Synthesis of different glutathione–sulfur mustard adducts of verified and potential biomarkers

Sulfur Mustard (SM) is a blistering agent used as a chemical weapon. Glutathione (GSH) is involved in the β-lyase degradation pathway of SM and recently, bioadducts between SM and GSH were observed in vitro. While these bioadducts have never been isolated from in vivo tests or real poisoning with SM, they could be of interest as potential future biomarkers for the retrospective validation of exposure. We herein report the synthesis of different observed and new potential GSH–SM bioadducts as reference materials for analytical investigation. Two distinct approaches were investigated: a building-block pathway and the direct reaction with GSH. The availability of these references will aid future studies and may lead to the discovery of new GSH–SM biomarkers

Supramolecular agent–simulant correlations for the luminescence based detection of V-series chemical warfare agents with trivalent lanthanide complexes

Solution spectroscopic investigations into the interactions of eight potential bidentate V-series organophosphorus chemical warfare agent (OP CWA) simulants with [Eu(phen)₂(NO₃)₃]·2H₂O demonstrated that the chemical and structural composition of the secondary binding site within the simulant was of paramount importance. Only simulants containing both phosphoryl/phosphonyl and amine moieties generated analogous spectroscopic behaviours to V-series OP CWAs seen in previous studies. The results demonstrated that the bidentate chelation mechanism was driven by the phosphoryl/phosphonyl moieties and that the presence of the amine moieties induced a significant secondary dynamic luminescence quenching mechanism. The binding modes of the simulants VO and TEEP to trivalent lanthanides (Eu and La) were further investigated using ¹H and ³¹P NMR spectroscopic titrations and kinetic IR experiments. VO, with both the phosphonyl and amine binding sites was found to be the most appropriate simulant for V-series OP CWAs in supramolecular studies with trivalent lanthanide ions and we recommend VO for use in supramolecular studies of this type

Advice from the Scientific Advisory Board of the Organisation for the Prohibition of Chemical Weapons on riot control agents in connection to the Chemical Weapons Convention

Compounds that cause powerful sensory irritation to humans were reviewed by the Scientific Advisory Board (SAB) of the Organisation for the Prohibition of Chemical Weapons (OPCW) in response to requests in 2014 and 2017 by the OPCW Director-General to advise which riot control agents (RCAs) might be subject to declaration under the Chemical Weapons Convention (the Convention). The chemical and toxicological properties of 60 chemicals identified from a survey by the OPCW of RCAs that had been researched or were available for purchase, and additional chemicals recognised by the SAB as having potential RCA applications, were considered. Only 17 of the 60 chemicals met the definition of a RCA under the Convention. These findings were provided to the States Parties of the Convention to inform the implementation of obligations pertaining to RCAs under this international chemical disarmament and non-proliferation treaty.Peer reviewe

innovative technologies for chemical security

AbstractAdvances across the chemical and biological (life) sciences are increasingly enabled by ideas and tools from sectors outside these disciplines, with information and communication technologies playing a key role across 21st century scientific development. In the face of rapid technological change, the Organisation for the Prohibition of Chemical Weapons (OPCW), the implementing body of the Chemical Weapons Convention ("the Convention"), seeks technological opportunities to strengthen capabilities in the field of chemical disarmament. The OPCW Scientific Advisory Board (SAB) in its review of developments in science and technology examined the potential uses of emerging technologies for the implementation of the Convention at a workshop entitled "Innovative Technologies for Chemical Security", held from 3 to 5 July 2017, in Rio de Janeiro, Brazil. The event, organized in cooperation with the International Union of Pure and Applied Chemistry (IUPAC), the National Academies of Science, Engineering and Medicine of the United States of America, the Brazilian Academy of Sciences, and the Brazilian Chemical Society, was attended by 45 scientists and engineers from 22 countries. Their insights into the use of innovative technological tools and how they might benefit chemical disarmament and non-proliferation informed the SAB's report on developments in science and technology for the Fourth Review Conference of the Convention (to be held in November 2018), and are described herein, as are recommendations that the SAB submitted to the OPCW Director-General and the States Parties of the Convention. It is concluded that technologies exist or are under development that could be used for investigations, contingency, assistance and protection, reducing risks to inspectors, and enhancing sampling and analysis

Arsenic Biogeochemistry Affected by Eutrophication in Lake Biwa, Japan (INTERFACE SCIENCE-Separation Chemistry)

The seasonal variations of arsenic species were studied in the mesotrophic northern and eutrophic southern basins of Lake Biwa in Japan. The variations of arsenic species in lake water largely depend on biological processes, such as the metabolism of phytoplankton, decomposition of organic matter by bacteria, and microbial reduction of iron and manganese oxides in sediments. These results show that eutrophication affects the concentration and speciation of arsenic in the lake water

A Rapid, highly sensitive and selective phosgene sensor based on 5,6‐pinenepyridine

The toxicity of phosgene (COCl2) combined with its extensive use as a reactant and building block in the chemical industry make its fast and accurate detection a prerequisite. We have developed a carboxylic derivative of 5,6-pinenepyridine which is able to act as colorimetric and fluorimetric sensor for phosgene in air and solution. For the first time, the formation of a pyrido-[2,1-a]isoindolone was used for this purpose. In solution, the sensing reaction is extremely fast (under 5 s), selective and highly sensitive, with a limit of detection (LOD) of 9.7 nM/0.8 ppb. When fixed on a solid support, the sensor is able to detect the presence of gaseous phosgene down to concentrations of 0.1 ppm, one of the lowest values reported to date

Qualitative colorimetric analysis of a Ir(iii)/Eu(iii) dyad in the presence of chemical warfare agents and simulants on a paper matrix

The addition of G- and V-series organophosphorus chemical warfare agents and simulants to a paper-based assay of a dual-luminescent Ir(iii)/Eu(iii) dyad generated different emissive responses between the classes and compound types. The emission responses are complex and based not only on altering the balance between red Eu(iii)-based and blue Ir(iii)-based luminescent components, but also incorporate other factors such as analyte volatility, concentration and UV absorption. The extent of this emission colour change was analysed colorimetrically and related to the change in RGB output over time