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1.
Luminescence ; 39(4): e4731, 2024 Apr.
Article in English | MEDLINE | ID: mdl-38566570

ABSTRACT

Nerve agents are becoming serious issues for the healthy and sustainable environment of modern civilization. Therefore, its detection and degradation are of paramount importance to the scientific community. In the present contribution, we have introduced a chromo-fluorogenic pyrene-based  probe, (E)-2-methoxy-3-(pyren-1-ylimino)-3,8a-dihydro-2H-chromen-4-ol (PMCO) to detect sarin stimulant diethylchlorophosphate (DCP) in solution and gaseous phases. On inserting DCP in PMCO solution, a visual colorimetric change from yellow to clear colourless in daylight and highly intensified blue fluorescence was observed instantly under a 365 nm portable UV lamp light. PMCO has outstanding selectivity and high sensitivity with a limit of detection of 1.32 µM in dimethyl sulfoxide (DMSO) medium and 77.5 nM in 20% H2O-DMSO. A handy strained paper strip-based experiment was demonstrated to recognize DCP in a mixture of similar toxic analytes. A dip-stick experiment was performed to identify DCP vapour, and may be used as an effective photonic tool. We also demonstrated real sample analysis utilizing different DCP-spiked water samples and validating DCP detection even in various types of soils such as sand, field, and mud. Therefore, this present study provides an effective chemosensor for instant and on-site detection of toxic nerve agents in dangerous circumstances.


Subject(s)
Nerve Agents , Organophosphorus Compounds , Sarin , Sarin/analysis , Nerve Agents/analysis , Fluorescent Dyes , Dimethyl Sulfoxide , Gases
2.
Environ Monit Assess ; 196(9): 829, 2024 Aug 21.
Article in English | MEDLINE | ID: mdl-39167268

ABSTRACT

In the presented study, an efficient and fast analytical method was developed for the determination of parathion ethyl as sarin simulant by gas chromatography-mass spectrometry (GC-MS). Dispersive solid phase extraction (DSPE) was performed to concentrate parathion ethyl from soil, plant and water samples. Reduced graphene oxide-iron (II, III) oxide (rGO-Fe3O4) nanocomposite was used as an adsorbent to collect the target analyte from the aqueous sample solutions. After the optimization of extraction/preconcentration parameters, optimum conditions for adsorbent amount, eluent type, mixing type/period, eluent volume and initial sample volume were determined as 15 mg, acetonitrile, vortex/30 s, 100 µL and 10 mL, respectively. Under the optimum conditions, analytical performance of the developed DSPE-GC-MS method was evaluated in terms of limit of detection (LOD), limit of quantitation (LOQ) and dynamic range. Dynamic range, LOD and LOQ values were figured out to be 0.94-235.15 µg/kg, 0.41 µg/kg and 1.36 µg/kg (mass based), respectively. Satisfactory percent recovery results (90.3-125% for soil, 93.5-108.7% for plant, 88.5-112.9% for tap water) were achieved for soil, plant and tap water samples which proved the accuracy and applicability of the developed method. It is predicted that the DSPE-GC-MS method can be accurately used for the detection of sarin in soil, plant and water samples taken from war territories.


Subject(s)
Gas Chromatography-Mass Spectrometry , Sarin , Soil Pollutants , Soil , Solid Phase Extraction , Water Pollutants, Chemical , Solid Phase Extraction/methods , Gas Chromatography-Mass Spectrometry/methods , Sarin/analysis , Soil Pollutants/analysis , Soil/chemistry , Water Pollutants, Chemical/analysis , Environmental Monitoring/methods , Parathion/analysis , Nerve Agents/analysis , Plants/chemistry , Limit of Detection , Graphite/chemistry
3.
Molecules ; 28(23)2023 Nov 21.
Article in English | MEDLINE | ID: mdl-38067417

