Determination of thiodiglycol, a mustard gas hydrolysis product by gas chromatography-mass spectrometry after tert-butyldimethylsilylation

A method for determining thiodiglycol (TDG), a mustard gas hydrolysis product in water, serum and urine samples using gas chromatography-mass spectrometry (GC-MS) after tert-butyldimethylsilylation (TBDMS) is described. Quantitation of TDG was performed by measuring the respective peak area on the extracted ion chromatogram of m/z 293, using an internal standard, the TDG homologue, thiodipropanol, peak area of which was measured as m/z 321. The presence of salts in the sample solution not only suppressed the loss of TDG by vaporization during the evaporation of water, but also facilitated the rate of production of di-silylated derivative, bis(tert-butyldimethylsilyoxylethyl)sulfide (TDG-(TBDMS)2). Under the pretreatment conditions used, in which 0.5 ml of water sample supplemented with 100 microM potassium chloride was evaporated to dryness under reduced pressure, followed by reaction with N-methyl-N-(tert-butyldimethylsilyl)trifluoroacetamide at 60 degrees C for 1 h, TDG-(TBDMS)2 was reproducibly detected with about a 55% recovery and a limit of detection (LOD, scan mode, S/N = 3) of 5.4 ng/ml. TDG was also determined by GC-MS from a 0.5 ml serum sample (after perchloric acid deproteinization) and from a 0.1 ml urine sample, after TBDMS derivatization. The LOD was determined to be 7.0 and 110 ng/ml for serum and urine, respectively.     

Quantitative analysis of the sulfur mustard hydrolysis product thiodiglycol (2,2'-sulfobisethanol) in in vivo microdialysates using gas chromatography coupled with pulsed flame photometric detection

An analytical method employing gas chromatography is presented for assessing the concentrations of the sulfur mustard hydrolysis product thiodiglycol (TDG) in cutaneous in vivo microdialysates. The use of a pulsed flame photometric detector allows for selective detection of the analyte following solvent exchange and derivatization with heptafluorobutyric anhydride. Quantitative assessment is performed using thiodipropanol (TDP) as a surrogate internal standard. A linear relationship and a very significant correlation (r2 = 0.9982) between the ratio of TDG and TDP concentrations and the ratio of the square root of peak heights is demonstrated. The suitability of the analytical method is verified by the evaluation of blank in vivo microdialysates spiked with known amounts of TDG. The limit of detection in microdialysates is 0.200 nmol/mL (24.4 ng/mL) and the limit of quantitation was 0.364 nmol/mL (44.4 ng/mL). The presented method provides selective, sensitive, rapid, and high-throughput analysis of microdialysates containing TDG, providing an efficient alternative for high-performance liquid chromatography and capillary electrophoresis techniques.     

Methods for the analysis of thiodiglycol sulphoxide, a metabolite of sulphur mustard, in urine using gas chromatography-mass spectrometry.

Two methods have been developed for the analysis of thiodiglycol sulphoxide, a metabolite of sulphur mustard, in urine. The first method recovers thiodiglycol sulphoxide from urine by extraction from a solid absorbent tube and clean up on Florisil. In the second method thiodiglycol sulphoxide is reduced to thiodiglycol with acidic titanium trichloride prior to extraction. This method detects thiodiglycol, thiodiglycol sulphoxide, and their acid-labile esters, as the single analyte thiodiglycol. In both cases the recovered analytes were converted to the bis(pentafluorobenzoyl) derivative of thiodiglycol and detected by gas chromatography-mass spectrometry using negative ion chemical ionisation. The limits of detection were 1 ng per 0.5-ml sample of urine. Urine from five normal human subjects showed low background levels of thiodiglycol sulphoxide in the range 2-8 ng/ml. However, a sixth subject was found to be excreting levels of thiodiglycol sulphoxide as high as 36 ng/ml. The first method has been used in toxicokinetic studies of sulphur mustard and the second method is intended to be used for the retrospective confirmation of mustard poisoning in casualties of chemical warfare.     

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 %.

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Graphical abstract The article describes an amperometric sensor for the determination of thiodiglycol, the main hydrolysis product of sulfur mustard. The electrode was constructed by using graphene nanosheets, silver nanoparticles and an ionic liquid electrode, and it was successfully applied to the determination of thiodiglycol in (spiked) waste water samples.

     

Determination of the sulfur mustard hydrolysis product thiodiglycol by microcolumn liquid chromatography coupled on-line with sulfur flame photometric detection using large-volume injections and peak compression.

A selective, direct and relatively rapid method has been developed for the determination of thiodiglycol (TDG) in aqueous samples. TDG is the main hydrolysis product of the chemical warfare agent sulfur mustard. The method of analysis is based on the on-line coupling of reversed-phase microcolumn liquid chromatography and sulfur-selective flame photometric detection. To improve sensitivity and efficiency, peak compression by displacement was used in combination with large-volume injections. A concentration of 1% n-propanol was added to the sample to obtain the best sensitivity and efficiency after a 10 microliters injection. Detection limits of 0.25 microgram/ml were achieved with efficiencies of 4.10(5) plates per meter. The method was successfully applied during the Fourth Official Proficiency Test organized by the Technical Secretariat of the Organization for Prohibition of Chemical Weapons for the determination of TDG in a soil sample.     

