Detection Of Nerve Agents Research Articles

A Versatile Photoinduced Electron Transfer‐Based Upconversion Fluorescent Biosensing Platform for the Detection of Disease Biomarkers and Nerve Agent

AbstractUpconversion nanoparticles (UCNPs) have emerged to be a new family of fluorescent probes for bioanalytical applications. In a typical design, the UCNPs act as the energy donors in a fluorescence resonance energy transfer (FRET) system, in which the target molecules mediate the energy transfer from the UCNPs to the acceptors, and their quantity information is consequently converted into the “on‐off” upconverting signals for readout. However, each UCNP contains thousands of emitting center ions and most of them are beyond the FRET critical distance, which hinders the fluorescence energy transfer efficiency, resulting in a low signal‐to‐background ratio (SBR). Herein, a new design is presented in which the energy of UCNPs is transferred to the o‐quinones on their surface via the photoinduced electron transfer (PET) mechanism. In this system, the quenching efficiency of UCNPs' fluorescence can be up to 94.73%, providing a high SBR. The performance of the PET‐based design is systematically testified, and the high‐sensitivity detection of disease biomarkers (tyrosinase and alkaline phosphatase) is demonstrated. Moreover, this UCNP‐PET platform is also capable of sensing the simulant of nerve agent sarin. This work will pave new ways to the design of UCNP‐based platforms toward bioanalytical applications.

A flavonoid-based fluorescent test strip for sensitive and selective detection of a gaseous nerve agent simulant

Developing fluorescent sensors with ability of monitoring gaseous nerve agents in a sensitive and selective manner is of great importance due to the extreme toxicity and volatility of organophosphorus nerve agents. Herein we reported a novel oxime-modified flavonoid sensor and carefully investigated its sensing behavior towards nerve agent simulants, diethylchlorophosphate (DCP). In the presence of DCP, a remarkable fluorescence enhancement accompanied with emission color change could be observed by naked eyes in solution. The response time was less than 90 s and LOD value was calculated as 0.78 μmol/L in solution. The sensing mechanism could be ascribed to the specific reaction between halophosphate and hydroxyl group of oxime. Furthermore, sensor strips have been successfully constructed by using PEG as matrix with a simple preparation process, and also achieved the sensitive and selective detection of DCP vapor. These results in this study may provide important references for further design of dye-based sensor strips for detection of nerve agents both in solution and gas phase.

Tubes for detection of cholinesterase inhibitors—Unique effects of Neusilin on the stability of butyrylcholinesterase-impregnated carriers

Detection tubes are small devices for the colorimetric enzymatic detection of cholinesterase inhibitors such as sarin, soman, VX nerve agents and substances denoted as Novichok. These detectors contain carriers in the form of pellets with immobilized cholinesterase, substrate and detection reagent. Their advantages are portability, sensitivity and simplicity, enabling fast detection of such compounds from air and water in case of a terrorist attack or war. In general, maintaining the stability of an enzyme for a longer time is very problematic; therefore, its further enhancement is required for safety and financial reasons. In this study, the stability of our patented carriers in the form of pellets with immobilized butyrylcholinesterase containing an increasing amount of the unique sorbent Neusilin® US2 was evaluated. The samples containing Neusilin maintained the stability of the immobilized enzyme for a longer time even at higher temperature and humidity than the currently commercially used carrier without Neusilin, allowing improved detection of nerve agents.

Fabrication and Optimization of Conductive Paper Based on Screen-Printed Polyaniline/Graphene Patterns for Nerve Agent Detection

In this work, a high-performance sensor capable of effectively detecting nerve gas, a type of chemical warfare agent, was realized by conductive paper with polyaniline (PANI) nanofiber and graphene...

Polymer-Bound 4-Pyridyl-5-hydroxyethyl-thiazole Fluorescent Chemosensors for the Detection of Organophosphate Nerve Agent Simulants.

Fluorescent sensors have been synthesized for organophosphate nerve agent detection. The resulting 4-pyridyl-5-hydroxyethyl structures react with organophosphate nerve agent simulants such as diethylchlorophosphate and diisopropylfluorophosphate and cyclize to form a dihydroquinolizinium ring that results in an increased fluorescence response to long-wave UV excitation. These sensors have been functionalized with monomeric substitutions that allow for covalent incorporation into a polymer matrix for organophosphate detection to develop a fieldable sensor. In addition, inclusion of silicon dioxide into the polymer matrix eliminated false-positive responses from mineral acids, greatly advancing this class of sensors.

The Application of a Single-Column GC-MS-MS Method for the Rapid Analysis of Chemical Warfare Agents and Breakdown Products.