ABSTRACT

Dried urine spot (DUS) is a micro-sample collection technique, known for its advantages in handling, storage and shipping. It also uses only a small volume of urine, an essential consideration in working with small animals, or in acute medical situations. Alkyl-phosphonic acids are the direct and indicative metabolites of organophosphorus chemical warfare agents (OP-CWAs) and are present in blood and urine shortly after exposure. They are therefore crucially important for monitoring casualties in war and terror scenarios. We report here a new approach for the determination of the metabolites of five CWAs in urine using DUS. The method is based on a simple and rapid sample preparation, using only 50 µL of urine, spotted and dried on DBS paper, extracted using 300 µL methanol/water and analyzed via targeted LC-MS/MS. The detection limits for the five CWAs, sarin (GB), soman (GD), cyclosarin (GF), VX and RVX in human urine were from 0.5 to 5 ng/mL. Recoveries of (40-80%) were obtained in the range of 10-300 ng/mL, with a linear response (R2 > 0.964, R > 0.982). The method is highly stable, even with DUS samples stored up to 5 months at room temperature before analysis. It was implemented in a sarin in vivo exposure experiment on mice, applied for the time course determination of isopropyl methylphosphonic acid (IMPA, sarin hydrolysis product) in mice urine. IMPA was detectable even with samples drawn 60 h after the mice's (IN) exposure to 1 LD50 sarin. This method was also evaluated in a non-targeted screening for multiple potential CWA analogs (LC-Orbitrap HRMS analysis followed by automatic peak detection and library searches). The method developed here is applicable for rapid CWA casualty monitoring.


Subject(s)
Chemical Warfare Agents , Mice , Humans , Animals , Chemical Warfare Agents/analysis , Sarin/analysis , Chromatography, Liquid/methods , Tandem Mass Spectrometry/methods , Organophosphorus Compounds/analysis
4.
Anal Bioanal Chem ; 414(13): 3863-3873, 2022 May.
Article in English | MEDLINE | ID: mdl-35396608

ABSTRACT

Sarin is a highly toxic nerve agent classified by the Chemical Weapon Convention as a Schedule 1 chemical with no use other than to kill or injure. Moreover, in recent times, chemical warfare agents have been deployed against both military and civilian populations. Chemical warfare agents always contain minor impurities that can provide important chemical attribution signatures (CAS) that can aid in forensic investigations. In order to understand the trace molecular composition of sarin, various analytical approaches including GC-MS, LC-MS and NMR were used to determine the chemical markers of a set of sarin samples. Precursor materials were studied and the full characterisation of a synthetic process was undertaken in order to provide new insights into potential chemical attribution signatures for this agent. Several compounds that were identified in the precursor were also found in the sarin samples linking it to its method of preparation. The identification of these CAS contributes critical information about a synthetic route to sarin, and has potential for translation to related nerve agents.


Subject(s)
Chemical Warfare Agents , Nerve Agents , Chemical Warfare Agents/analysis , Chromatography, Liquid/methods , Gas Chromatography-Mass Spectrometry , Nerve Agents/analysis , Sarin/analysis , Tandem Mass Spectrometry
5.
Molecules ; 26(15)2021 Jul 30.
Article in English | MEDLINE | ID: mdl-34361784

ABSTRACT

The field of gas chromatography-mass spectrometry (GC-MS) in the analysis of chemical warfare agents (CWAs), specifically those involving the organophosphorus-based nerve agents (OPNAs), is a continually evolving and dynamic area of research. The ever-present interest in this field within analytical chemistry is driven by the constant threat posed by these lethal CWAs, highlighted by their use during the Tokyo subway attack in 1995, their deliberate use on civilians in Syria in 2013, and their use in the poisoning of Sergei and Yulia Skripal in Great Britain in 2018 and Alexei Navalny in 2020. These events coupled with their potential for mass destruction only serve to stress the importance of developing methods for their rapid and unambiguous detection. Although the direct detection of OPNAs is possible by GC-MS, in most instances, the analytical chemist must rely on the detection of the products arising from their degradation. To this end, derivatization reactions mainly in the form of silylations and alkylations employing a vast array of reagents have played a pivotal role in the efficient detection of these products that can be used retrospectively to identify the original OPNA.


Subject(s)
Nerve Agents/analysis , Organophosphates/analysis , Organophosphorus Compounds/analysis , Organothiophosphorus Compounds/analysis , Sarin/analysis , Soman/analysis , Alkylation , Fluorobenzenes/chemistry , Gas Chromatography-Mass Spectrometry/methods , Humans , Hydrolysis , Methylation , Nerve Agents/chemistry , Organophosphates/chemistry , Organophosphorus Compounds/chemistry , Organothiophosphorus Compounds/chemistry , Sarin/chemistry , Soman/chemistry
6.
Anal Bioanal Chem ; 412(5): 1097-1110, 2020 Feb.
Article in English | MEDLINE | ID: mdl-31907592

