A Miniaturized Method for Evaluating the Dynamic Gas-Phase Adsorption and Degradation of Sarin on Porous Adsorbents at Different Humidity Levels.

Metal organic frameworks based on zirconium nodes (Zr-MOFs) have impressive adsorption capacities, and many can rapidly hydrolyze toxic organophosphorus nerve agents. They could thus potentially replace commonly used adsorbents in respiratory filters. However, current test methodologies are poorly adapted to screen the large number of available MOFs, and data for nerve agent adsorption by MOFs are scarce. This paper presents a miniaturized method for assessing the capacity of Zr-MOFs for dynamic gas phase adsorption and degradation of sarin (GB) into the primary hydrolysis product isopropyl methyl phosphonic acid (IMPA). The method was validated by comparing the dynamic adsorption capacities of activated carbon (AC) and NU-1000 for GB under dry and humid conditions. Under dry conditions, unimpregnated AC had a greater capacity for GB uptake (0.68 ± 0.06 g/g) than pelletized NU-1000 (0.36 ± 0.03 g/g). At 55% relative humidity (RH), the capacity of AC was largely unchanged (0.72 ± 0.10 g/g) but that of NU-1000 increased slightly, to 0.46 ± 0.10 g/g. However, NU-1000 exhibited poor water retention at 55% RH. For both adsorbents, the degree of hydrolysis of GB into IMPA was significantly greater at 55% RH than under dry conditions, but the overall degree of hydrolysis was limited in both cases. Further tests at higher relative humidities are needed to fully evaluate the ability of NU-1000 to degrade GB after adsorption from the gas phase. The proposed experimental setup uses very small amounts of both adsorbent material (20 mg) and toxic agent, making it ideal for assessing new MOFs. However, future methodological challenges are reliable generation of sarin at higher RH and exploring sensitive methods to monitor degradation products from nerve agents in real-time.

In vitro human skin decontamination efficacy of MOF-808 in decontamination lotion following exposure to the nerve agent VX.

Metal-organic frameworks (MOFs) have shown promising properties for removal of chemical warfare agents, in particular for material decontamination and functionalized fabrics. The MOF-properties could also be beneficial for skin decontamination, especially when exposed to highly toxic and low volatile nerve agents. In such exposures, efficient decontamination is crucial for adequate medical management. In the present study, seven zirconium-based MOFs were evaluated for their ability to degrade VX and subsequently tested in vitro for decontamination of VX on human dermatomed skin. Of the MOFs evaluated, MOF-808 showed the greatest ability to degrade VX in an alkaline buffer with complete degradation of VX within 5 min. PCN-777, Zr-NDC and NU-1000 displayed degradation half-lives of approximately 10 min. When including MOF-808 in a skin friendly carrier with slightly acidic pH, a decreased agent degradation rate was observed, requiring over 24 h to reach complete degradation. In skin decontamination experiments, MOF-808 enhanced the efficacy compared to the carrier alone, essentially by improved agent absorption. Adding MOF-808 to Reactive Skin Decontamination Lotion (RSDL) did not improve the high effectiveness of RSDL alone. The present study showed that including MOF in skin decontamination lotions could be beneficial. Further studies should include optimizing the particulates and formulations.

Attribution of fentanyl analogue synthesis routes by multivariate data analysis of orthogonal mass spectral data.

Chemical attribution signatures (CAS) can be used to obtain useful forensic information and evidence from illicit drug seizures. A CAS is typically generated using hyphenated chemical analysis techniques and consists of a fingerprint of the by-products and additives present in a sample. Among other things, it can provide information on the sample's origin, its method of production, and the sources of its precursors. This work investigates the possibility of using multivariate CAS analysis to identify the synthetic methods used to prepare seized fentanyl analogues, independently of the analogues' acyl derivatization. Three chemists working in two labs synthesized three different fentanyl analogues, preparing each one in duplicate by six different routes. The final collection of analogues (96 samples) and two intermediates (16 + 32 samples) were analysed by GC-MS and UHPLC-HRMS, and the resulting analytical data were used for multivariate modelling. Independently of analogue structure, the tested fentanyls could be classified based on the method used in the first step of their synthesis. The multivariate model's ability to classify unknown samples was then evaluated by applying it to six new fentanyl analogues. Additionally, seized fentanyl samples was analysed and classified by the model.