Establishment Of Functional Probe Sensing Arrays And Their Performance For Detecting Chemical Warfare Agents

Chemical Warfare Agents(CWAs)are characterized by their potent toxicity,enduring toxic effects,swift action,extensive damage range,and challenges in protection and treatment.Nerve agents and blister agents are two important types of traditional CWAs.They are the most dangerous,widely equipped,and historically most used.Although the Chemical Weapons Convention has explicitly banned the production and utilization of CWAs since 1997,these agents have still been misused in modern terrorist attacks and asymmetric conflicts.The persistence of the remnants of chemical agents from historical wars has been presenting considerable threats to public safety and individual health.Research on the development of detection and protection,investigation and forensics,treatments and decontamination has been continued,in which the rapid recognition and evaluation for CWAs by sensitive and accurate detection approaches are crucial to response to the CW threats,chemical terror incidents and the follow up treatments.Currently,the rapid detection technologies for CWAs are primarily centered around portable instruments and colorimetric detections.Many studies have documented the application of fluorescence and chemiluminescence for detecting various simulants for CWAs.While these approaches have shown sensitive,rapid and convenient advantages,however with discrepancies in the detection of actual toxic CWAs.Furthermore,the subtle chemical property differences of different nerve agents and different blister agents pose a significant challenge for their rapid distinguishing.Consequently,in this paper four functionalized materials were designed to develop sensor array detection systems to rapidly detect and distinguish different nerve agents and blister agents.The primary research content and findings are as follows:1.Discrimination of OPNAs via a chemiluminescence sensing array regulated by organophosphorus-H2O2 reactionDrawing upon the principles of rapid detection of organophosphorus nerve agents using chemiluminescence technology and the advantages of dimensionality reduction analysis visualization,two chemiluminescent systems,Luminol-H2O2 and MgAl-LDHsLuminol-H2O2,were designed to establish a chemiluminescence sensing array for the identification and differentiation of Sarin,Soman,Cyclosarin,and VX.The intermediate product of Peroxyphosphonate was successfully detected by 31P NMR in the sensing system,which proved the redox reaction mechanism.By processing the data with linear discriminant analysis(LDA)and hierarchical cluster analysis(HCA),characteristic two-dimensional coordinate plots for each agent were obtained,facilitating the effective distinction of the four organophosphorus nerve agents at a concentration of 1.0 μg/mL.The constructed chemiluminescence sensing array was evaluated using 20 blind samples of single organophosphorus nerve agent with an accuracy of 100%.2.Rapid detection and distinguish of carbamate nerve agent analogues using dually functionalized gold nanoclusters sensor arrayAccording to the structural and toxicology characteristics of carbamate nerve agents,ambenonium chloride(AC)was chosen as a simulant of CMNAs in this study.Bifunctional Aurum nanoclusters(CD/MUA-AuNCs)were designed using βcyclodextrin and 11-mercaptoundecanoic acid as double ligands,based on the electrostatic interaction between the quaternary ammonium sites in AC and carboxyl group in MU A,as well as the host-guest interaction between the aromatic rings and βcyclodextrin,to achieve rapid and selective detection of AC with a detection limit as low as 10.0 ng/mL.The method demonstrated good recovery and precision for AC in various samples,including natural river water,human urine,and the "water waste"samples from an OPCW proficiency test,with a relative standard deviation(RSD)of ≤5.47.Furthermore,a fluorescence sensing array composed of four types of AuNCs was designed and constructed,based on the rapid detection characteristics of nanoclusters,achieving effective differentiation of six types of carbamate toxicants and analogues at a concentration of 5.0 μg/mL.The quenching mechanism was studied and confirmed using nuclear magnetic resonance to detect the chemical shift changes.The feasibility and scope of using AC as a simulation agent for carbamate nerve agents were also proposed.The study provides a preparedness and an approach for the rapid,sensitive,and selective detection of carbamate nerve agents.3.Rapid identification and differentiation of blister agents and simulant based on TPy-TPE fluorescent probe sensing arrayTwo types of TPy-TPE fluorescent probes were synthesized using pyridine as a reactive group and tetraphenylethylene(TPE)as a fluorophore,based on the alkylation properties of blister agents.The pyridine nitrogens of the two probes reacted with blister agents to form pyridine salts,resulting in a red shifting in fluorescence.A fluorescence sensing array was constructed based on the different fluorescence responses of mustard gas,ethyl nitrogen mustard,and 2-chloroethyl ethyl sulfide to the different TPy-TPE fluorescent probes,achieving effective differentiation of the three types of agents at a concentration of 1.25 μg/mL.The machenism was validated by Q-TOF/MS detection of the alkylation products.Analysis of 12 blind samples achieved 100%identification and differentiation.In addition,the fluorescence color change in response to the two probes allows for easy differentiation of HD,HN1,and CEES at a concentrations as low as 5.0μg/mL by naked eyes.4.Rapid identification and differentiation of organophosphorus nerve agents based on AZAMON-type fluorescent probe sensor arrayBased on the sensitivity of AZAMON fluorescent probes to acidic or alkaline,a fluorescence sensing recognition method for organophosphorus nerve agents was constructed in aqueous system.Two fluorescent probes,AZAMON and MAZAMON,were synthesized.According to the different fluorescence changes of the probes when exposed to GB,GD and VX in water solutions,a fluorescence sensing array was designed to identify the three agents.The mechanism of the probe fluorescence sensing was investigated through the detection of the hydrolytic products,and by monitoring the pH value and fluorescence intensity of the system.Effective differentiation of organophosphate nerve agents was achieved at a concentration of 0.5 μg/mL.The sensing array successfully detected 12 blind samples with an accuracy of 100%.