ABSTRACT

A three-layered composite wipe was fabricated by laminating individual layers of non-woven polypropylene, activated carbon fabric (ACF) and aramid fabric for the sampling and investigation of chemical warfare agents (CWA)-contaminated urban porous and non-porous surfaces. The material of main ACF layer was characterized to ascertain its suitability to act as an efficient adsorbent for the surface wipe sampling. The performance of ACF-based composite wipe was determined by evaluating its extraction efficiency, wiping efficacy and adsorption capacity for the sampling of blister and nerve agent class of CWA-contaminated surfaces using gas chromatography-mass spectrometry (GC-MS). Parameters like amount of wipe required, solvent selection, amount of solvent, time of extraction etc. were optimized to achieve the maximum recovery of contaminating analytes required for the forensic investigations. Overall recoveries of contaminating analytes after sampling and extraction were found to be in the range of 45-85% for all types of surfaces. No breakthrough in wiping process was noticed up to contamination density (CD) 1.6 mg/cm2 for non-porous surface and 3.2 mg/cm2 for porous surfaces. ACF-based wipe was found capable to significantly reduce the vapour hazards from liquid sulphur mustard (HD) and sarin (GB). Contamination from surfaces could be preserved within the wipe up to 15 days for the extended forensic investigation purposes. Limit of detections (LOD) of contaminants was determined in the range of 0.8-6.8 ng/cm2 while limit of quantitation (LOQ) was achieved up to the range of 2.4-14.4 ng/cm2 for wipe sampling of different surfaces. Graphical abstract.


Subject(s)
Chemical Warfare Agents/analysis , Mustard Gas/analysis , Sarin/analysis , Specimen Handling/instrumentation , Textiles , Adsorption , Environmental Monitoring/methods , Gas Chromatography-Mass Spectrometry/methods , Limit of Detection , Microscopy, Electron, Scanning , Reference Standards , Solvents/chemistry , Surface Properties
7.
Anal Chem ; 91(17): 10927-10931, 2019 09 03.
Article in English | MEDLINE | ID: mdl-31305982

ABSTRACT

Simple and fast detection of chemical warfare agents vapor is necessary and urgent to fight against uncertain terrorist attacks and wars. In this contribution, inspired by the design of the hybrid locally excited and charge transfer (HLCT) excited state, two fast and highly sensitive visualization and fluorescence probes for DCP detection with relative small interstate coupling (J) TPA-2AC and TPA-9AC are reported. Upon exposure to saturated DCP vapor, the TPA-9AC test strips exhibited a rapid fluorescent response in no more than 1 s, accompanied by a change of the color from green to red. The detection limit of the test strips can be estimated as sensitive as 0.15 ppb, which is far superior to the "harmless" level (7 ppb) of human response to acute sarin exposure. More impressively, the fluorescent intensity of the test strips can be quickly restored when exposed to ammonia vapor for cyclic utilization, demonstrating an application prospect in the real-time detection of chemical warfare agents.


Subject(s)
Chemical Warfare Agents/analysis , Fluorescent Dyes/chemistry , Organophosphorus Compounds/analysis , Sarin/analysis , Spectrometry, Fluorescence/methods , Equipment Reuse , Humans , Limit of Detection , Reagent Strips/analysis , Static Electricity
8.
Anal Chem ; 91(17): 10979-10983, 2019 09 03.
Article in English | MEDLINE | ID: mdl-31373196

ABSTRACT

The highly selective and sensitive fluorescence "light-up" probe, 5'-(dimethylamino)-2'-formyl-N-hydroxy-[1,1'-biphenyl]-2-carboxamide(PTS), has been fabricated for the nerve-agent mimic diethyl chlorophosphate (DCP). The probe is designed by combining two novel strategies of "covalent assembly" and Lossen rearrangement. Formation of a phosphoryl intermediate from DCP and a hydroxamic acid group in PTS yields an isocyanate that quickly undergoes Lossen rearrangement to produce an aniline that condenses intramolecularly to a fluorescent phenanthridine system. PTS shows superior properties to probe DCP, such as rapid response (within 100 s), low detection limit (10.4 nM), specificity, and excellent linearity (R2 = 0.9993) in the range from 2 to 16 µM. More importantly, its application of detecting DCP vapor has also been achieved with satisfying results.


