revealed that Zn12O12 nanocages doped with metal atoms enhance reactivity. In this study, the adsorption energy, dipole moment, charges from natural bond orbitals (NBO), global reactivity parameters, and frontier molecular orbitals (FMOs) were analyzed. The results show that phosgene and thiophosgene are physisorbed on Zn12O12 nanocage with adsorption energies of -10.63, and -9.41 kcal/mol, respectively. The decoration of Zn12O12 nanocage with transition metals (Cu, Ni, Ti, and Cr), efficiently enhanced the adsorption of H2CO, COCl2, and CSCl2. The adsorption of these harmful gases on TM-decorated Zn12O12 nanocage resulted in strong chemisorption. Among the selected warfare agents, CSCl2@Cr-Zn12O12 and H2CO@Ti-Zn12O12 show the highest value of adsorption energy (− 77.86 and − 75.37 kcal/mol, respectively). These complexes also exhibit high chemical hardness value and low softness value suggesting their higher stability and lower reactivity as compared to other complexes. Moreover, the results of recovery time suggested that COCl2 can be desorbed from Ni-Zn12O12 with a recovery time of 0.014 s. Therefore, it is suggested that the Ni-Zn12O12 nanocage may be used as a potential reusable sensor for the detection of phosgene at room temperature due to its high sensitivity and short recovery time. Additionally, the results suggested that the adsorption energy and electrical conductivity of toxic gases on decorated Zn12O12 nanocage increase, potentially improving sensitivity towards these toxic gases. [ABSTRACT FROM AUTHOR]

(S)-1-Methyl-2-oxoimidazolidine-4-carboxylic acid 1 is an analog of (S)-pyroglutamic acid, a key component of naturally occurring peptide hormones and synthetic pharmaceutical candidates. The reaction of (S)-2-amino-3-(methylamino)propionic acid with COCl2 and aqueous NaHCO3 followed by ion exchange afforded 1, which was recrystallized from acetonitrile and then characterized by IR, 1H NMR, 13C NMR, polarimetry, elemental microanalysis, high-resolution mass spectrometry and single-crystal X-ray diffraction. The acid 1 crystallized in the orthorhombic chiral space group P212121 with cell constants a = 6.2275(4) Å, b = 8.3963(5) Å, c = 24.9490(14) Å. The X-ray crystal structure revealed that two distinct conformers of 1 occur at alternating positions within helices which are supported by hydrogen bonds. Each molecule of 1 is linked to its two neighbors in the helix by a total of three hydrogen bonds, and four molecules of 1 are contained within each turn of the helix. The pattern of hydrogen bonds illustrates a preference for the carboxylic acid group to act as a hydrogen bond donor and for the urea unit to be a hydrogen bond acceptor. [ABSTRACT FROM AUTHOR]

Carbonyl dichloride (COCl2), also known as phosgene, is a highly toxic gas, whose exposure or acute inhalation causes severe respiratory complications, such as pulmonary edema, pulmonary emphysema, and even death. In this study, we theoretically investigated the complexes formed by the interaction between the COCl2 (phosgene) and OCY molecules (Y = S, Se, and Te). Complex geometry optimization yielded three distinct types of conformations. Conformation-I complexes were stabilized by two concurring chalcogen-bonding interactions (i.e. O⋯Y and Cl⋯Y) by forming a ring structure. However, only a single linear interaction (O⋯C) or (O⋯Cl) occurred in conformation-II and III complexes, forming complexes with the nature of tetrel and halogen bonds, respectively. According to the results of the molecular electrostatic potential (MEP), interaction energy (ΔET), natural bond orbital (NBO), and so on, the σ-hole of the Y atom in the OCY molecule exhibited higher acidic strength and formed more stable complexes than those resulting from the σ- and π-holes of the COCl2 molecule. [ABSTRACT FROM AUTHOR]