The development of one comprehensive gas chromatographic-triple quadrupole mass spectrometric (GC-MS-MS) method for the analysis of nerve agents and their breakdown products can pose a challenge due to significant differences in analyte volatility. Nerve agent breakdown products typically have a low volatility, requiring a derivatization step prior to analysis by gas chromatography (GC). However, nerve agent parent compounds are generally more volatile, which eliminates the need for derivatization and allows for direct analysis. Therefore, the analysis of these analytes is typically performed using separate analytical methods. This may require the use of multiple columns composed of different stationary phases to ensure the most efficient separation. With the wide selection of GC columns and derivatizing agents, it is potentially possible to develop a single-column/analytical method that is suitable for the detection of nerve agents and their breakdown products. We evaluated six nerve agents (tabun, sarin, soman, cyclosarin, VX and Russian VX) and the six corresponding breakdown products (EDPA, IMPA, PMPA, CMPA EMPA and MMPA). Chromatographic separation and multiple-reaction mode electron ionization detection of the nerve agents and silylated breakdown product derivatives were performed using an Agilent 7890 A gas chromatography (GC) equipped with a mid-polarity column, coupled to a 7000 triple quadrupole mass spectrometry system. A fast (12.5 min), highly sensitive (picogram) and selective method was achieved. The feasibility of this method for nerve agent and breakdown product detection in real samples was demonstrated using nerve agent-spiked human plasma at various exposure times (3 min, 1 h and 24 h). Five of the six nerve agents and all six breakdown products were successfully detected. This robust method has utility as a rapid screening tool to identify a specific nerve agent in a potential exposure event by simultaneous detection of the parent and or its corresponding breakdown product in plasma.

Synthesis and Applications of Stenhouse Salts and Derivatives.

In recent years, Stenhouse salts have attracted much attention as intermediates for the synthesis of cyclopenten-2-enones. This Minireview aims to present an overview of the methods for preparation, further transformation and applications of Stenhouse and Stenhouse-like salts. In this context, the Piancatelli rearrangement and its variants, and the recently reported donor-acceptor Stenhouse salts (DASA) will be addressed. The photophysical properties of DASA and its applications in colorimetric detection of amines, functionalization of polymers for detection of heat and nerve agents, photolithography and orthogonal photoswitching systems are discussed.

Recent Advances in the Development of Chromophore-Based Chemosensors for Nerve Agents and Phosgene.

The extreme toxicity and ready accessibility of nerve agents and phosgene has caused an increase in the demand to develop effective systems for the detection of these substances. Among the traditional platforms utilized for this purpose, chemosensors including surface acoustic wave (SAW) sensors, enzymes, carbon nanotubes, nanoparticles, and chromophore based sensors have attracted increasing attention. In this review, we describe in a comprehensive manner recent progress that has been made on the development of chromophore-based chemosensors for detecting nerve agents (mimic) and phosgene. This review comprises two sections focusing on studies of the development of chemosensors for nerve agents (mimic) and phosgene. In each of the sections, the discussion follows a format which concentrates on different reaction sites/mechanisms involved in the sensing processes. Finally, chemosensors uncovered in these efforts are compared with those based on other sensing methods and challenges facing the design of more effective chemosensors for the detection of nerve agents (mimic) and phosgene are discussed.

A Pyrene Derived CO2-Responsive Polymeric Probe for the Turn-On Fluorescent Detection of Nerve Agent Mimics with Tunable Sensitivity

A pyrene based turn-on fluorescent polymeric probe was developed for the tunable detection of nerve agent mimics. Glycidyl methacrylate (GMA) and dimethylacrylamide (DMA) were copolymerized by reversible addition–fragmentation chain transfer (RAFT) polymerization to yield poly-(glycidyl methacrylate-co-dimethylacrylamide) [p(GMA-co-DMA)](P1). The subsequent reaction of the secondary amine of 2-(2-((pyren-1-ylmethyl)-amino)-ethoxy)-ethanol with the epoxide unit of P1 yielded P2, which can detect diethyl cyanophosphate (DCNP), a nerve agent mimic, very efficiently by the turn-on fluorescence technique, induced by DCNP promoted intramolecular N-alkylation in both the solution and vapor phase. The lowest detection limit of P2 to DCNP was obtained as 0.1 mM, which is close to the toxicity limit of Tabun. Moreover, the detection of DCNP was successfully controlled by altering the purging of CO2/N2 gases or tuning the pH of the solution. P2 showed an efficient ON/OFF reversible fluorescence response toward CO2 a...