Subject(s)
Biphenyl Compounds/chemistry , Chemical Warfare Agents/analysis , Fluorescent Dyes/chemistry , Organophosphorus Compounds/analysis , Spectrometry, Fluorescence/methods , Aniline Compounds/chemistry , Humans , Isocyanates/chemistry , Kinetics , Limit of Detection , Molecular Mimicry , Organophosphates/analysis , Phenanthridines/chemistry , Sarin/analysis , Soman/analysis
9.
Chemistry ; 23(16): 3903-3909, 2017 Mar 17.
Article in English | MEDLINE | ID: mdl-28117920

ABSTRACT

The G-class nerve agents, which include sarin, soman, and cyclosarin, react readily with nucleophilic reagents to produce fluoride. Thus, a chemosensing protocol has been designed for these agents that pairs the nucleophilic reactivity of oximates for generating fluoride with an autoinductive target amplification reaction to amplify the quantity of fluoride for facile colorimetric and fluorescent optical quantification. The chemosensing protocol was demonstrated by using the nerve agent surrogate diisopropyl fluorophosphate (DFP) and benzaldoxime as the nucleophile. Autoinductive fluoride amplification responds to fluoride released from DFP by amplifying the fluoride concentration and a yellow reporter molecule. The reporter is a conjugated oligomer with a nominal repeating unit that originates from 4-aminobenzaldehyde. Exposure of the amplified fluoride to a fluoride-specific ratiometric fluorescent reporter provides a fluorescent readout, in which three fluorophores are generated per fluoride. Both colorimetric and fluorescent readouts enable quantitative assays with low micromolar limits of detection for fluoride resulting from DFP. More importantly, this work demonstrates the successful merging of multiple complex reactions for achieving selective, sensitive, and quantitative chemosensing.


Subject(s)
Colorimetry/methods , Fluorides/analysis , Isoflurophate/analysis , Nerve Agents/analysis , Spectrometry, Fluorescence/methods , Fluorescent Dyes/chemistry , Organophosphorus Compounds/analysis , Oximes/chemistry , Phosphates/analysis , Sarin/analysis , Soman/analysis
10.
Anal Chem ; 88(12): 6523-30, 2016 06 21.
Article in English | MEDLINE | ID: mdl-27161086

ABSTRACT

Several methods for the bioanalysis of nerve agents or their metabolites have been developed for the verification of nerve agent exposure. However, parent nerve agents and known metabolites are generally rapidly excreted from biological matrixes typically used for analysis (i.e., blood, urine, and tissues), limiting the amount of time after an exposure that verification is feasible. In this study, hair was evaluated as a long-term repository of nerve agent hydrolysis products. Pinacolyl methylphosphonic acid (PMPA; hydrolysis product of soman) and isopropyl methylphosphonic acid (IMPA; hydrolysis product of sarin) were extracted from hair samples with N,N-dimethylformamide and subsequently analyzed by liquid chromatography-tandem mass spectrometry. Limits of detection for PMPA and IMPA were 0.15 µg/kg and 7.5 µg/kg and linear ranges were 0.3-150 µg/kg and 7.5-750 µg/kg, respectively. To evaluate the applicability of the method to verify nerve agent exposure well after the exposure event, rats were exposed to soman, hair was collected after approximately 30 days, and stored for up to 3.5 years prior to initial analysis. PMPA was positively identified in 100% of the soman-exposed rats (N = 8) and was not detected in any of the saline treated animals (N = 6). The hair was reanalyzed 5.5 years after exposure and PMPA was detected in 6 of the 7 (one of the soman-exposed hair samples was completely consumed in the analysis at 3.5 years) rat hair samples (with no PMPA detected in the saline exposed animals). Although analysis of CWA metabolites from hair via this technique is not appropriate as a universal method to determine exposure (i.e., it takes time for the hair to grow above the surface of the skin and typical analysis times are >24 h), it complements existing methods and could become the preferred method for verification of exposure if 10 or more days have elapsed after a suspected exposure.


Subject(s)
Chemical Warfare Agents/analysis , Hair/chemistry , Nerve Agents/analysis , Organophosphorus Compounds/analysis , Soman/analogs & derivatives , Chemical Warfare Agents/metabolism , Chromatography, High Pressure Liquid/methods , Hair/metabolism , Humans , Limit of Detection , Nerve Agents/metabolism , Organophosphorus Compounds/metabolism , Sarin/analysis , Sarin/metabolism , Soman/analysis , Soman/metabolism , Spectrometry, Mass, Electrospray Ionization/methods , Tandem Mass Spectrometry/methods
11.
Chemistry ; 22(32): 11138-42, 2016 Aug 01.
Article in English | MEDLINE | ID: mdl-27124609

ABSTRACT

Test strips that in combination with a portable fluorescence reader or digital camera can rapidly and selectively detect chemical warfare agents (CWAs) such as Tabun (GA), Sarin (GB), and Soman (GD) and their simulants in the gas phase have been developed. The strips contain spots of a hybrid indicator material consisting of a fluorescent BODIPY indicator covalently anchored into the channels of mesoporous SBA silica microparticles. The fluorescence quenching response allows the sensitive detection of CWAs in the µg m(-3) range in a few seconds.


