Biochemistry weapon is raising new tools of war and terror.This research is an experiment about portable system for CWAs (chemical warfare agents) detection using micro array gas system.CWAs were divided into four typ...Biochemistry weapon is raising new tools of war and terror.This research is an experiment about portable system for CWAs (chemical warfare agents) detection using micro array gas system.CWAs were divided into four types such as blood, nerve,vesicant,and choking agent.To detect various CWAs,semiconductor thick film sensor array based on tin oxide was fabricated and their gas responses were examined.Operating temperature was range of 250℃to 350℃and gas concentration was range of 0.1μg/g to 10μg/g.Sensor array was measured as operating temperatures,concentrations for four simulant agents of CWAs.Extracted parameters from results were carried out classification among CWAs through the principal component analysis (PCA).Also,classification of gases is studied using adaptive resonance theory (ART) that is one of neural network algorithm.Results displayed using PDA system.展开更多
In this review, we summaries the past few year work on the chemistry of CWA’s and their simulants on various heterogeneous surfaces of zeolites, composites of zeolites and doped zeolite with transition metal oxides. ...In this review, we summaries the past few year work on the chemistry of CWA’s and their simulants on various heterogeneous surfaces of zeolites, composites of zeolites and doped zeolite with transition metal oxides. This review elaborates an updated literature overview on the degradation of CWA’s and its simulants. The data written in this review were collected from the peer-reviewed national and international literature.展开更多
We present in this paper a numerical study of the validity limit of the geometrical optics approximation compared with a differential method which is established according to rigorous formalisms based on the electroma...We present in this paper a numerical study of the validity limit of the geometrical optics approximation compared with a differential method which is established according to rigorous formalisms based on the electromagnetic theory. The precedent studies show that this method is adapted to the study of diffraction by periodic rough surfaces. We determine by two methods the emissivity of gold and tungsten for surfaces with a rectangular or sinusoidal profile, for a wavelength equal to 0.55 microns. The monochromatic directional emissivity of these surfaces clearly depends on the angle of incidence, the surface profile, height, period and the nature of the material. We perform our calculations by a method of coupled wave analysis (CWA) and a geometric optics method (GOA). The latter method is theoretically valid only when the dimensions of the cavities are very large compared to the wavelength, while the CWA is theoretically correct whatever these dimensions. The main purpose of this work is to investigate the validity limit of GOA compared with CWA. The obtained results for a fixed height of the grating, allowed us to delimit the validity domain of the optic geometrical approximation for the treated cases. Finally, the agreement between the emissivity calculated by the differential method and that given on the basis of the homogenization theory is satisfactory when the period is much smaller than the wavelength.展开更多
Chemical warfare agents(CWAs),including organophosphate nerve agents(e.g.,sarin,tabun,soman,VX,etc.)and phosgene,are weapons of mass destruction(WMD)and agents of bioterrorism,posing a serious threat to public safety ...Chemical warfare agents(CWAs),including organophosphate nerve agents(e.g.,sarin,tabun,soman,VX,etc.)and phosgene,are weapons of mass destruction(WMD)and agents of bioterrorism,posing a serious threat to public safety and national security.The current detection methods often lack a faster response,portability,and poor selectivity/sensitivity for specific biochemical threats.Therefore,developing reliable,direct,simpler,and sensitive optical sensors for such toxic biochemical hazards is critically important.Herein,we have rationally designed a Ru(Ⅱ)-based emissive chemodosimeter possessing a reactive site in the peripheral ligand for the selective detection of a G-series CWA mimic(diethyl chlorophosphate,DCP)and phosgene(COCl_(2))in the presence of relevant interferents.The Ru(Ⅱ)complex,[Ru(phen)_(2)(phen-Napen)](PF_(6))_(2)[1],where phen is 1,10-phenanthroline and phen-Nap-en is 1,10-phenanthroline functionalized with a naphthalic anhydride conjugated 2-aminoethylamino group as the reactive site,was synthesized and characterized for the selective‘turn-ON’detection of a nerve agent mimic(DCP)and toxic phosgene at distinct excitation wavelengths.The structural integrity of the probe[1]was confirmed,and the solution chemistry and photophysical properties of the probe were studied using various spectroscopic techniques to evaluate its optical parameters.The probe functions as a