Rapid detection of Chemical Warfare Agents (CWAs) is of great significance in protecting civilians in public places and military personnel on the battlefield. Two-dimensional (2D) molybdenum disulfide (MoS2) nanosheets (NSs) can be integrated as a gas sensor at room temperature (25°C) due to their large specific surface area and excellent semiconductor properties. However, low sensitivity and long response-recovery time hinder the pure MoS2 application in CWAs gas sensors. In this work, we developed a CWAs sensor based on in-situ niobium-doped MoS2 NSs (Nb-MoS2 NSs) via direct chemical-vapor-deposition (CVD) growth. Characterization results show that the high content of Nb elements (7.8 at%) are homogeneously dispersed on the large-area 2D structure of MoS2. The Nb-MoS2 NSs-based CWAs sensor exhibits higher sensitivity (−2.09% and −3.95% to 0.05 mg/m3 sarin and sulfur mustard, respectively) and faster response speed (78 s and 30 s to 0.05 mg/m3 sarin and sulfur mustard, respectively) than MoS2 and other 2D materials at room temperature. And the sensor has certain specificity for sarin and sulfur mustard and is especially sensitive to sulfur mustard. This can be attributed to the improvement of adsorption properties via electronic regulation of Nb doping. This is the first report about CWAs detection based on two-dimensional (2D) transition metal dichalcogenides (TMDs) sensing materials, which demonstrates that the high sensitivity, rapid response, and low limit of detection of 2D TMDs-based CWAs sensor can meet the monitoring needs of many scenarios, thus showing a strong application potential.
Chemical warfare agents (CWAs) are known as poor man’s bombs because of their small lethal dose, cheapness, and ease of production. Therefore, the highly sensitive and rapid detection of CWAs at room temperature (RT = 25 °C) is essential. In this paper, we have developed a resistive semiconductor sensor for the highly sensitive detection of CWAs at RT. The gas-sensing material is SnS2/rGO nanosheets (NSs) prepared by hydrothermal synthesis. The lower detection limits of the SnS2/rGO NSs-based gas sensor were 0.05 mg/m3 and 0.1 mg/m3 for the typical chemical weapons sarin (GB) and sulfur mustard (HD), respectively. The responsivity can reach −3.54% and −10.2% in 95 s for 1.0 mg/m3 GB, and in 47 s for 1.0 mg/m3 HD. They are 1.17 and 2.71 times higher than the previously reported Nb-MoS2 NSs-based gas sensors, respectively. In addition, it has better repeatability (RSD = 6.77%) and stability for up to 10 weeks (RSD = 20.99%). Furthermore, to simplify the work of later researchers based on the detection of CWAs by two-dimensional transition metal sulfur compounds (2D-TMDCs), we carried out calculations of the SnS2 NSs-based and SnS2/rGO NSs-based gas sensor-adsorbing CWAs. Detailed comparisons are made in conjunction with experimental results. For different materials, it was found that the SnS2/rGO NSs-based gas sensor performed better in all aspects of adsorbing CWAs in the experimental results. Adsorbed CWAs at a distance smaller than that of the SnS2 NSs-based gas sensor in the theoretical calculations, as well as its adsorption energy and transferred charge, were larger than those of the SnS2 NSs-based gas sensor. For different CWAs, the experimental results show that the sensitivity of the SnS2/rGO NSs-based gas sensor for the adsorption of GB is higher than that of HD, and accordingly, the theoretical calculations show that the adsorption distance of the SnS2/rGO NSs-based gas sensor for the adsorption of GB is smaller than that of HD, and the adsorption energy and the amount of transferred charge are larger than that of HD. This regularity conclusion proves the feasibility of adsorption of CWAs by gas sensors based on SnS2 NSs, as well as the feasibility and reliability of theoretical prediction experiments. This work lays a good theoretical foundation for subsequent rapid screenings of gas sensors with gas-sensitive materials for detecting CWAs.