Subject(s)
Boron Compounds/chemistry , Chemical Warfare Agents/chemistry , Nerve Agents/chemistry , Organophosphates/chemistry , Prothrombin Time/methods , Sarin/chemistry , Silicon Dioxide/chemistry , Soman/chemistry , Chemical Warfare Agents/analysis , Nerve Agents/analysis , Organophosphates/analysis , Sarin/analysis , Soman/analysis
12.
Sensors (Basel) ; 15(8): 18302-14, 2015 Jul 28.
Article in English | MEDLINE | ID: mdl-26225975

ABSTRACT

A linear hydrogen-bond acidic (HBA) linear functionalized polymer (PLF), was deposited onto a bare surface acoustic wave (SAW) device to fabricate a chemical sensor. Real-time responses of the sensor to a series of compounds including sarin (GB), dimethyl methylphosphonate (DMMP), mustard gas (HD), chloroethyl ethyl sulphide (2-CEES), 1,5-dichloropentane (DCP) and some organic solvents were studied. The results show that the sensor is highly sensitive to GB and DMMP, and has low sensitivity to HD and DCP, as expected. However, the sensor possesses an unexpected high sensitivity toward 2-CEES. This good sensing performance can't be solely or mainly attributed to the dipole-dipole interaction since the sensor is not sensitive to some high polarity solvents. We believe the lone pair electrons around the sulphur atom of 2-CEES provide an electron-rich site, which facilitates the formation of hydrogen bonding between PLF and 2-CEES. On the contrary, the electron cloud on the sulphur atom of the HD molecule is offset or depleted by its two neighbouring strong electron-withdrawing groups, hence, hydrogen bonding can hardly be formed.


Subject(s)
Acids/chemistry , Acoustics/instrumentation , Chemical Warfare Agents/analysis , Polymers/chemistry , Computer Systems , Hydrogen Bonding , Mustard Gas , Organophosphorus Compounds/analysis , Sarin/analysis , Volatilization
13.
Biomed Microdevices ; 16(2): 269-75, 2014 Apr.
Article in English | MEDLINE | ID: mdl-24288016

ABSTRACT

This paper reports a lab-on-a-chip for the detection of Sarin nerve agent based on rapid electrochemical detection. The chemical warfare agent Sarin (C4H10FO2P, O-isopropyl methylphosphonofluoridate) is a highly toxic organophosphate that induces rapid respiratory depression, seizures and death within minutes of inhalation. As purified Sarin is colourless, odourless, water soluble and a easily disseminated nerve agent, it has been used as a weapon in terrorist or military attacks. To ascertain whether potable water supplies have been adulterated with this extremely potent poison, an inexpensive, sensitive and easy to use portable test kit would be of interest to first responders investigating such attacks. We report here an amperometric-based approach for detecting trace amounts of Sarin in water samples using a screen-printed electrode (SPE) integrated in a microfluidic chip. Enzymatic inhibition was obtained by exposing the immobilised biosensor in the microfluidic platform to Sarin in water samples. With the aid of cobalt phthalocyanine modified SPE, the device could detect Sarin at part-per-billion levels with concentration as low as 1 nM. The detection method reported here represents a significant improvement over the authors'previous optical-based detection method.


Subject(s)
Chemical Warfare Agents/analysis , Electrochemical Techniques , Indoles/chemistry , Lab-On-A-Chip Devices , Sarin/analysis , Electrochemical Techniques/instrumentation , Electrochemical Techniques/methods , Isoindoles , Sensitivity and Specificity
14.
Org Biomol Chem ; 12(43): 8745-51, 2014 Nov 21.
Article in English | MEDLINE | ID: mdl-25260024

