Thiodiglycol Research Articles

Overcoming the BSTFA: Study on Trimethylsilylation Derivatization Procedures for Chemical Weapons Convention-Related Alcohols in Field Analysis

After the use of chemical weapons, there is a gradual spontaneous decomposition of chemical warfare agents (CWAs), and only degradation products can be present at the time of sample collection. Depending on the type of parent compound, these are most often acids, alcohols, or thiols. This article deals with the development and optimization of methods for the trimethylsilylation of controlled alcohols that outperforms the currently widely used method with N,O-bis(trimethylsilyl)trifluoroacetamide (BSTFA) prior to gas chromatographic identification. Thiodiglycol (TDG) was chosen as a model alcohol for the development and optimization of methods. Nine trimethylsilylating agents were tested as derivatization agents. For each reagent, the method was optimized in terms of reaction medium (seven tested solvents), reaction time, and temperature. The temporal stability of the resulting derivatives and the effect of the addition of the reaction catalyst were also monitored. Subsequently, optimal methods were applied in the derivatization of N-ethyldiethanolamine, N-methyldiethanolamine, triethanolamine, 2-diisopropylaminoethanol (DIAE), and 3-quinuclidinol. The developed methods were compared in all monitored properties with the standard BSTFA-method (in acetonitrile for 30 min at 60 °C). From the developed methods, three were selected that showed similar or better sensitivity parameters than BSTFA, and at the same time were less demanding to perform. Trimethylsilylation via trimethylsilyl cyanide (TMSCN) appears to be the most successful method. In conclusion, the selected methods were applied in the analysis of contaminated environmental and urban samples – sand, acrylic paint, asphalt-aluminum paint, and concrete. The samples were measured on both a benchtop and a field gas chromatograph.

Design Analysis of Mid IR DIAL System for Detection of Hazardous Chemical Species

Nowadays, both military and public agencies are concerned with the remote detection of toxic gases and chemical warfare agents in the atmosphere. A promising method for the remote detection of such harmful chemicals in the atmosphere is Differential Absorption Lidar (DIAL). In the current paper, system design analysis has been carried out to build a DIAL system for the detection of toxic chemical warfare agents, chemical warfare simulants, explosive precursors, and pollutants. The proposed DIAL system comprises an Optical Parametric Oscillator (OPO) based tuneable laser, a 203 mm diameter Cassegrain telescope, a TE-cooled MCT detector, suitable data acquisition hardware, etc. The DIAL output parameters like return signals, SNR, and minimum measurable concentrations have been simulated under different weather conditions such as clear sky, moderately hazy sky, and hazy atmospheric conditions for given system input parameters (pulse energy, detectivity, bandwidth, DAQ resolution, etc.). We have considered chemicals such as Sarin, Thiodiglycol (TDG), acetone, and methane to be detected using the system. Analysis has been carried out for these chemicals present at different locations with varying concentrations. Our analysis reveals that the DIAL system with a laser transmitter of 5 mJ energy and 203 mm receiver telescope is capable of detecting a few ppm concentrations of toxic chemicals present anywhere between the ranges from a few tens of meters to 2 km with topographic target present. The sensitivity of the system in terms of minimum detectable concentrations for the considered chemicals is also estimated for different atmospheric conditions. It is seen that the minimum detectable concentration of TDG is 3.2 ppm in clear weather conditions which increases to 9.2 ppm under a hazy atmosphere. A similar analysis has been carried out for other toxic chemicals and has been discussed in the paper.

Electrostatic assemblies of molecularly imprinted polymers on the surface of electrospun nanofiber membranes for the point-of-care detection of thiodiglycol, a sulfur mustard poisoning metabolic marker.