Poor selectivity is one of the main bottlenecks restricting the development of metal oxide semiconductor (MOS) sensors. In this paper, using hydrogen cyanide (HCN) as the target gas, CeMnOx as the catalytic layer material and Pt@SnO2 as the gas-sensitive layer material, we have proposed a scheme to improve the selectivity of a catalytic layer/gas-sensitive layer-laminated MOS sensor under dynamic temperature modulation. We tested HCN and 12 kinds of battlefield environment simulation gases, and the results showed that the CeMnOx/Pt@SnO2 sensor, under the condition of temperature dynamic modulation (a constant temperature of 400 °C for the gas-sensitive layer and a variable temperature of room temperature to 400 °C for the catalytic layer; the heating and cooling rates were 200 °C/s, the highest temperature was maintained for 2 s, and the lowest temperature was maintained for 2 s), distinct characteristic peaks appeared on the G-T curves of the resistance response to HCN only. The quantification of the characteristic peaks was performed by peak heights, and the peak height of 5 mg/m3 HCN was obtained up to 0.104, while the peak heights of the other gases at the same concentration were up to 0.034. The peak height of HCN was significantly higher than that of other gases, which verified the high selectivity of the sensor for HCN. Meanwhile, the sensor also showed good sensitivity, response/recovery time, stability and anti-interference for HCN under the above temperature dynamic modulation. This work provides an important reference for the selectivity improvement of MOS sensors for HCN.
Melittin, a naturally occurring antimicrobial peptide, demonstrates broad-spectrum activity, effectively suppressing and eliminating both Gram-positive and Gram-negative bacteria, including specific drug-resistant strains. In this study, molecular simulation software was employed to investigate and modify the structure of melittin with the aim of synthesizing a modified peptide exhibiting enhanced antibacterial potency and assessing its bacteriostatic and antibacterial properties. The primary research objectives were as follows: 1. Preparation and characterization of melittin-modified peptide—Using molecular simulation software, the structure of the melittin-modified peptide was adjusted to predict its activity and select the most appropriate amino acid sequence. The peptide was synthesized through solid-phase peptide synthesis employing the Fmoc strategy and subsequently purified using liquid chromatography. The yield of the purified modified melittin was determined to be 30.97%, and the identity of the product was confirmed by LC-MS and MALDI-TOF-MS. 2. Evaluation of the antimicrobial activity of the melittin-modified peptide—The minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) of melittin and its modified peptide were measured using gradient dilution and plate counting techniques. The results revealed that both melittin and its modified peptide exhibited strong antibacterial efficacy against Gram-positive and Gram-negative bacteria, as well as certain drug-resistant strains. This showed that melittin and its modified peptide have the same antibacterial (killing) effect. A scanning electron microscope analysis indicated that both melittin and its modified peptide were capable of disrupting bacterial cell structures, leading to bacterial cell death.
Sarin is an extremely toxic and fast-acting chemical warfare nerve agent that poses a serious threat to human health, necessitating the development of appropriate sensing technologies. Dimethyl methylphosphonate (DMMP), which has a chemical structure similar to that of sarin but is non-toxic, is often used as a simulation agent in related research. Among promising gas-sensing materials, CuFe2O4 exhibits suitable thermal stability. It is easily produced and has low toxicity. Its performance can be enhanced using heterogeneous ion doping to increase the number of surface defects and content of adsorbed oxygen. Therefore, a solvothermal method was adopted in this study to prepare CuFe2O4 hollow microspheres that were subsequently doped with different ratios of Sn4+ or Sn2+. Detailed characterizations of the obtained materials were conducted, and the corresponding CuFe2O4-based gas sensors were fabricated. Their gas-sensing performance against DMMP was studied to analyze and discuss the gas-sensing and sensitization mechanisms associated with Sn4+ and Sn2+ doping. The CuFe2O4-based sensor doped with 2 mol% Sn2+ exhibited excellent gas-sensing performance in response to a 1 ppm concentration of DMMP, with response and recovery times of 12 and 63 s, respectively. Notably, its response to 1 ppm DMMP (16.27) was 3.3-fold higher than that to 1 ppm 2-CEES (4.98). The doped CuFe2O4 sensor exhibited superior response–recovery characteristics and enhanced moisture resistance compared to the undoped sensor.