ABSTRACT

A novel colorimetric probe (P4) for the selective differential detection of DFP (a Sarin and Soman mimic) and DCNP (a Tabun mimic) was prepared. Probe P4 contains three reactive sites; i.e. (i) a nucleophilic phenol group able to undergo phosphorylation with nerve gases, (ii) a carbonyl group as a reactive site for cyanide; and (iii) a triisopropylsilyl (TIPS) protecting group that is known to react with fluoride. The reaction of P4 with DCNP in acetonitrile resulted in both the phosphorylation of the phenoxy group and the release of cyanide, which was able to react with the carbonyl group of P4 to produce a colour modulation from pink to orange. In contrast, phosphorylation of P4 with DFP in acetonitrile released fluoride that hydrolysed the TIPS group in P4 to yield a colour change from pink to blue. Probe P4 was able to discriminate between DFP and DCNP with remarkable sensitivity; limits of detection of 0.36 and 0.40 ppm for DCNP and DFP, respectively, were calculated. Besides, no interference from other organophosphorous derivatives or with presence of acid was observed. The sensing behaviour of P4 was also retained when incorporated into silica gel plates or onto polyethylene oxide membranes, which allowed the development of simple test strips for the colorimetric detection of DCNP and DFP in the vapour phase. P4 is the first probe capable of colorimetrically differentiating between a Tabun mimic (DCNP) and a Sarin and Soman mimic (DFP).


Subject(s)
Boron Compounds/chemistry , Chemical Warfare Agents/analysis , Molecular Probes/chemistry , Organophosphates/analysis , Sarin/analysis , Soman/analysis , Acetonitriles , Boron Compounds/chemical synthesis , Color , Colorimetry , Humans , Limit of Detection , Membranes, Artificial , Molecular Mimicry , Molecular Probes/chemical synthesis , Phosphorylation , Reagent Strips , Sarin/analogs & derivatives , Silica Gel , Solvents , Soman/analogs & derivatives , Substrate Specificity
15.
Environ Sci Technol ; 48(18): 10912-8, 2014 Sep 16.
Article in English | MEDLINE | ID: mdl-25133545

ABSTRACT

Mild treatment with hydrogen peroxide solutions (3-30%) efficiently decomposes adsorbed chemical warfare agents (CWAs) on microporous activated carbons used in protective garments and air filters. Better than 95% decomposition of adsorbed sulfur mustard (HD), sarin, and VX was achieved at ambient temperatures within 1-24 h, depending on the H2O2 concentration. HD was oxidized to the nontoxic HD-sulfoxide. The nerve agents were perhydrolyzed to the respective nontoxic methylphosphonic acids. The relative rapidity of the oxidation and perhydrolysis under these conditions is attributed to the microenvironment of the micropores. Apparently, the reactions are favored due to basic sites on the carbon surface. Our findings suggest a potential environmentally friendly route for decontamination of adsorbed CWAs, using H2O2 without the need of cosolvents or activators.


Subject(s)
Charcoal/chemistry , Chemical Warfare Agents/analysis , Decontamination , Hydrogen Peroxide/chemistry , Adsorption , Chemical Warfare Agents/chemistry , Hydrolysis , Kinetics , Magnetic Resonance Spectroscopy , Mustard Gas/analysis , Mustard Gas/chemistry , Organothiophosphorus Compounds/analysis , Organothiophosphorus Compounds/chemistry , Oxidation-Reduction , Sarin/analysis , Sarin/chemistry , Solutions , Temperature , Water/chemistry
16.
Chirality ; 26(12): 817-24, 2014 Dec.
Article in English | MEDLINE | ID: mdl-25298066

ABSTRACT

Chemical warfare nerve agents (CWNAs) are extremely toxic organophosphorus compounds that contain a chiral phosphorus center. Undirected synthesis of G-type CWNAs produces stereoisomers of tabun, sarin, soman, and cyclosarin (GA, GB, GD, and GF, respectively). Analytical-scale methods were developed using a supercritical fluid chromatography (SFC) system in tandem with a mass spectrometer for the separation, quantitation, and isolation of individual stereoisomers of GA, GB, GD, and GF. Screening various chiral stationary phases (CSPs) for the capacity to provide full baseline separation of the CWNAs revealed that a Regis WhelkO1 (SS) column was capable of separating the enantiomers of GA, GB, and GF, with elution of the P(+) enantiomer preceding elution of the corresponding P(-) enantiomer; two WhelkO1 (SS) columns had to be connected in series to achieve complete baseline resolution. The four diastereomers of GD were also resolved using two tandem WhelkO1 (SS) columns, with complete baseline separation of the two P(+) epimers. A single WhelkO1 (RR) column with inverse stereochemistry resulted in baseline separation of the GD P(-) epimers. The analytical methods described can be scaled to allow isolation of individual stereoisomers to assist in screening and development of countermeasures to organophosphorus nerve agents.