Round-patterned ZnO nanostructure coated with siloxane-based polymer for nerve agent detection

The alignment of zinc oxide (ZnO) nanostructures is expected to improve device sensitivities due to large surface areas which can be utilized to capture significant quantities of gas particles. In this study, we investigated patterned ZnO nanorods modified with polystyrene monolayers synthesized directly onto a quartz crystal microbalance (QCM) cell to increase the coating surface area of the sensing material. Also, we designed and synthesized a siloxane-based polymer (S1 polymer) as a sensing material. The patterned ZnO nanorods coated with S1 polymers were fabricated and used for the detection of dimethyl methylphosphonate (DMMP). The resonance frequency of QCM was shifted due to the adsorption and desorption of a compound at the surface of the modified electrodes. We have synthesized an S1 polymer that exhibited high sensitivity to DMMP. The patterned ZnO nanorods coated with the polymer also exhibited improved sensitivity due to an enhanced surface area capable of adsorbing more DMMP vapor.

3D Printed Electrodes for Detection of Nitroaromatic Explosives and Nerve Agents.

Three-dimensional (3D) printing has proven to be a versatile and useful technology for specialized applications in industry and also for scientific research. We demonstrate its potential use toward the electrochemical detection of nitroaromatic compounds 2,4,6-trinitrotoluene (TNT), 2,4-dinitrotoluene (DNT), and fenitrothion (FT). The detection of these compounds is of utmost importance in military and forensic applications. Stainless steel electrodes were fabricated by 3D printing, and the surface was electroplated with gold. The electrochemical performance of the 3D printed electrodes was compared to that of the conventionally employed glassy carbon electrode (GCE) and proved to be more sensitive toward the detection of all three nitroaromatic compounds. 3D printing of customizable electrodes provides a viable alternative to traditional electrodes for the analysis of samples with electrochemical methods.

A simple and sensitive surface-enhanced Raman spectroscopic discriminative detection of organophosphorous nerve agents.

Organophosphorous nerve agents (NAs) pose a great threat to nations and people because of their acute and extreme toxicities. The rapid detection of NAs has attracted growing interest in the first emergency response field. In this work, we demonstrate a simple and sensitive surface-enhanced Raman spectroscopic (SERS) method for NAs detection, and G- and V-agents discrimination. The results show that VX (V-agents) can be directly detected at a 20ngmL-1 level with pinhole shell-isolated gold nanoparticles (pinSHINs) as the substrate. Moreover, combined with a specific and prompt alkaline keto-oxime transformation approach in a full aqueous solution, G-agents can be measured as low as 10ngmL-1 with excellent discrimination from V-agents and other common organophosphorous pesticides within several minutes. The achieved discriminative detection of G-agents and VX could be significant not only for reducing the false positive and negative signals but also for providing an appropriate recommendation on the effective medical rescue. A decontamination outcome occurred alongside, any highly toxic G-agents were converted to a less toxic phosphate, and the generated cyanide was fully and firmly adsorbed onto the surface of pinSHINs substrate, which may be further used for on-site detection of extremely toxic NA prototypes. Graphical abstract ᅟ.

Identification of V-type nerve agents in vapor samples using a field-portable capillary gas chromatography/membrane-interfaced electron ionization quadrupole mass spectrometry instrument with Tri-Bed concentrator and fluoridating conversion tube.

A field-portable gas chromatography-mass spectrometry (GC-MS) system (Hapsite ER) was evaluated for the detection of nonvolatile V-type nerve agents (VX and Russian VX (RVX)) in the vapor phase. The Hapsite ER system consists of a Tri-Bed concentrator gas sampler, a nonpolar low thermal-mass capillary GC column and a hydrophobic membrane-interfaced electron ionization quadrupole mass spectrometer evacuated by a non-evaporative getter pump. The GC-MS system was attached to a VX-G fluoridating conversion tube containing silver nitrate and potassium fluoride. Sample vapors of VX and RVX were converted into O-ethyl methylphosphonofluoridate (EtGB) and O-isobutyl methylphosphonofluoridate (iBuGB), respectively. These fluoridated derivatives were detected within 10min. No compounds were detected when the VX and RVX samples were analyzed without the conversion tube. A vapor sample of tabun (GA) was analyzed, in which GA and O-ethyl N,N-dimethylphosphoramidofluoridate were detected. The molar recovery percentages of EtGB and iBuGB from VX and RVX vapors varied from 0.3 to 17%, which was attributed to variations in the vaporization efficiency of the glass vapor container. The conversion efficiencies of the VX-G conversion tube for VX and RVX to their phosphonate derivatives were estimated to be 40%. VX and RVX vapors were detected at concentrations as low as 0.3mg m-3 . Gasoline vapor was found to interfere with the analyses of VX and RVX. In the presence of 160mg m-3 gasoline, the detection limits of VX and RVX vapor were increased to 20mg m-3 . Copyright © 2017 John Wiley & Sons, Ltd.

New Autoinductive Cascade for the Optical Sensing of Fluoride: Application in the Detection of Phosphoryl Fluoride Nerve Agents.

