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.

Three New Lanostanoids with Anti-HCV Effects from Abies nukiangensis.

Three new lanostane derivatives (1-3) and twelve known triterpenoids (4-15) were isolated from the twigs and leaves of Abies nukiangensis. The structures of the new compounds were elucidated mainly by detailed analysis of their NMR and HR-ESI-MS spectroscopic data. Evaluation of the anti-HCV effects of all isolates showed that 3 exhibited moderate effect with the EC50 value of 11.09 µM.

Sensitive and selective detections of mustard gas and its analogues by 4-mercaptocoumarins as fluorescent chemosensors in both solutions and gas phase.

Mustard gas has been used as a chemical warfare agent for a century, and is the most likely chemical weapon used in wars or by terrorists. Thus, it is important to develop a facile, rapid and highly selective method for the detection of mustard gas. In this paper, two fluorescent probe molecules, 4-mercaptocoumarins, have been developed for rapid and sensitive detections of SM and its analogues (CEES and NH1) in both solutions and gas phase. The sensing reaction is a nucleophilic addition at three-membered hetercyclic sulfonium/ammonium formed from SM, CEES/NH1 in ethanol. Two fluorescent probes (4-mercaptocoumarins, ArSH) in ethanol deprotonate to form thiophenol anions (ArS-) resulting from their low pKa values (3.2-3.4), and the nucleophilic addition of the anion ArS- generates the corresponding thioethers, giving a turn-on fluorescence response. The thiophenol anion can fast sense SM, CEES and NH1 (within 1-4 min) with high sensitivity (~nM level) at 60 °C, and high selectivity through adding a tertiary amine, and two probes exhibit excellent chemical and photostability in detection systems. Furthermore, a facile test strip with the sensor was fabricated for the detection of CEES vapor with rapid response (3 min), high sensitivity (9 ppb) and high selectivity.

Quinoline-2-thione-based fluorescent probes for selective and sensitive detections of mustard gas and its analogues.

Sulfur mustard (SM, also called as mustard gas (HD)) is a persistent and highly toxic gas used as chemical weapon in wars and military conflicts. Moreover, owing to its simple structure and easy synthesis, it is the most likely chemical agent used by terrorists. For this reason, it is vital important to develop a facile, rapid and reliable detection system for SM. In this paper, we have developed four quinoline-2-thiones as fluorescent probes, 2a-2d, for the detection of SM and its analogues, half sulfur mustard (CEES) and a nitrogen mustard NH1. In the presence of KOH, these quinoline-2-thiones deprotonated to quinoline-2-thiophenol anions, which react with SM and its analogues rapidly to form quinoline-2-thiethers with highly efficient fluorescence, giving turn-on fluorescence response. The sensing products with CEES were isolated and fully characterized, thereby, the sensing mechanism was firmly established. The fluorescent probes with 4-trifluoromethyl group, 2b and 2d, exhibit rapid response to SM, CEES and NH1 (within 1 min at 60 °C for CEES and NH1), high sensitivity (limit of detection, 50 nM for SM and 20 nM for NH1) and high selectivity. Furthermore, polymer film test strips were fabricated with probe-embedded poly(ethylene oxide) for the detection of CEES vapor. These test strips displayed a rapid response (<4 min) to gaseous CEES with high sensitivity (0.2 ppm) and high selectivity. These results show that fluorescent probes 2b and 2d have a good application prospect in the field detection of mustard gas.

Synthesis of Oxadiazolones with Hydrazides: The Mechanism and the Sensing Application as Sensitive, Rapid, and Visual Fluorescent Sensors for Phosgene.

The reaction of hydrazides with triphosgene in the presence of triethylamine is a facile method to construct various oxadiazolones. Utilizing this reaction, a new class of colorimetric and fluorogenic phosgene chemosensors were developed with the BODIPY as fluorophore, five BODIPY-based hydrazides, which exhibited highly effective reactions with phosgene. The mechanism was updated. Finally, the test paper with a hydrazide was fabricated for facile, selective, and visual detection of phosgene gas.