In this study, molecularly imprinted polymers (MIPs) were assembled on the surface of ethylene imine polymer (PEI)/poly(vinyl alcohol) (PVA) electrospun nanofiber membranes for the point-of-care testing (POCT) of thiodiglycol (TDG), a sulfur mustard poisoning metabolic marker, using concentrated gold nanoparticles (AuNPs) as the signal reporting units. The MIPs/PEI/PVA nanofiber membranes could capture TDG specifically through the recognition interaction between MIPs and TDG. Then, AuNPs were adsorbed onto the MIPs/PEI/PVA nanofiber membranes through the Au-S interaction between TDG and AuNPs to produce a visible red color. In order to improve the sensitivity, the silver-enhanced solutions were used to deepen the color of the nanofiber membranes and the software Image J was used to read the gray value as the signal response for subsequent analysis. There was a good linear relationship between the color change of the MIPs/PEI/PVA nanofiber membranes and the TDG concentration from 0.1 ng mL-1 to 1.0 μg mL-1, and the limit of detection was 38 pg mL-1. This method was applied for the selective detection of TDG in urine, showing great potential for the clinical diagnosis of mustard gas poisoning.

Preparation of a molecularly imprinted test strip for point-of-care detection of thiodiglycol, a sulfur mustard poisoning metabolic marker

Conventional methods for the detection of the sulfur mustard poisoning metabolic marker, thiodiglycol (TDG), require expensive instruments and reagents as well as professional operators. To address these problems, a novel test strip based on a molecularly imprinted sensitive membrane (MIM) was developed in this work for point-of-care (POC) detection of TDG. The TDG test strip was prepared conveniently by coating molecular imprinted polymers (MIPs) on a nitrocellulose membrane. When the sample contained TDG, the MIPs could specifically bind with TDG. A great number of AuNPs (AuNPs) could then be adsorbed on the test strip via the formation of an Au–S bond between TDG and AuNPs, giving the test strip the obvious red color of AuNPs. In the absence of TDG, the test strip exhibited much lighter color because it could not adsorb AuNPs. By monitoring the color change of the test strip, TDG could be detected from 1.0 ng/mL to 100.0 μg/mL with a detection limit of 0.23 ng/mL (3σ) under the optimal conditions (the molar ratio of TDG to MAA was 1:2; the eluent was chloroform; the elution time was 50 min; the reaction time between MIPs and TDG was 15 min; the adsorption time of AuNPs was 40 min; the temperature of the reaction system was 35 °C). This method has excellent selectivity and has been used to detect TDG in urine, showing great potential for POC detection of TDG in clinical samples.

Rapid detection of sulfur mustard hydrolysis products based on microextraction by packed sorbent combined with nano-electrospray ionization mass spectrometry.

Sulfur mustard is a blister agent prohibited by the Chemical Weapons Convention, and the detection of its hydrolysis product, thiodiglycol (TDG), is an important indicator of blister agent contamination. Due to the poor volatility and low extraction efficiency of TDG, derivatization gas chromatography or liquid chromatography is required for conventional methods, and the detection process is cumbersome and time-consuming. A microextraction by packed sorbent (MEPS) device and a nano-electrospray ionization (nano-ESI) device were used. The central composite design (CCD) model of Response Surface Methodology was used to optimize the elution procedure; the variance analysis under equal repeated trials with multiple factors was used to quantitatively analyze the significance of the impact of related factors on the nano-ESI efficiency. The MEPS-nano-ESI-MS experimental conditions were optimized. A new detection method of sulfur mustard hydrolysis products in water based on MEPS-nano-ESI-MS was established; the detection limit was 1ng/mL and was linear between 5ng/mL and 100 ng/mL (R2 = 0.9911) with a precision of ≤7.2%, and the recovery rate was 107.89% when the sample concentration was 40 ng/mL. The experimental results showed that the proposed method could quickly detect the contaminated water samples without chromatographic separation and derivatization, thereby verifying the contamination of sulfur mustard on site.

Non-contact detection of thiodiglycol vapors and associated degradation products using atmospheric flow tube mass spectrometry.