Background: Phosgene is a chemical material widely used worldwide. No effective method has been developed to reverse its pathological injuries. Some studies have shown that neuronal inflammation in lung tissue is involved, but the specific mechanism has not been reported. Objective: To analyze the expression alterations of whole transcriptome gene sequencing bioinformatics and protein expression profile in lung tissue after phosgene aspiration lung injury (P-ALI) and find the main factors and pathways affecting the prognosis of P-ALI. Methods: Rat models of P-ALI were made by phosgene. Rats were divided into a P-ALI group and a blank group. Hematoxylin-eosin (HE) staining and lung wet/dry ratio measurement were used to evaluate the lung injury. The levels of inflammatory factors were measured by ELISA. High-throughput sequencing was used to measure the expression profile of each gene. Protein expression profiles were determined by label-free relative quantification of the differential proteome. Results: Lung injury such as the disordered structure of alveolar wall and inflammatory factors (IL-1ß, IL-18, and IL-33) were significantly increased in the P-ALI group (p < 0.05). There were 225 differentially expressed lncRNAs, including 85 upregulated and 140 downregulated genes. They were also the genomes with the most significant changes in transcriptome gene expression, mainly constituting cytoplasmic, synaptic structures and transporters, and involved in amino acid and carbon metabolism. There were 42 differentially expressed circRNAs, including 25 upregulated genes and 17 downregulated genes, mainly involved in cell composition, growth, differentiation, and division. There were only 10 differentially expressed miRNAs genes, all upregulated and mainly involved in the inflammatory response pathway. Proteome identification showed 79 differentially expressed proteins. KEGG enrichment analysis showed that it was mainly involved in the N-glycan biosynthesis pathway. Conclusion: We discovered that differentially regulated genes (lncRNAs, circRNAs, and miRNAs) were primarily associated with neuronal reflexes and synaptic signaling, including neurotransmitter transmission, ion signaling pathway conduction, neuronal projection, and synaptic vesicle circulation. They affected inflammatory factors and other metabolic pathways. This finding could be explored in future studies. [ABSTRACT FROM AUTHOR]

A fluorescent probe, 4-(di-phenylamino)-benzaldehyde oxime (DPBO), was developed comprising 4-(diphenylamino) benzaldehyde as the fluorophore and hydroxyl amine, where the resultant oxime group leads to the formation of a recognition site for the selective "on–off" fluorescence detection of lethal phosgene with the dimer formation of DPBO through carbonate linkage generated from phosgene. The probe DPBO also exhibits notable spectrofluorometric response in different solvents, as demonstrated by SEM analysis. The detection limit of the probe DPBO towards phosgene was calculated as 21.53 μM, with a fast reaction response time within 30 s and the fluorescence quenching efficiency of DPBO by phosgene was measured through the Stern–Volmer quenching constant (KSV) estimated at 1.03 × 104 M−1. Confirmation of the sensing mechanism was achieved through various spectroscopic techniques such as UV-vis, emission spectroscopy, mass spectrometry, and computational studies. For practical applications, the sensor DPBO can be utilized for the detection of phosgene in household bleach, soil analysis and dipstick method. [ABSTRACT FROM AUTHOR]

Exposure to phosgene, a colourless poisonous gas, can lead to various health issues including eye irritation, a dryand burning throat, vomiting, coughing, the production of foamy sputum, difficulty in breathing, and chest pain. Thissystematic review aims to provide a comprehensive overview of the clinical manifestations and treatment of phosgenetoxicity by systematically analyzing available literature. The search was carried out on various scientific online databasesto include related studies based on inclusion and exclusion criteria with the use of PRISMA guidelines. The quality ofthe studies was assessed using the Mixed Methods Appraisal Tool (MMAT). Thirteen articles were included in thisstudy after the screening process. Inhalation was found to be the primary health problem of phosgene exposure withrespiratory symptoms such as coughing and dyspnea. Chest pain and pulmonary oedema were also observed in somecases. Furthermore, pulmonary crackle was the most common reported physical examination. Beyond respiratory tracthealth issues, other organs involvements such as cardiac, skin, eye, and renal were also reported in some studies. Thesymptoms can occur within minutes to hours after exposure, and the severity of symptoms depends on the amount ofinhaled phosgene. The findings showed that bronchodilators can alleviate symptoms of bronchoconstriction causedby phosgene. Oxygen therapy is essential for restoring oxygen levels and improving respiratory function in casesof hypoxemia. In severe cases, endotracheal intubation and invasive mechanical ventilation are used for artificialrespiration, along with the removal of tracheal secretions and pulmonary oedema fluid through suctioning as crucialcomponents of supportive therapy.