Subject(s)
Chemical Warfare Agents/isolation & purification , Chromatography, Supercritical Fluid/methods , Chemical Warfare Agents/analysis , Chemical Warfare Agents/chemistry , Mass Spectrometry , Organophosphates/analysis , Organophosphates/chemistry , Organophosphates/isolation & purification , Organophosphorus Compounds/analysis , Organophosphorus Compounds/chemistry , Organophosphorus Compounds/isolation & purification , Sarin/analysis , Sarin/chemistry , Sarin/isolation & purification , Soman/analysis , Soman/chemistry , Soman/isolation & purification , Spectrometry, Mass, Electrospray Ionization/methods , Stereoisomerism
17.
Anal Methods ; 16(25): 4066-4073, 2024 Jun 27.
Article in English | MEDLINE | ID: mdl-38881395

ABSTRACT

Nerve agents have posed a huge threat to national and human security, and their sensitive detection is crucial. Herein, based on the oxidation of Ce4+ and the aggregation-induced emission (AIE) of glutathione-protected gold nanoclusters (GSH-Au NCs), a cascade reaction was designed to prepare oxidized 3,3',5,5'-tetramethylbenzidine (oxTMB) and GSH-Au NCs crosslinked by Ce3+ (Ce3+-GSH-Au NCs). oxTMB had a broad UV-visible absorption range (500-700 nm) and was capable of quenching the fluorescence of Ce3+-GSH-Au NCs at 590 nm through the internal filtration effect (IFE). Thiocholine (TCh), the hydrolysis product of acetylthiocholine chloride (ATCl) catalyzed by acetylcholinesterase (AChE), reduced oxTMB completely, resulting in a decrease in the absorption of oxTMB and the recovery of IFE-quenched fluorescence of Ce3+-GSH-Au NCs. Nerve agent sarin (GB) hindered the production of TCh and the reduction of oxTMB by inhibiting the AChE activity, leading to the fluorescence of Ce3+-GSH-Au NCs being quenched again. The dual-output sensing system (AChE + ATCl + oxTMB + Ce3+-GSH-Au NCs) exhibited a low limit of detection to GB (2.46 nM for colorimetry and 1.18 nM for fluorimetry) and excellent selectivity toward common interferences being unable to inhibit AChE. Moreover, the intelligent logic gate constructed based on the sensing system showed promising applications in the field of smart sensing of nerve agents.


Subject(s)
Acetylcholinesterase , Gold , Metal Nanoparticles , Nerve Agents , Sarin , Acetylcholinesterase/chemistry , Acetylcholinesterase/metabolism , Sarin/chemistry , Sarin/analysis , Nerve Agents/chemistry , Nerve Agents/analysis , Gold/chemistry , Metal Nanoparticles/chemistry , Biosensing Techniques/methods , Cerium/chemistry , Glutathione/chemistry , Humans , Benzidines/chemistry , Spectrometry, Fluorescence/methods , Limit of Detection
18.
Anal Chem ; 85(1): 308-12, 2013 Jan 02.
Article in English | MEDLINE | ID: mdl-23153113

ABSTRACT

Rapid and sensitive detection methods are in urgent demand for the screening of extensively used organophosphorus pesticides and highly toxic nerve agents for their neurotoxicity. In this study, we developed a novel Fe(3)O(4) magnetic nanoparticle (MNP) peroxidase mimetic-based colorimetric method for the rapid detection of organophosphorus pesticides and nerve agents. The detection assay is composed of MNPs, acetylcholinesterase (AChE), and choline oxidase (CHO). The enzymes AChE and CHO catalyze the formation of H(2)O(2) in the presence of acetylcholine, which then activates MNPs to catalyze the oxidation of colorimetric substrates to produce a color reaction. After incubation with the organophosphorus neurotoxins, the enzymatic activity of AChE was inhibited and produced less H(2)O(2), resulting in a decreased catalytic oxidation of colorimetric substrates over MNP peroxidase mimetics, accompanied by a drop in color intensity. Three organophosphorus compounds were tested on the assay: acephate and methyl-paraoxon as representative organophosphorus pesticides and the nerve agent Sarin. The novel assay displayed substantial color change after incubation in organophosphorus neurotoxins in a concentration-dependent manner. As low as 1 nM Sarin, 10 nM methyl-paraoxon, and 5 µM acephate are easily detected by the novel assay. In conclusion, by employing the peroxidase-mimicking activity of MNPs, the developed colorimetric assay has the potential of becoming a screening tool for the rapid and sensitive assessment of the neurotoxicity of an overwhelming number of organophosphate compounds.