Thiodiglycol (TDG) is a synthetic precursor and an environmental degradation product of sulfur mustard (HD). Consequently, its presence can be indicative of illicit preparation or historical presence of chemical weapons, but its lower toxicity lends itself to use as an HD simulant for testing and method development. Detection of TDG vapor often proves elusive with existing techniques exhibiting undesirably high detection limits in the gas phase (>ppm). Moreover, traditional approaches to detecting TDG vapor rely upon non-specific approaches that do not provide the certainty afforded by mass spectrometry. Using atmospheric flow tube mass spectrometry (AFT-MS), which has previously demonstrated the capacity to detect parts-per-quadrillion levels of vapor, we evaluate the capacity of this approach for non-contact residue analysis based upon TDG vapor sampling and nitrate clustering chemistry. Furthermore, we discuss challenges with ambient vapor detection using the AFT-MS system and associated observations related to TDG degradation into 2,2'-sulfonyldiglycol from exposure to ambient conditions with vapor detection being possible even after 7-weeks of sample aging.

Open field testing of mid IR DIAL for remote detection of thiodiglycol vapor plumes in the topographic target configuration

A tunable mid-infrared differential absorption lidar (DIAL) mounted on a mobile platform has been built for long range remote detection of thiodiglycol (TDG) vapor plumes. The IR spectra of TDG have been analyzed from available spectroscopy database and from the laboratory measurement. Based on the analysis, laser wavelengths at 3.190 and 3.300 μm have been selected as λon (strong absorption) and λoff (weak absorption) in the measurements. The influence of interfering molecules at these wavelengths has been also studied. The lidar return signal and sensitivity of the system have been numerically simulated based on the system parameters. The experimental DIAL system has been built using an optical parametric oscillator (OPO) based tunable laser operating in the wavelength band 3.0–3.45 μm as a transmitter and Cassegrain telescope having 200 mm diameter mirror integrated with thermoelectric cooled mercury cadmium telluride (MCT) detector as a receiver. The trans-receiver system is mounted on a pan-tilt that enables the aerial scanning operations. The lidar subsystems have been assembled and integrated on a mobile platform for conducting field experiments. An initial field testing of the system has been carried out at a remote site using the enclosed chamber containing the TDG vapor. The chamber was erected at a distance of about 950 m acted as a topographic target that reflected the laser radiation. The differential absorption signal in terms of signal ratio has been monitored continuously in real time during the trial period. The varying column content ranging from 10 to 200 ppm × m under dynamic atmospheric conditions has been calculated and discussed in this paper.

Portland Cement Based Immobilization/Destruction of Chemical Weapon Agent Degradation Products

The direct immobilization and destruction of two compounds relevant to chemical warfare agents, ethyl methylphosphonic acid (EMPA) and thiodiglycol (TDG), within a freshly mixed Portland cement pas...

Forensic evidence of sulfur mustard exposure in real cases of human poisoning by detection of diverse albumin-derived protein adducts.

We present the forensic analyses of plasma samples of human victims exposed to sulfur mustard (SM) in a crisis region in the Middle East in 2015. A few hours after exposure, poisoned persons showed typical signs and symptoms of percutaneous SM exposure including erythema and later on blisters and hardly healing skin wounds. Blood samples were collected 15days after poisoning to be analyzed for the presence of long-lived protein-adduct biomarkers to verify SM poisoning. We applied a novel bioanalytical toolbox targeting four human serum albumin-derived biomarkers that were made accessible after plasma proteolysis. These adducts contained the SM-specific hydroxyethylthioethyl moiety either bound to the thiol group of a cysteine residue (C34*) or to the side-chain carboxylic group of a glutamic acid residue (E230*). Peptide biomarkers were produced from plasma of the victims using proteinase K (C34*PF), pronase (C34*P) and pepsin (AE230*VSKL and LQQC34*PFEDHVKL) for enzymatic protein cleavage. Separation and detection were carried out by selective micro-liquid chromatography-electrospray ionization high-resolution tandem mass spectrometry (µLC-ESI MS/HR MS). In addition to this site-specific adduct detection, a general approach after alkaline hydrolysis of the plasma protein fraction was applied. Liberated thiodiglycol (TDG) was derivatized with heptafluorobutyric anhydride and detected by gas chromatography-electron ionization mass spectrometry (GC-EI MS). The different bioanalytical methods yielded congruent results confirming SM poisoning for all patients who showed clinical signs and symptoms. This is the first time that real cases of SM poisoning were confirmed and presented by such a broad compilation of protein-derived biomarkers.