Nonisocyanate polyurethanes (NIPUs) are an emerging class of polyurethanes produced by circumventing the use of hazardous isocyanates and phosgene in their synthetic routes. In this study, we introduce a novel class of water-soluble/dispersible nonisocyanate polyurethanes (NIPUs) containing phosphate pendant groups, referred to as NIPU phosphate monoesters, by applying green chemistry principles. Linear NIPU polymers with number average molecular weight (Mn) values ranging between 7400 and 13 600 Da and weight average molecular weight (Mw) values between 13 900 and 27 800 Da were synthesised by the polymerization of bio-derived cyclic biscarbonates 4,4′-(((furan-2,5-diylbis(methylene)) bis(oxy))bis(methylene)) bis(1,3-dioxolan-2-one) (FuBCC) and bis((2-oxo-1,3-dioxolan-4-yl)methyl) succinate (SuBCC) with 1,5-pentanediamine (cadaverine) by utilizing green solvents. Subsequent functionalization of the resultant NIPUs via mild and selective phosphorylation using tetrabutylammonium dihydrogenphosphate (TBAP) as a phosphate source delivered NIPU phosphate monoesters containing up to 50% phosphate functionality as determined by 1H NMR. Interestingly, these phosphate-containing NIPUs were soluble/dispersible in water without the need for any external surfactants/co-solvents and demonstrated inherent aerobic biodegradability (56–75% in 28 days). Furthermore, the NIPU phosphate monoesters exhibited remarkable biocompatibility, showing slight to no growth inhibition of human keratinocyte HaCaT cells at concentrations up to 1 mg mL−1. In vitro skin irritation assays on reconstructed human epidermis confirmed their non-skin irritant properties. These NIPU phosphate monoesters also exhibited multifunctional characteristics including oil-in-water emulsion stabilization ability and antimicrobial activity. This work emphasizes the scope and potential of these bio-derived, non-toxic and biodegradable nonisocyanate polyurethane phosphate monoesters as multifunctional additives in personal care/cosmetic applications. [ABSTRACT FROM AUTHOR]

Phosgene is a highly concealed and highly toxic gas that seriously threatens human health and public security. Therefore, the detection of phosgene is of great significance to world security. Herein, a new type of fluorescent probe based on 2-(2-aminophenyl) imidazo [1,5-a] pyridine is reported for the rapid detection of phosgene. The probe itself only emits a faint green fluorescence, while phosgene allows it to produce a strong blue fluorescence. During the recognition process, phosgene interacts simultaneously with both amino site and imidazole moiety in the probe molecule, resulting in a four-ring-fused rigid structure with high fluorescence quantum yield. The probe not only has the characteristics of high efficiency, high sensitivity (detection limit 2.68 nM), and high selectivity, but also has remarkable spectral changes. Finally, a portable test strip is used to detect phosgene in the gas phase, and the fluorescent color change of the test strip can be easily observed. The most exciting thing is that the portable test strip with the probe PMPY-NH2 can produce a strong fluorescence response to 1 ppm of phosgene, which is far lower than the level of phosgene that seriously threatens to human health. [ABSTRACT FROM AUTHOR]

Inhalation of high concentrations of phosgene often causes pulmonary edema, which obstructs the airway and causes tissue hypoxia. There is currently no specific antidote. This study was performed to investigate the effect behind pentoxifylline (PTX) treatment for phosgene-induced lung injury in rat models. Rats were exposed to phosgene. The protein levels of hypoxia-inducible factor-1α (HIF-1α), vascular endothelial growth factor (VEGF), and occludin proteins in lung tissue were determined. The effect of both prophylactic and therapeutic administration of PTX (50 mg/kg and 100 mg/kg) was evaluated. The lung permeability index and HIF-1α protein level increased, the arterial blood oxygenation index (PaO2/FIO2 ratio) and occludin protein level decreased significantly 6 h after phosgene exposure (P < 0.05). PTX exerted protective effects by HIF-1α-VEGF-occludin signaling pathway to some extent. Moreover, prophylactic, but not therapeutic administration of PTX (100 mg/kg), exhibited a significant protective effect. Pretreatment with PTX protected against phosgene-induced lung injury, possibly by inhibiting differential expression of HIF-1α, VEGF, and occludin. [ABSTRACT FROM AUTHOR]