highly effective chemodosimetric agent for the dual sensing of the CWA mimic(DCP)and phosgene.The probe exhibits a fast‘turn-ON’response(<10 s)and shows excellent selectivity over competing interferents with high sensitivity for phosgene[LOD=126 nM]and DCP[LOD=73 nM].The appended 2-aminoethylamino group acts as the reactive site for the analyte-specific reaction.It reacts with phosgene or CWAs via nucleophilic or phosphorylation reactions to form cyclized or phosphorylated products,respectively.The final adducts,[1]-phos and[1]-DCP,containing 2-imidazolidinone or phosphorylated products,were identified using ESI-MS and ^(1)H,^(13)C and ^(31)P NMR spectroscopy.This reaction mechanism was thoroughly investigated and supported by ESI-MS analysis,NMR spectroscopy,and theoretical calculations.The enhanced red luminescence of[1]upon reaction with phosgene or DCP is attributed to the perturbation of the ^(3)MLCT state in the resulting products.Furthermore,a portable test kit utilizing[1]loaded on solid surface was developed for the realtime,selective,rapid,and highly sensitive visual monitoring of phosgene and nerve gases at the nM level.展开更多
Chemical warfare agents(CWAs)can cause significant harm to health and even death in a very short time even when inhaled in small amounts(~100 mg min/m^(3)).Detection equipment based on conventional techniques,includin...Chemical warfare agents(CWAs)can cause significant harm to health and even death in a very short time even when inhaled in small amounts(~100 mg min/m^(3)).Detection equipment based on conventional techniques,including gas chromatography-mass spectrometry,Raman spectroscopy,fluorescence spectroscopy,and ion mobility spectrometry,have the disadvantages of high cost,long detection time,and high power consumption.Rapid,portable,and convenient equipment for target CWAs detection under interference is a challenge.In this study,we propose an alarm system comprising a multitype micro sensor array and a field-programmable gate array-based readout circuit for CWAs simulants detection.Under common volatile organic compound,temperature,and water vapor interference,the proposed multitype sensor-based detection system realizes an alarm function in less than 20 s with thresholds of 1 ppm dimethyl methylphosphonate(DMMP),4.6 ppm 2,2'-dichlorodiethyl ether(DCE),and 20 ppm SO_(2).Furthermore,the proposed detection system was evaluated outside the laboratory and passed the wilderness test,demonstrating its reliability in the atmosphere.We believe that the proposed alarm system will contribute to the development of intelligent,portable,low-cost,and anti-interference CWAs detection technology.展开更多
Metal clusters represent a promising class of catalysts for various reactions,but the simultaneous improvement of their stability and catalytic activity is a longstanding challenge.Herein,we created a stable dual-clus...Metal clusters represent a promising class of catalysts for various reactions,but the simultaneous improvement of their stability and catalytic activity is a longstanding challenge.Herein,we created a stable dual-cluster metal-organic framework(MOF)that featured atomically synergistic bimetallic pair sites colocalized within sub nanometer pockets.The pair sites,consisting of Ni and Mo sites respectively originating from defective MOF and Polyoxometalate(POM)clusters,were rationally constructed by size-matched ligand exchange.The as-obtained dual-cluster MOF(MnMo_(6)-lg-PCN-601)exhibited superior catalytic activity,rate performance(t_(1/2)<1 min,TOF=140 min^(-1)),and stability toward the degradation of the chemical warfare agent simulant 2-chloroethyl ethyl sulfide(CEES).In-situ Fourier transform infrared(FTIR)studies and density functional theory(DFT)calculations demonstrated that the atomic synergy between colocalized pair sites favored the adsorption and activation of the CEES substrate,moreover,it also promoted H_(2)O_(2) decomposition for the selective oxidation of CEES.Our work opens a new avenue for the construction of stable metal clusters with high catalytic activity for application in various multi-substrate reactions.展开更多
文摘Biochemistry weapon is raising new tools of war and terror.This research is an experiment about portable system for CWAs (chemical warfare agents) detection using micro array gas system.CWAs were divided into four types such as blood, nerve,vesicant,and choking agent.To detect various CWAs,semiconductor thick film sensor array based on tin oxide was fabricated and their gas responses were examined.Operating temperature was range of 250℃to 350℃and gas concentration was range of 0.1μg/g to 10μg/g.Sensor array was measured as operating temperatures,concentrations for four simulant agents of CWAs.Extracted parameters from results were carried out classification among CWAs through the principal component analysis (PCA).Also,classification of gases is studied using adaptive resonance theory (ART) that is one of neural network algorithm.Results displayed using PDA system.