Determination of Thiodiglycol and Its Oxide in Biomedical Samples by Gas Chromatography–Mass Spectrometry

A unified procedure is proposed for the determination of thiodiglycol (TDG) and its oxide (TDGO) as markers of exposure to sulfur mustard in biomedical samples (urine, blood plasma, hairs) by gas chromatography–electron ionization mass spectrometry. The limit of detection of the procedure is comparable with the lowest level of endogenous TDG in biosamples (1 ng mL–1). Solid-phase microextraction of the derivatized analytes from the reaction mixture decreases the matrix effect. The procedure was tested in the analysis of rat biosamples obtained after in vivo exposure to sulfur mustard. The procedure was found to offer a higher potential in the retrospective determination of the total TDG and TDGO level in rat urine (within 7 days after exposure to 2 mg kg–1 of sulfur mustard) compared to the determination of the same markers in blood plasma. Blood plasma can be used for confirmatory analysis, provided the samples are taken within 2 days after exposure. Hair was found to be the least suitable biomatrix in view of the variability of the TDG background level in these samples and the possibility of contamination with TGD from other sources.

Unexpected Reaction Pathways Leading to Thiodiglycol During the Degradation of Long-Chain Sulfur Mustards.

Degradation of long-chain sulfur mustards with various commercial decontaminants unexpectedly forms thiodiglycol (TDG) through unreported reaction pathways. Chemical warfare agents (CWAs) degradation products have to be unambiguously related to their reference compounds in order to fulfill international verification protocols. Thus, the formation of TDG using water-based decontaminants introduces an uncertainty in the origin of this chemical that has been systematically used to unambiguously demonstrate the presence of yperite in environmental and biomedical samples. Therefore, these novel and unprecedented degradation pathways will result either in modifications of the international verification protocols for forensic purposes or in the exclusion of TDG as an exclusive marker of yperite.

Evaluation of carbon aerogel-based solid-phase extraction sorbent for the analysis of sulfur mustard degradation products in environmental water samples

In this study, SPE method using a carbon aerogel(CA)-based sorbent was developed and evaluated for the simultaneous extraction of sulfur mustard (HD) degradation products from environmental water samples. Applied CAs proved to be very promising materials for use as SPE sorbents, due to their high porosity, very low density and a large specific surface area. 10 degradation products of HD, both aliphatic and cyclic (thiodiglycol (TDG), TDG sulfoxide, TDG sulfone, 3,5-dithia-1,7-heptanediol, 3,6-dithia-1,8-octanediol, 1,4-thioxane, 1,3-dithiolane, 1,4-dithiane, 1,2,5-trithiepane, and 1,4,5-oxadithiepane) were extracted on a CA-based SPE cartridge. The concentrations of target analytes in the eluate were determined by HPLC-DAD and CE-DAD. Several parameters affecting the extraction efficiency, including the kind and volume of the eluting solvent, sample loading flow rate, volume and ionic strength as well as the reusability of the cartridge, were investigated and optimized to achieve the best performance for the analytes. A series of quantitative parameters such as linear range, coefficient of determination, LOD, LOQ and precision were examined under the optimized conditions. High sensitivity (LODs 0.17–0.50 μM) and high precision (intraday RSD = 2.0–7.7% and interday RSD = 2.7–9.9%) for all the analytes were achieved. The performance of the CA-based sorbent was compared with that of commonly used SPE sorbents. Applied for the analysis of spiked pore water samples collected from the Bornholm Basin, one of the largest chemical warfare dumping sites in the Baltic Sea, the proposed method allowed high SPE recoveries of all the analytes ranging from 83.5 to 99.7% to be obtained.