Ph3P is found to be inert to sodium in toluene even on heating. This phenomenon leads to the finding that in toluene Ph3PS reacts with sodium efficiently and selectively to produce quantitative yields of highly valuable Ph3P and anhydrous Na2S. By applying this finding, anhydrous Na2S can be safely and conveniently prepared using a Ph3P-mediated reaction from sodium and sulfur. This finding also leads to the establishment of a feasible alternative strategy (the sulfur method) for the restoration of the Ph3PO waste to Ph3P that is greener and safer than the currently operating "chlorine method" using phosgene. [ABSTRACT FROM AUTHOR]

In order to scrutinize the impact of the decoration of Au upon the sensing performance of an YN nanotube (YNNT and X = B, Al, or Ga) in detecting phosgene oxime (PO), the density functionals M06-2X, τ-HCTHhyb, and B3LYP were utilized. The interaction of the pristine YNNT with PO was physical adsorption. The sensing response (SR) of approximately 8.0. Decoration of the Au metal into the surface of the YN led to an increase in the adsorption energy of PO from − 3.4 to − 18.2 (for boron nitride nanotube = BNNT), from − 3.8 to − 19.1 (for aluminum nitride nanotube = AlNNT), and − 4.3 to − 19.8 (for gallium nitride nanotube = GaNNT) kcal/mol, respectively. Also, there was a significant increase in the corresponding SR to 30.5, 61.5, and 102.5, and the sensitivity of metal decorated YNNT (metal@YNNT) increased. We found that Au-decorating increases the sensitivity of GaNNT toward PO compare to AlNNT and BNNT. Also, the recovery time for PO to be desorbed from the Au@GaNNT surface was found to be short (26.8 s). Thus, Au@GaNNT is suggested as a promising chemical sensor for PO detection. [ABSTRACT FROM AUTHOR]

The interaction of gaseous chlorine with granules based on zirconium dioxide and carbon-containing material was studied. The most probable chemical processes occurring in the ZrO2–C–Cl2 system. The interaction of granules with gaseous chlorine was analyzed on the basis of ideas about the chain mechanism of chlorination. [ABSTRACT FROM AUTHOR]

The introduction of poison gases by the Germans at Ypres in April 1915 marked a new era in modern warfare. The cylinder attack of the German Army against the French and the British positions at Ypres on April 22, 1915, became the first large-scale appearance of the new kind of weapons, chemical weapons, on the battlefields of World War 1. The widespread use of chemical munitions of different types, numerous toxic agents and their delivery systems (field and heavy artillery, mortars and Livens projectors) by all the belligerents influenced military tactics and operational art at World War 1. In 1915-1916, during the period of trench warfare, the use of chemical weapons for breaking through the enemy`s first defence lines changed the structure of combat orders and led to their dispersal and the deployment in depth of the defensive zone. In 1917 chemical weapons made it possible to overcome the contradiction between the lengthy preliminary artillery bombardment and the surprise of the offensive. The unprecedented artillery chemical bombardments fired by the German Army, artillery chemical battle, resulted in the significant success of the Germans in spring offensives in 1918, when large parts of the front were given up by the retiring Allied forces. The dynamics of the growth of the chemical warfare agents` (CWA) production, the development of means and methods for delivering the agents efficiently to the target by the Allied countries allowed the authors to suggest that in case Germany had not signed the armistice of 11 November 1918 with the Allies, the large-scale battlefield use of chemical weapons could multiply both in quality and in quantity. The development of the bombardment aviation and the inability of Germany to carry out a retaliatory chemical attack, that became obvious at the end of 1918, offered a golden opportunity for the Allies to use chemical agents in 1919 without any legal or humanitarian limitation on the methods of warfare. This article is concerned also with tactical and operational objectives and targets the belligerents tried to achieve by using chemical weapons during separate battles, the evolution of chemical weapons and chemical warfare agents and their joint impact on military operations at the battlefields of World War 1.