Observations of metabolite formation and variable yield in thiodiglycol biodegradation process

The complete microbial degradation of thiodiglycol (TDG), the primary hydrolysis product of sulfur mustard, byAlcaligenes xylosoxydans ssp.xylosoxydans (SH91) was accomplished in laboratory-scale stirredtank reactors. An Andrews substrate inhibition model was used to describe the cell growth. The yield factor was not constant, but a relationship with initial substrate concentration has been developed. Using a substrate-inhibition and variable-yield kinetic model, we can describe the cell growth and substrate consumption in batch and repeated batch fermentations. Several reactor-operating modes successfully degrade TDG concentration to below 0.5 g/L. According to the experimental results, the two-stage repeated batch operation has the best degradation efficiency, and it also can degrade 500 mM TDG (≈60 g/L) to 5 mM (≈0.7 g/L) in <5 d. A hypothesis for explaining variable-yield and byproduct formation based on the capacity and utilization of metabolic loads is presented.     

Determination of nitrogen mustard hydrolysis products, ethanolamines by gas chromatography-mass spectrometry after tert-butyldimethylsilyl derivatization

A method for determining N-ethyldiethanolamine (EDEA), N-methyldiethanolamine (MDEA) and triethanolamine (TEA), hydrolysis products of nitrogen mustards, in water, urine and blood samples using gas chromatography-mass spectrometry (GC-MS) after derivatization by tert-butyldimethylsilylation (TBDMS) is described. The sample solution was evaporated to dryness, and reacted with N-methyl-N-(tert-butyldimethylsilyl)trifluoroacetamide (MTBSTFA) at 60 degrees C for 1h. The TBDMS derivatives were separated on a DB-5 column and detected by electron-ionization MS. The quantitation of EDEA, MDEA and TEA was performed by measuring the respective peak areas on the extracted ion chromatograms of m/z 216, m/z 202 and m/z 346, respectively, using nonadecane (C19), the peak area of which was measured at m/z 268, as an internal standard. When the water sample was initially analyzed, considerable loss of EDEA, MDEA and TEA occurred by evaporation. The addition of hydrochloric acid (HCl) to the water sample (final 1 mM), however, permitted quantitative recoveries to be achieved (88%, 88% and 79% for EDEA-(TBDMS)2, MDEA-(TBDMS)2 and TEA-(TBDMS)3, respectively). The limits of detections (LODs, scan mode, S/N = 3) were 2.5, 2.5 and 10 ng/ml for EDEA, MDEA and TEA, respectively. Ethanolamines could be also determined in urine samples (volume 0.1 ml), with reasonable recoveries of 72-100% by the addition of HCl (final 1 mM). For the analysis of serum samples, the sample was precipitated by the addition of perchloric acid (final 3.2%), and the resulting supernatant was neutralized with potassium carbonate, and then acidified by the addition of HCl. The recovery of TBDMS derivatives of ethanolamines was found to rather low (7-31%).     

Structure of a boron-free hydrolysis product from boromycin

The structure of des-boron-des-valine-boromycin C₄₀H₆₈O₁₄ · H₂O (DBDVB), the product obtained by hydrolysis of the antibiotic boromycin C₄₅H₇₄BNO₁₅, has been determined by X-ray analysis. The molecule is remarkably similar in constitution, configuration and even in conformation to those of boromycin and des-valine-boromycin determined previously [2], showing that the overall molecular shape is retained on removal of the spiro boron atom.     

乙酰胆碱酯酶催化水解产物的电化学行为

报道了乙酰硫代胆碱水解产物硫代胆碱在玻碳电极上的电化学行为。以乙酰硫代胆碱作底物,在一定条件下乙酰胆碱酯酶催化底物水解,生成电活性物质硫代胆碱。利用循环伏安法和线性扫描伏安法研究了酶催化水解产物硫代胆碱在玻碳电极上的电化学行为。结果表明:在0.1mol/L的B-R缓冲溶液(pH7.0)中,硫代胆碱有一灵敏的氧化峰,峰电位EP=0.32V(vs.SCE);该体系属具有吸附性的不可逆过程。实验测得电子转移数为2,电极反应速率常数k=0.29s-1。     

Detection of trace levels of thiodiglycol in blood, plasma and urine using gas chromatography-electron-capture negative-ion chemical ionisation mass spectrometry

A sensitive method has been developed for the detection and quantitative determination of thiodiglycol in blood, plasma and urine. Samples were extracted from Clin Elut columns and cleaned up on C18 Sep-Pak cartridges (blood, plasma) or Florisil Sep-Pak cartridges (urine). Tetradeuterothiodiglycol was added to the sample prior to extraction as internal standard. Thiodiglycol was converted to its bis-(pentafluorobenzoate) derivative and analysed by capillary gas chromatography-electron-capture negative-ion chemical ionisation mass spectrometry using selected ion monitoring. Levels of thiodiglycol down to 1 ng/ml (1 ppb) could be detected in 1-ml spiked blood and urine samples; calibration curves were linear over the range 5- or 10-100 ng/ml. Blood and urine samples from a number of control subjects were analysed for background levels of thiodiglycol. Concentrations up to 16 ng/ml were found in blood, but urine levels were below 1 ng/ml.     