Simultaneous quantification of four metabolites of sulfur mustard in urine samples by ultra-high performance liquid chromatography-tandem mass spectrometry after solid phase extraction

Four HD urinary metabolites including hydrolysis metabolite thiodiglycol (TDG), glutathione-derived metabolite 1,1′-sulfonylbis[2-S-(N-acetylcysteinyl)ethane] (SBSNAE), as well as the β-lyase metabolites 1,1′-sulfonylbis[2-(methylsulfinyl)ethane] (SBMSE) and 1-methylsulfinyl-2-[2-(methylthio) ethylsulfonyl]ethane (MSMTESE) are considered as important biomarkers for short-term retrospective detection of HD exposure. In this study, a single method for simultaneous quantification of the four HD metabolites in urine samples was developed using ultra high performance liquid chromatography-tandem mass spectrometry (UHPLC–MS/MS). The four urinary metabolites were simultaneously extracted from urinary samples using a solid phase extraction (SPE) method with high extraction recoveries for all four metabolites varied in the range of 71.1–103% followed by UHPLC–MS/MS analysis. The SPE is simple and high effective only requiring 0.1mL of urinary samples and 0.5h time consuming. The problem of previous co-elution of TDG and SBSNAE in UHPLC was well solved, and complete separation of TDG, SBSNAE, SBMSE and MSMTESE from SPE-processed urine matrix was obtained to increase specificity and sensitivity. A full method validation was performed for each analyte in urine matrix. The linear range of calibration curves for the four analytes were respectively from 0.50–500ngmL−1 for TDG and SBSNAE, 0.05–500ngmL−1 for SBMSE and MSMTESE with coefficient of determination value (R2) ≥0.990. The limit of detection was 0.25ngmL−1 for TDG and SBSNAE, 0.01ngmL−1 for SBMSE and MSMTESE spiked in normal urine. The intra/inter-day precision for each analyte at three QC levels had relative standard deviation (%RSD) of ≤10.3%, and the intra/inter-day accuracy ranged between 88.0–108%. This developed method allows for simultaneous and trace measurement of four HD urinary metabolites within one single determination with the lowest usage amount of urine samples over all previous methods This study provides a useful tool for early diagnosis and monitoring of HD poisoning for medical treatment with high confidence, avoiding the need for application of several analysis methods.

Electrochemical sensing of thiodiglycol, the main hydrolysis product of sulfur mustard, by using an electrode composed of an ionic liquid, graphene nanosheets and silver nanoparticles

The authors describe a method for amperometric determination of thiodiglycol (TDG), the main hydrolysis product of sulfur mustard. The electrode consists of a mixture of graphene nanosheets, silver nanoparticles and the ionic liquid octylpyridinium hexafluorophosphate. Electrochemical oxidation of TDG was performed by cyclic voltammetry at pH 4 and revealed a pair of well-defined redox peaks at potentials of 0.43 and 0.19 V (vs. Ag/AgCl). Amperometric detection was accomplished over a dynamic range that is linear in the 10–3700 μM concentration range. The detection limit (at an S/N of 3) is 6 μM. The electrode was applied to the determination of TDG in (spiked) waste water and gave recoveries that ranged from 98.2 to 103.3 %.

Development of a capillary electrophoresis method with direct UV detection for the analysis of thiodiglycol and its oxidation products.