In May 2016 a special expedition by Russia’s Defence Ministry and Russian Geographical Society was organized in order to explore the island of Matua located near the centre of the Kuril Islands chain. By the beginning of World War II the island has been turned into the veritable fortress by the Japanese. There were certain reasons to suggest that the island could be used by the Japanese military for the development, production and stockpiling of weapons of mass destruction. Because of that an NBC control group, formed from the specialists of several scientific research institutions of the Radiological, Chemical and Biological Defence Troops of the Armed Forces of the Russian Federation was included in the joint team. The tasks of the group were to reveal and evaluate the NBC environment on Matua Island, to provide the protection of the personnel and the mitigation of any possible NBC contamination of the terrain and the Japanese military installations on the island. The group was also supposed to check the operational characteristics of NBC reconnaissance equipment and to conduct biological analysis at high northern latitudes without any fixed-site laboratories. The expedition has been working on the island from April 20 until June 29, 2016. The survey of the fortifications and engineering constructions on Matua Island, as well as the analysis of the contents of several chemical tanks and bottles, found on the island, revealed the absence of any evidence of the production of chemical, biological and nuclear weapons on Matua at the time of the Japanese military presence until August 1945. The analysis of the environmental samples (soil and water), taken at the locations of the surveys, and of the biological samples, taken from the organs of several mouse-like rodents, caught near the expedition camp, did not reveal any causative agents of infectious and particularly dangerous diseases. The radioactive contamination, residual radiation and gamma-rays were not detected on the territory of the island.

Fluorescent chemosensor detecting a widely used but highly toxic chemical warfare agent (CWA) such as phosgene is of great importance due to its high sensitivity along with low cost and simple method of preparation. In this study a biphenyl-benzoimidazole based (BPCI) chemodosimeter, which displayed a rapid, sensitive and ratiometric detection of the lethal pulmonary agent phosgene, has been developed. Upon the addition of phosgene to the BPCI solution in THF, we observed a fluorescence color change from blue to cyan-green. The chemodosimeter (BPCI) undergoes nucleophilic substitution reaction with phosgene followed by ring closure to yield the carbamylated final product and shows an explicit ratiometric fluorescence response towards phosgene. The carbamylation was accelerated due to the formation of a six-member ring, which restricts the C–C bond rotation. The probe (BPCI) selectively detected phosgene over other toxic relevant analytes. The detection limit (LOD) of BPCI for phosgene was established to be in the order of 10−7 M in the solution phase, which implied that BPCI can detect phosgene at a very minuscule level. This ratiometric switch, which we developed, can be used as a potential portable kit for detecting phosgene in the vapour phase, as well as in the solid phase when supported upon TLC plates. Theoretical calculations using the DFT/B3LYP/6-31+G(d) method were performed to unveil the electronic properties theoretically and to interpret the probable sensing mechanism. [ABSTRACT FROM AUTHOR]

Three existent states of carbon were introduced in FeOCl, namely graphite carbon, carbon dots and lattice carbon. The excellent photo-Fenton performance of C-FeOCl were attributed to the exposure of CUISs on the inner/outer surfaces of FeOCl and the efficient transportation-separation of photogenerated electrons in the horizontal and vertical directions of FeOCl. [Display omitted] The photo-Fenton process is promising for sincerely treating contaminated water. In this work, carbon-decorated iron oxychloride (C-FeOCl) is synthesized as a photo-Fenton catalyst for removing tetracycline (TC) from water. Three actual states of carbon are identified and their different roles in enhancing photo-Fenton performance are revealed. All carbon on/in FeOCl, including graphite carbon, carbon dots and lattice carbon, enhance visible light adsorption. More importantly, a homogeneous graphite carbon on the outer surface of FeOCl accelerates the transportation-separation of photo-excited electrons along the horizontal direction of FeOCl. Meanwhile, the interlayered carbon dots offer a Fe O C bridge in helping the transportation-separation of photo-excited electrons along the vertical direction of FeOCl. In this way, C-FeOCl acquires isotropy in conduction electrons to ensure an efficient Fe(II)/Fe(III) cycle. These interlayered carbon dots extend the layer spacing (d) of FeOCl to about 1.10 nm, exposing the internal iron centers. The lattice carbon significantly increases the amounts of coordinatively unsaturated iron sites (CUISs) in activating hydrogen peroxide (H 2 O 2) to hydroxyl radical (OH). Density functional theory (DFT) calculations confirm this activation on inner and external CUISs with a significantly low activation energy of about 0.33 eV. [ABSTRACT FROM AUTHOR]