文摘In this review, we summaries the past few year work on the chemistry of CWA’s and their simulants on various heterogeneous surfaces of zeolites, composites of zeolites and doped zeolite with transition metal oxides. This review elaborates an updated literature overview on the degradation of CWA’s and its simulants. The data written in this review were collected from the peer-reviewed national and international literature.
文摘We present in this paper a numerical study of the validity limit of the geometrical optics approximation compared with a differential method which is established according to rigorous formalisms based on the electromagnetic theory. The precedent studies show that this method is adapted to the study of diffraction by periodic rough surfaces. We determine by two methods the emissivity of gold and tungsten for surfaces with a rectangular or sinusoidal profile, for a wavelength equal to 0.55 microns. The monochromatic directional emissivity of these surfaces clearly depends on the angle of incidence, the surface profile, height, period and the nature of the material. We perform our calculations by a method of coupled wave analysis (CWA) and a geometric optics method (GOA). The latter method is theoretically valid only when the dimensions of the cavities are very large compared to the wavelength, while the CWA is theoretically correct whatever these dimensions. The main purpose of this work is to investigate the validity limit of GOA compared with CWA. The obtained results for a fixed height of the grating, allowed us to delimit the validity domain of the optic geometrical approximation for the treated cases. Finally, the agreement between the emissivity calculated by the differential method and that given on the basis of the homogenization theory is satisfactory when the period is much smaller than the wavelength.
基金the Ministry of Human Resource and Development(MHRD)for the fellowship,N.S.thanks the Council of Scientific and Industrial Research(CSIR)the Anusandhan National Research Foundation(ANRF)(erstwhile SERB)for financial assistance(CRG/2021/000527)Council of Scientific and Industrial Research(CSIR)for financial support(No.01(3048)/21/EMR-II).
文摘Chemical warfare agents(CWAs),including organophosphate nerve agents(e.g.,sarin,tabun,soman,VX,etc.)and phosgene,are weapons of mass destruction(WMD)and agents of bioterrorism,posing a serious threat to public safety and national security.The current detection methods often lack a faster response,portability,and poor selectivity/sensitivity for specific biochemical threats.Therefore,developing reliable,direct,simpler,and sensitive optical sensors for such toxic biochemical hazards is critically important.Herein,we have rationally designed a Ru(Ⅱ)-based emissive chemodosimeter possessing a reactive site in the peripheral ligand for the selective detection of a G-series CWA mimic(diethyl chlorophosphate,DCP)and phosgene(COCl_(2))in the presence of relevant interferents.The Ru(Ⅱ)complex,[Ru(phen)_(2)(phen-Napen)](PF_(6))_(2)[1],where phen is 1,10-phenanthroline and phen-Nap-en is 1,10-phenanthroline functionalized with a naphthalic anhydride conjugated 2-aminoethylamino group as the reactive site,was synthesized and characterized for the selective‘turn-ON’detection of a nerve agent mimic(DCP)and toxic phosgene at distinct excitation wavelengths.The structural integrity of the probe[1]was confirmed,and the solution chemistry and photophysical properties of the probe were studied using various spectroscopic techniques to evaluate its optical parameters.The probe functions as a highly effective chemodosimetric agent for the dual sensing of the CWA mimic(DCP)and phosgene.The probe exhibits a fast‘turn-ON’response(<10 s)and shows excellent selectivity over competing interferents with high sensitivity for phosgene[LOD=126 nM]and DCP[LOD=73 nM].The appended 2-aminoethylamino group acts as the reactive site for the analyte-specific reaction.It reacts with phosgene or CWAs via nucleophilic or phosphorylation reactions to form cyclized or phosphorylated products,respectively.The final adducts,[1]-phos and[1]-DCP,containing 2-imidazolidinone or phosphorylated products,were identified using ESI-MS and ^(1)H,^(13)C and ^(31)P NMR spectroscopy.This reaction mechanism was thoroughly investigated and supported by ESI-MS analysis,NMR spectroscopy,and theoretical calculations.The enhanced red luminescence of[1]upon reaction with phosgene or DCP is attributed to the perturbation of the ^(3)MLCT state in the resulting products.Furthermore,a portable test kit utilizing[1]loaded on solid surface was developed for the realtime,selective,rapid,and highly sensitive visual monitoring of phosgene and nerve gases at the nM level.