A novel method based on CE with precolumn derivatization and direct UV detection for the determination of thiodiglycol (TDG), TDG sulfoxide, and TDG sulfone in water samples was developed. The lack of a UV chromophore of target analytes was overcome by derivatization with phthalic anhydride. The reactant concentrations, as well as the derivatization dependence on heating temperature and time, were carefully investigated. The baseline separation of three derivatives was achieved in less than 8 min by applying a simple BGE composed of a 30 mM borate buffer at pH 8.5. Several parameters affecting the separation efficiency (buffer pH and concentration, capillary temperature, and applied voltage) were evaluated. Calibration curves of all compounds showed good linear correlations (R(2) > 0.9994). The LODs of the TDG and its oxidation products were in the range of 98-154 ng/mL. The precision tests resulted in RSDs for migration times and peak areas of less than 1.2 and 3.6%, respectively. The developed method was successfully applied for the analysis of TDG and oxidation products in seawater, utilizing the carbon aerogel-based adsorbents for sample purification and concentration. Additionally, the method has the potential to be transformed into a portable CE format.

Oral toxicity evaluation of thiodiglycol in Sprague-Dawley rats.

Thiodiglycol (TDG) is the main product of sulfur mustard hydrolysis and is an environmental contaminant. Subacute and subchronic oral toxicity studies with TDG were conducted in Sprague-Dawley rats. Neat TDG was administered by gavage at doses of 157, 313, 625, 1250, 2500, 5000, and 9999 mg/kg/d, 5 days per week, for 14 days. In the 14-day study, decreased body weight and food consumption were observed at 5000 mg/kg/d. In the 90-day study, rats received neat TDG at doses of 50, 500, or 5000 mg/kg/d for 5 days per week. A fourth group served as a sham control. Individual body weight and food consumption were measured weekly. At termination of the experiment, urine, blood, and tissue samples were collected. Rats displayed significant decreased body weight with no effect on food consumption following administration of TDG at 5000 mg/kg/d. Both male and female rats showed significant increased kidney weights at 5000 mg/kg/d. The organ to body weight ratios increased significantly for liver, kidneys, testes, and brain in males and adrenals in females for 5000 mg/kg/d. At all doses of TDG, hematological and clinical parameters and tissue histopathology remained unaltered. The no observed adverse effect level (NOAEL) for oral subchronic toxicity was 500 mg/kg/d. Benchmark dose (BMD) was derived from the decreased gain in body weight that was seen in male rats. A BMD based on a 10% decrease in body weight was 1704 mg/kg/d, and the lower confidence limit on the dose BMD, the BMDL, was 372 mg/kg/d.

Monitoring urinary metabolites resulting from sulfur mustard exposure in rabbits, using highly sensitive isotope-dilution gas chromatography-mass spectrometry.

A highly sensitive method for the determination of sulfur mustard (SM) metabolites thiodiglycol (TDG) and thiodiglycol sulfoxide (TDGO) in urine was established and validated using isotope-dilution negative-ion chemical ionization (NICI) gas chromatography-mass spectrometry (GC-MS). TDGO in the samples was reduced with TiCl3, and then determined together with TDG as a single analyte. The sample preparation procedures, including two solid-phase-extraction (SPE) clean-up steps, were optimized to improve the sensitivity of the method. The limits of detection (LOD) for both TDG and TDG plus TDGO (TDG + TDGO) were 0.1 ng mL(-1), and the limits of quantitation (LOQ) for both were 0.3 ng mL(-1). The method was used in a rabbit cutaneous SM exposure model. Domestic rabbits were exposed to neat liquid SM at three dosage levels (0.02, 0.05, and 0.15 LD50), and the urinary excretion of four species of hydrolysis metabolites, namely free TDG, free plus conjugated TDG (total TDG), free TDG + TDGO, and free plus conjugated TDG + TDGO (total TDG + TDGO), was evaluated to investigate the metabolic processes. The total urinary excretion profiles of the metabolites, including the peak time, time window, and dose-response and time-response relationships, were clarified. The results revealed that the concentrations of TDG and TDG + TDGO in the urine increased quickly and then decreased rapidly in the first two days after SM exposure. The cumulative amount of total TDG + TDGO excreted in urine during the first five days accounted for 0.5-1% of the applied dose of SM. It is also concluded that TDG and TDGO in urine existed mainly in free form, the levels of glucuronide and of sulfate conjugates of TDG or TDGO were very low, and most hydrolysis metabolites were present in the oxidized form (TDGO). The study indicates that the abnormal increase of TDG and TDGO excretion levels can be used as a diagnostic indicator and establishes a reference time-window for retrospective analysis and sampling after SM exposure.