Phosgene is classified as a chemical warfare agent, yet data on its short-duration high concentration toxicity in a nose-only exposure rat model is sparse and inconsistent. Hence, an exposure system for short-term/high concentration exposure was developed and characterized. Herein, we report the median lethal concentration (LC50) for a 10-min nasal exposure of phosgene in a 24-h rat survival model. Male Wistar rats (Envigo) weighing 180-210 g on the day of exposure, were exposed to phosgene gas via nose-only inhalation using a system specifically designed to allow the simultaneous exposure and quantification of phosgene. After 24 h, the surviving rats were euthanized, the lung/body mass ratio determined, and lung tissues analyzed for histopathology. Increased terminal airway edema in the lungs located primarily at the alveoli (resulting in an increased lung/body mass ratio) coincided with the observed mortality. An LC50 value of 129.2 mg/m3 for a 10-min exposure was determined. Furthermore, in agreement with other highly toxic compounds, this study reveals a LC50 concentration value supportive of a nonlinear toxic load model, where the toxic load exponent is >1 (ne = 1.17). Thus, in line with other chemical warfare agents, phosgene toxicity is predicted to be more severe with short-duration, high-concentration exposures than long-duration, low-concentration exposures. This model is anticipated to be refined and developed to screen novel therapeutics against relevant short-term high concentration phosgene exposures expected from a terrorist attack, battlefield deployment, or industrial accident.

The facile light‐driven insertion reaction of oxygen into metal carbon bonds of the BPI (1,3‐bis(2‐pyridylimino)isoindole) complexes [Pt(BPI)Me] and [Pd(BPI)Me] has been investigated by LED‐NMR in CDCl3. The initial insertion reaction leads to peroxo complexes [Pt(BPI)OOMe] and [Pd(BPI)OOMe], which undergo further reactions over time. Spectra were recorded at 1 minute time intervals, which enabled the tracking of the methyl substituent, which eventually generates formaldehyde (and methanediol) and methanol in almost equal proportions. Degradation of the solvent CDCl3 to phosgene and DCl in the presence of oxygen and light leads to several side reactions. DCl reacts with [M(BPI)Me] and [M(BPI)OOMe] to form [M(BPI)Cl], whereas phosgene reacts with in situ generated methanol to chloro methylformate and dimethyl carbonate. [ABSTRACT FROM AUTHOR]

It is of great significance to develop environment-friendly piezoelectric materials. CO2-based polyurea (PU) was synthesized by using CO2 as raw material instead of phosgene and isocyanate to react with different diamines. The electrospinning technology was used to prepare PU nanofiber films. The structure of PU nanofiber films was investigated by SEM, XRD, FT-IR, and TG, and the films were assembled as piezoelectric sensors to test the piezoelectric properties. The results show that with the increasing carbon chain length of diamine, the piezoelectric properties of PU nanofiber films gradually decreased. PU-6 nanofiber film has the best fiber morphology and piezoelectric property with the output voltage of 4 V. It has good stability and durability, and can be used in the field of smart wearable. [ABSTRACT FROM AUTHOR]

Public health and safety are gravely jeopardised by phosgene, a highly toxic gas. In this study, phosgene was detected by the excited-state intramolecular proton transfer (ESIPT) and photoelectron transfer (PET) mechanisms utilising a fluorescent probe built from a triphenylamine-anthraquinone core structure (TPAAQ) with carbonyl and imidazole moieties as recognition sites. TPAAQ undergoes nucleophilic substitution and cyclization reactions with phosgene to form a six-membered ring. This results in a quick reaction with good selectivity, high sensitivity, and a detection limit of 22.83 nM. With the aid of high-resolution mass spectrometry and 1H NMR spectroscopy, the mechanism for sensing was verified. The ESIPT and PET mechanism of the probe was confirmed through DFT and TDDFT studies. In addition, we could detect phosgene in soil samples with detection limits of 0.1583 ppm, 0.233 ppm and 1.047 ppm for field soil, clay soil and sandy soil, respectively, and created a fluorescent test strip to identify phosgene. The fluorescent test strip's colour change from light reddish to yellow is visible to the unaided eye under 365 nm UV light. [ABSTRACT FROM AUTHOR]

In this study, we introduced a novel fluorescent probe RNP, which demonstrated outstanding sensitivity and specificity for phosgene detection. Upon phosgene exposure, the probe exhibited rapid fluorescence turn-on within a short re-sponse time (6 s). RNP was also effective in both cellular and murine experiments, where fluorescence enhancement was observed in the respiratory tract of mice. [ABSTRACT FROM AUTHOR]