A new autoinductive cascade employing benzoyl fluoride as a latent source of fluoride is reported for signal amplification and optical detection of fluoride. The autoinduction leads to a maximum 4-fold signal enhancement for each fluoride generated, as well as a self-propagating cycle that generates three fluorophores for each single fluoride released. A two-step integrated protocol creates a more rapid autoinductive cascade than previously reported, as well as a highly sensitive diagnostic assay for the ultratrace quantitation of a phosphoryl fluoride nerve agent surrogate.

Triphenylamine–benzimidazole based switch offers reliable detection of organophosphorus nerve agent (DCP) both in solution and gaseous state

Triphenylamine-conjugated imidazole dye acts as a potential sensor for the liquid and vapour phase detection of nerve agent simulantDCP.

Highly selective and sensitive chromogenic detection of nerve agents (sarin, tabun and VX): a multianalyte detection approach.

A novel strategy using ferrocenyl dye (1) was developed for highly selective chromogenic detection of all nerve agents. The protocol was first established with nerve agent mimics (DFP, DCNP, and malaoxon) and then implemented on real agents, i.e. sarin, tabun and VX. The developed chemosensor showed no interferences from the most probable interferents such as acetyl chloride, sulfur mustard, oxygen mustard and DMMP. Real-time visual detection with a lower limit of detection (below LD50) made the present protocol highly appealing and versatile.

Photonic crystal hydrogel sensor for detection of nerve agent

Nowadays the photonic crystal hydrogel materials have shown great promise in the detection of different chemical analytes, including creatinine, glucose, metal ions and so on. In this paper, we developed a novel three-dimensional photonic crystal hydrogel, which was hydrolyzed by sodium hydroxide (NaOH) and immobilized with butyrylcholinesterase (BuChE) by 1-(3-Dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride(EDC). They are demonstrated to be excellent in response to sarin and a limit of detection(LOD) of 1×10−9 mg mL−1 was achieved.

A microneedle biosensor for minimally-invasive transdermal detection of nerve agents.

A microneedle electrochemical biosensor for the minimally invasive detection of organophosphate (OP) chemical agents is described. The new sensor relies on the coupling of the effective biocatalytic action of organophosphorus hydrolase (OPH) with a hollow-microneedle modified carbon-paste array electrode transducer, and involves rapid square-wave voltammetric (SWV) measurements of the p-nitrophenol product of the OPH enzymatic reaction in the presence of the OP substrate. The scanning-potential SWV transduction mode offers an additional dimension of selectivity compared to common fixed-potential OPH-amperometric biosensors. The microneedle device offers a highly linear response for methyl paraoxon (MPOx) over the range of 20-180 μM, high selectivity in the presence of excess co-existing ascorbic acid and uric acid and a high stability sensor upon exposure to the interstitial fluid (ISF). The OPH microneedle sensor was successfully tested ex vivo using mice skin samples exposed to MPOx, demonstrating its promise for minimally-invasive monitoring of OP agents and pesticides and as a wearable sensor for detecting toxic compounds, in general.

Smart hydrogel sensor for detection of organophosphorus chemical warfare nerve agents

ABSTRACTA novel “turn-off” fluorescence, smart hydrogel sensor for detection of a nerve agent simulant has been developed and tested. The smart hydrogel chemosensor has demonstrated an extremely fast and select fluorescence quenching detection response to the Sarin simulant diethylchlorophosphate (DCP) in the aqueous and vapor phases. The fluorogenic sensor utilizes 6,7-dihydroxycoumarin embedded in an polyacrylamide hydrogel matrix as the fluorescent sensing material. The rapid fluorescence quenching of the smart hydrogel films could easily be observed with the naked eye using a hand-held UV light at λ = 365 nm which demonstrates their practical application in real-time on-site monitoring.

SERS-based ultrasensitive detection of organophosphorus nerve agents via substrate’s surface modification

Highly efficient detection of the organicphosphor nerve agents such as sarin and soman, based on surface enhanced Raman scattering (SERS) effect, has been in challenge due to their weak adsorption property on coin metals. In this paper, a new strategy is presented to achieve the SERS-based ultrasensitive detection of sarin-simulated agent methanephosphonic acid (MPA) via the surface modification of SERS-substrates. The Au-coated Si nanocone array is surface-modified with 2-aminoethanethiol and used as SERS-substrate for detection of MPA. It has been shown that the modified substrate could preferentially capture MPA molecules in the solution with coupling agent and induce amidation reaction. The reaction products are still bound or anchor on the substrate’s surface. The MPA molecules can thus be detected by Raman spectral measurement of the solution-soaked SERS-substrate. The minimum detection level is down to ∼1ppb. The Raman peak intensity versus the MPA concentration is subject to a linear double logarithmic relation from ∼1ppb to ∼1000ppm, which is attributed to Freundlich adsorption of MPA on the surface-modified SERS substrate. This study provides a new way for the highly efficient SERS-based detection of the organophosphorus nerve agents and some other target molecules weakly interacted with metal substrates.