Determination of mustard gas hydrolysis products thiodiglycol and thiodiglycol sulfoxide by gas chromatography-tandem mass spectrometry after trifluoroacetylation.

A method for detecting mustard gas degradation products thiodiglycol (TDG) and thiodiglycol sulfoxide (TDGO) in water and sediment samples using gas chromatography-tandem mass spectrometry (GC-MS/MS) after derivatization with 1-(trifluoroacetyl)imidazole (TFAI) was described. Selected reaction monitoring mode (SRM) of tandem mass spectrometry was developed for analysis of TDG and TDGO derivatives while analysis by gas chromatography-atomic emission detector (GC-AED) was performed using the 181 nm sulfur canal. TFAI derivatization conditions were optimized and the method validated. Two derivatization agents were compared, TFAI and N,O-bis(trimethylsilyl) trifluoroacetamide (BSTFA), where derivatization using TFAI occurred quicker and under milder conditions than using BSTFA. Water samples containing TDG and TDGO were evaporated to dryness under nitrogen, dissolved in organic solvent followed by reaction with TFAI. The limit of detection (LOD) for TDG and TDGO were 0.01 and 5 ng/mL, respectively. The limit of detection for TDG was decreased by two orders of magnitude if TFAI is used for derivatization rather than silyl derivatizing agents (e.g., BSTFA). TFAI has three major advantages in comparison to BSTFA, the first is much higher sensitvity, the second is a very clean background of chromatograms, and the last one is very mild conditions of derivatization. Moreover, by-products are not formed during derivatization of TDGO by TFAI in comparison to derivatization by silylating agents.

Vapor Pressure of Thiodiglycol

Thiodiglycol (TDG), also known as bis(2-hydroxyethyl) sulfide and thiodiethanol, is a precursor of the blister agent sulfur mustard (bis(2-chloroethyl) sulfide). It is also a hydrolytic degradation product, and as such, it is of considerable forensic interest to the chemical defense community. Experimental vapor pressure data have been reported previously for TDG at T = (283.15 to 353.15) K, in addition to reduced-pressure boiling points at T = (353.15 to 454.65) K. New data have been measured using two complementary American Society for Testing and Materials International methods at T = (417.75 to 538.58) K by differential scanning calorimetry and in the ambient temperature range using saturator methodology at T = (298.15 to 313.15) K. The new TDG vapor pressure data are in sharp contrast to widely accepted values from previous literature.

Graphene oxide as carboelectrocatalyst for in situ electrochemical oxidation and sensing of chemical warfare agent simulant

The graphene oxide (GO) was prepared via the chemical oxidation of natural graphite powder followed by microwave irradiation and then used to modify the surface of gold (Au) electrode. The morphology of GO was characterized using transmission electron microscopy, X-ray diffraction, scanning electron microscopy and Raman spectroscopy. The synthesized GO was used as a carboelectrocatalyst for the electrochemical oxidation of chemical warfare agent simulant thiodiglycol (TDG) at room temperature by modifying the gold (Au) electrode with GO. The electrochemical behavior of TDG on GO modified Au electrode (GO/Au electrode) was investigated by cyclic voltammetry and differential pulse voltammetry. The results with GO/Au electrode indicated involvement of excellent electrocatalytic activity toward the TDG oxidation and gas chromatography–mass spectrometry (GC–MS) results revealed the formation of 2-(2-hydroxy-ethanesulfinyl)-aldehyde as main oxidation product. Degradation studies were also performed and products were identified by GC–MS which indicated the formation of thioglycolic acid, 2-(2-hydroxy-ethanesulfinyl)-ethanol, 1,4-oxathione and 1,4-oxathiane 4 oxide as main degradation products.