Phosgene is a suffocating toxic gas that seriously threatens human health and public security. With this research, we developed a simple ratiometric fluorescent probe (1) bearing indole and benzimidazole moieties as the sensing sites and employed it for the aggregation-induced emission-based (AIE-based) detection of phosgene. It was the first time that the probe could detect phosgene in an almost pure aqueous solution (f w = 99.5 %). Probe 1 had AIE-activity, and the maximum emission peak was 392 nm with increasing water fraction (0–99.5 %). When reacting with phosgene, the emission peak at 392 nm gradually decreased, while a new peak appeared at 449 nm and continued to increase with increasing water fraction (0–99.5 %). Probe 1 exhibited a rapid response toward aqueous phosgene with high selectivity and sensitivity (limit of detection being 23.8 nM). Additionally, we fabricated 1 -loaded test strips for gas phosgene detection, enabling dual-channel detection under 245 nm and 365 nm hand-held UV lamps. Finally, this probe was used to monitor phosgene in bionic samples. [Display omitted] • A ratiometric phosgene fluorescence probe 1 based on AIE properties was obtained. • Probe 1 is the first fluorescence probe to detect phosgene in a 99.5 % aqueous medium. • Probe 1 can rapidly, sensitively, and selectively detect phosgene in the solution phase. • 1 -loaded test strips were applied to dual-channel monitor gas phosgene. • Probe 1 can image the trace amount of phosgene in biological sample. [ABSTRACT FROM AUTHOR]

[Display omitted] • A new nickel-catalyzed reductive carbonylation reaction of vinyl triflates and alkyl bromides has been developed. • A new procedure for synthesis of enones. • Oxalyl chloride was used as a safe and readily available carbonyl source. • Various alkyl alkenyl ketones were prepared in moderate to good yields. Herein, we report a nickel-catalyzed reductive carbonylation reaction of vinyl triflates and alkyl bromides for the preparation of enones. With oxalyl chloride as a safe and readily available carbonyl source, various alkyl alkenyl ketones were prepared in moderate to good yields under relatively mild conditions. Control experiments demonstrated that the combined action of DMF and zinc facilitated the release of CO from oxalyl chloride. [ABSTRACT FROM AUTHOR]

• Me 3 NO promotes decarbonylation and deprotonation on [M 2 Cp 2 (μ -PR 2)(CO) 2 (NO) 2 ]+ cations. • The title complexes are protonated at the C 5 H 4 group to give κ:η -NO-bridged cations. • [W 2 Cp(μ - κ:η 5-C 5 H 4)(μ -P t Bu 2)(CO)(NO) 2 ] is methylated to give a methoxyimido derivative. • κ:η -NO-bridged derivatives are computed to be less stable than their μ - κ:η -CO isomers. The title compounds were prepared upon reaction of BAr' 4 − salts of the known cations [M 2 Cp 2 (μ -PR 2)(CO) 2 (NO) 2 ]+ (M = Mo, W; R = Cy, t Bu; Ar' = 3,5-C 6 H 3 (CF 3) 2), with commercial Me 3 NO·2H 2 O in fluorobenzene solution at 273 K, this promoting decarbonylation and cyclopentadienyl deprotonation to yield complexes with cyclopentadienylidene ligands bridging the metal centres (W−W = 2.9917(5) Å when R = Cy). The use of dichloromethane as solvent, however, triggered a competitive chloride abstraction reaction by the Mo compounds that yielded the chloride complexes [Mo 2 Cp 2 Cl(μ -PR 2)(CO)(NO) 2 ], specifically formed with an anti disposition of the Cp ligands relative to the Mo 2 P plane, and cis positioning of carbonyl and chloride ligands relative to the P atom (Mo−Cl = 2.336(4) Å when R = t Bu). Protonation of the cyclopentadienylidene-bridged complexes with [H(OEt 2) 2 ](BAr' 4) yielded the BAr' 4 − salts of the dicyclopentadienyl cations [M 2 Cp 2 (μ - κ:η -NO)(μ -PR 2)(CO)(NO)]+ (Mo−Mo = 3.1027(2) Å when R = t Bu; W−W = 3.0446(7) Å when R = Cy), which display bridging nitrosyl ligands in the rare linear end-on:side-on coordination mode, and are kinetic rather than thermodynamic products, according to density functional theory calculations. When using HBF 4 ·OEt 2 as protonation reagent on the P t Bu 2 -bridged complexes, however, coordination of the external anion (in the κ 1-mode) also takes place, to yield the tetrafluoroborate complexes [M 2 Cp 2 (κ 1-BF 4)(μ -P t Bu 2)(CO)(NO) 2 ] as unique (Mo) or major (W) products. Methylation of the same cyclopentadienylidene complexes with [Me 3 O](BF 4) was only observed for the tungsten cation, and took place specifically at the O atom of one nitrosyl ligand to give [W 2 Cp(μ - κ:η 5-C 5 H 4)(NOMe)(μ -P t Bu 2)(CO)(NO)](BF 4), a complex displaying a linear methoxyimido ligand (W−N = 1.746(4) Å; W−N−O = 163.5(4)o). Synopsis Decarbonylation of cations [M 2 Cp 2 (μ -PR 2)(CO) 2 (NO) 2 ]+ with Me 3 NO·2H 2 O also resulted in deprotonation of a cyclopentadienyl ring to yield cyclopentadienylidene-bridged derivatives. Protonation of the latter restored the Cp ring and triggered nitrosyl rearrangement to yield rare linear κ:η -NO-bridged complexes, even if less stable than the corresponding κ:η -CO-bridged isomers, according to DFT calculations. Pictogram [Display omitted] [ABSTRACT FROM AUTHOR]