Subject(s)
Biomimetic Materials/metabolism , Chemical Warfare Agents/analysis , Colorimetry , Ferrosoferric Oxide/chemistry , Magnetite Nanoparticles/chemistry , Organophosphorus Compounds/analysis , Pesticides/analysis , Acetylcholinesterase/metabolism , Alcohol Oxidoreductases/metabolism , Biomimetic Materials/chemistry , Catalysis , Hydrogen Peroxide/chemistry , Organothiophosphorus Compounds/analysis , Oxidation-Reduction , Paraoxon/analogs & derivatives , Paraoxon/analysis , Phosphoramides , Sarin/analysis
19.
Eur J Mass Spectrom (Chichester) ; 19(3): 175-85, 2013.
Article in English | MEDLINE | ID: mdl-24308198

ABSTRACT

The chemical warfare agents (CWA) Sarin, Soman, Cyclosarin and Tabun were characterised by proton transfer mass spectrometry (PTRMS). It was found that PTRMS is a suitable technique to detect nerve agents highly sensitively, highly selectively and in near real-time. Methods were found to suppress molecule fragmentation which is significant under PTRMS hollow cathode ionisation conditions. In this context, the drift voltage (as one of the most important system parameters) was varied and ammonia was introduced as an additional chemical reagent gas. Auxiliary chemicals such as ammonia affect ionisation processes and are quite common in context with detectors for CWAs based on ion mobility spectrometry (IMS). With both, variation of drift voltage and ammonia as the reagent gas, fragmentation can be suppressed effectively. Suppression of fragmentation is crucial particularly concerning the implementation of an algorithm for automated agent identification in field applications. On the other hand, appearance of particular fragments might deliver additional information. Degradation and rearrangement products of nerve agents are not distinctive for the particular agent but for the chemical class they belong to. It was found that switching between ammonia doped and ordinary water ionisation chemistry can easily be performed within a few seconds. Making use of this effect it is possible to switch between fragment and molecular ion peak spectra. Thus, targeted fragmentation can be used to confirm identification based only on single peak detection. PTRMS turned out to be a promising technique for future CWA detectors. In terms of sensitivity, response time and selectivity (or confidence of identification, respectively) PTRMS performs as a bridging technique between IMS and GC-MS.


Subject(s)
Ammonia/chemistry , Chemical Warfare Agents/analysis , Mass Spectrometry/methods , Organophosphonates/analysis , Chemical Warfare Agents/chemistry , Models, Chemical , Organophosphates/analysis , Organophosphates/chemistry , Organophosphonates/chemistry , Organophosphorus Compounds/analysis , Organophosphorus Compounds/chemistry , Protons , Sarin/analysis , Sarin/chemistry , Soman/analysis , Soman/chemistry , Water/chemistry
20.
Nano Lett ; 12(6): 2797-802, 2012 Jun 13.
Article in English | MEDLINE | ID: mdl-22545863

ABSTRACT

Tailoring the morphology of materials in the nanometer regime is vital to realizing enhanced device performance. Here, we demonstrate flexible nerve agent sensors, based on hydroxylated poly(3,4-ethylenedioxythiophene) (PEDOT) nanotubes (HPNTs) with surface substructures such as nanonodules (NNs) and nanorods (NRs). The surface substructures can be grown on a nanofiber surface by controlling critical synthetic conditions during vapor deposition polymerization (VDP) on the polymer nanotemplate, leading to the formation of multidimensional conducting polymer nanostructures. Hydroxyl groups are found to interact with the nerve agents. Representatively, the sensing response of dimethyl methylphosphonate (DMMP) as a simulant for sarin is highly sensitive and reversible from the aligned nanotubes. The minimum detection limit is as low as 10 ppt. Additionally, the sensor had excellent mechanical bendability and durability.


Subject(s)
Conductometry/instrumentation , Nanotechnology/instrumentation , Nanotubes/chemistry , Nanotubes/ultrastructure , Polymers/chemistry , Sarin/analysis , Chemical Warfare Agents/analysis , Chemical Warfare Agents/chemistry , Equipment Design , Equipment Failure Analysis , Particle Size , Sarin/chemistry
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