基金supported by the National Natural Science Foundation of China(Grant Nos.61671368,62174130)Basic Public Welfare Research Planning Project of Zhejiang Province(Grant No.LGG19F040002)+2 种基金the Science and Technology Program of Shaanxi Province(Grant No.2021GY-061)the Opening Project of Key Laboratory of Microelectronic Devices&Integrated Technology,Institute of Microelectronics,Chinese Academy of Sciences,National Defense Foundation of China(Grant Nos.2022-JCJQ-JJ-1099,2022-JCJQ-JJ-1108)the Fundamental Research Funds for the Central Universities。
文摘Chemical warfare agents(CWAs)can cause significant harm to health and even death in a very short time even when inhaled in small amounts(~100 mg min/m^(3)).Detection equipment based on conventional techniques,including gas chromatography-mass spectrometry,Raman spectroscopy,fluorescence spectroscopy,and ion mobility spectrometry,have the disadvantages of high cost,long detection time,and high power consumption.Rapid,portable,and convenient equipment for target CWAs detection under interference is a challenge.In this study,we propose an alarm system comprising a multitype micro sensor array and a field-programmable gate array-based readout circuit for CWAs simulants detection.Under common volatile organic compound,temperature,and water vapor interference,the proposed multitype sensor-based detection system realizes an alarm function in less than 20 s with thresholds of 1 ppm dimethyl methylphosphonate(DMMP),4.6 ppm 2,2'-dichlorodiethyl ether(DCE),and 20 ppm SO_(2).Furthermore,the proposed detection system was evaluated outside the laboratory and passed the wilderness test,demonstrating its reliability in the atmosphere.We believe that the proposed alarm system will contribute to the development of intelligent,portable,low-cost,and anti-interference CWAs detection technology.
基金This work was supported by the National Natural Science Foundation of China(No.22175155)the opening project of the State Key Laboratory of Explosion Science and Technology(Beijing Institute of Technology)(No.KFJJ22-05M)the Science and Technology on Applied Physical Chemistry Laboratory,China(No.6142602230302).
文摘Metal clusters represent a promising class of catalysts for various reactions,but the simultaneous improvement of their stability and catalytic activity is a longstanding challenge.Herein,we created a stable dual-cluster metal-organic framework(MOF)that featured atomically synergistic bimetallic pair sites colocalized within sub nanometer pockets.The pair sites,consisting of Ni and Mo sites respectively originating from defective MOF and Polyoxometalate(POM)clusters,were rationally constructed by size-matched ligand exchange.The as-obtained dual-cluster MOF(MnMo_(6)-lg-PCN-601)exhibited superior catalytic activity,rate performance(t_(1/2)<1 min,TOF=140 min^(-1)),and stability toward the degradation of the chemical warfare agent simulant 2-chloroethyl ethyl sulfide(CEES).In-situ Fourier transform infrared(FTIR)studies and density functional theory(DFT)calculations demonstrated that the atomic synergy between colocalized pair sites favored the adsorption and activation of the CEES substrate,moreover,it also promoted H_(2)O_(2) decomposition for the selective oxidation of CEES.Our work opens a new avenue for the construction of stable metal clusters with high catalytic activity for application in various multi-substrate reactions.