Background: On February 3, 2023, a train derailment happened in Ohio, causing a massive chemical spill. The train was transporting several chemical compounds that are raw materials for the chemical industry, and due to the derailment, some wagons caught fire, and others were in danger of explosion due to overheating. Aims: This note aims to reflect on the study of the chemicals present in the derailment and whether it could be a different outcome. Methods: A simple survey was done on the internet, looking for information about the derailment and the main chemicals the train was carrying. The information about the chemicals was selected from the Material Safety Data Sheet (MSDS) from regular suppliers of the products. Results: The information collected regarding the derailment was unclear about the reasons for the fact, and the literature regarding the chemicals pointed out that the situation could get worse or worse than it already was. Discussion: at the time of the study, no conclusive information was available regarding the reasons for the derailment. The spill of a carcinogenic agent turned the derailment scenario more difficult to operate. The combustion of vinyl chloride can create phosgene gas (apparently did it) and increase the horror show that unfolded at the derailment site. Conclusions: The local population was suffering at the time and waiting for real proper support. The locomotive crew followed the company regulations, and the personnel working on the ground followed orders. Therefore, those do not appear to be the reasons for the derailment. [ABSTRACT FROM AUTHOR]

Synthesis of oxazolonone, benzoxazolononeby using amino hydroxy compound, alkyl haloformate, trialkylamine and DMF as solvents. Herein used simple carbonylation agent such as alkylhaloformate instead of phosgene and Triphosgene. Developed novel and simple synthesis method. [ABSTRACT FROM AUTHOR]

The use of a cellulose detection film as a carrier for a colorimetric sensor to detect phosgene and allied compounds to be evaluated primarily visually is studied. For the case study, a benzimidazole-rhodamine dye and an acetyl cellulose film were selected. The detection complex was modified using cyclic ether 18-crown-6 to achieve more desirable analytic properties. The chromatic properties of detection film was verified using reflectance colorimetry in the visible light spectrum. The employed detection agent demonstrated high sensibility to phosgene vapours, but acid gases, acyl chlorides, base organic solvents, and in higher concentrations, even some organophosphorus substances interfered. The detection film application was adjusted to the in-situ preparation of simple detection devices (a spray or a marker) as well as to manufacture detection strips with beforehand excluded polymer film.

We report on the preparation of synthetically versatile N-carboxyanhydrides (NCAs) directly from amino acids and CO2 using n-propylphosphonic anhydride. Most of the NCAs were isolated with >95% purity after simple workup, avoiding the need for tedious purification procedures typically required using conventional methods. Because the reagents and conditions employed are mild, tandem reactions with moisture-sensitive NCAs were carried out to transform them into the medicinally active alkaloids tryptanthrin and phaitanthrin A in one pot. A qualitative analysis revealed that our NCA synthesis approach is more green than conventional methods, which all directly or indirectly use the highly poisonous gas phosgene. [ABSTRACT FROM AUTHOR]