预富集装置在QCM传感器检测芥子气中的运用

在化学战剂的诸种检测方法中, 质量型微传感器以其响应快速、使用简便等优点成为一种理想的检测手段. 但是这种传感器的使用往往受到检出限的限制, 对于低浓度的毒剂不能及时报警. 预富集技术的运用可以提高微传感器的检测限. 本文研制了一种预富集装置并对其进行了初步测试. 芥子气通过此预富集装置之后在QCM(石英晶体微天平)传感器上的检出限可以达到0.1 mg/m3.     

Evaluation of PFO formation from the biodegradation of a fluorotelomer-based urethane polymer product in aerobic soils

This study is the first to evaluate the rate of formation of perfluorooctanoate (PFO) from the aerobic biodegradation of a fluorotelomer-based urethane polymer and to use this information to assess the global environmental significance of this source. A fluorotelomer-based urethane polymer product test substance was studied in four aerobic soils over two years to determine the rate at which the fluorotelomer side-chains covalently bonded to the polymer backbone were cleaved and subsequently transformed to form the anions of perfluorocarboxylic acids including PFO. Over the two year duration of the experimental study, a polymer biodegradation half-life of 102 years (range: 28-241) was calculated for the urethane polymer based on regression analysis of the rate of PFO formation in four test soils. When this half-life was applied to the estimated total historic production, use and disposal of fluorotelomer-based urethane polymer, the annual potential global generation of PFO was estimated to be less than one tonne per year.     

Structure of the product of the complete hydrolysis of 1,2-bisdiazoacetylethane

Conclusions The product of the complete hydrolysis of 1,2-bisdiazoacetylethane in aqueous HClO₄, is 2,5-dioxo-1,6-hexanediol, whose structure was established by x-ray diffraction structural and analysis. UV spectroscopy indicates that this compound does not undergo keto-equal tautomerism characteristic for-hydroxy ketone.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1184–1187, May, 1985.     

Computational study on the interactions of mustard gas with cucurbituril macrocycles

The study on the absorption of toxic gases such as mustard gas by organic host is essential to the development of inexpensive detection and decontamination equipments. Using quantum chemical methods, we propose cucurbituril as an effective host to capture mustard gas. It was found that stable complexes are formed with the inclusion of the toxic gas molecules inside the cucurbituril cavity, compared with the lateral and exterior interactions. Oxygen mustard has a comparable binding energy with sulfur mustard and hence can be used during experimental investigation. Additionally, during the inclusion complex formation, the presence of heteroatoms helps the guest molecules to undergo a larger structural reorganization to get accommodated inside the cucurbituril macromolecule. Atoms‐in‐molecules analysis shows the existence of strong intermolecular CH…O bonding between the guest molecules and cucurbituril macromolecule. The presence of an intramolecular CH…Cl type of bonding accounts for the higher stabilization of sulfur mustard inside the cucurbituril macromolecule. © 2015 Wiley Periodicals, Inc.     

Determination of nitrogen mustard hydrolysis products in rat urine samples using GC-MS

A gas chromatographic-mass spectrometric method was developed, validated and demonstrated by measuring the levels of nitrogen mustard hydrolysis products in the urine collected from dosed rats. The recovery values for trimethylsilyl derivatives of EDEA and MDEA are between 82-95% and 88-112%, respectively. In vivo studies performed by using three different doses (0.5 mg/kg, 1.0 mg/kg, and 2.0 mg/kg) of HN2 base of nitrogen mustard. MDEA concentrations were between 43.1-232.2 ng/mL. The limit of detection (S/N = 3) values are 2.5 ng/mL and 1.6 ng/mL for EDEA and MDEA, respectively, and the precision of the method in terms of RSD is between 5-8%.     

Computer comparisons of variables in capillary gas chromatography

A series of computer-constructed van Deemter curves that permits evaluation of a number of variables in capillary gas chromatography is presented. The graphs permit the comparison of inter-related parameters, including the choice of carrier gas (hydrogen vs helium vs nitrogen), column length (10-100 m), column diameter (0.20, 0.25, 0.32, 0.4 mm), solute partition ratios (0-10), and liquid phase film thickness (0.1, 0.25, 0.5, 1.0 μm). The curves are evaluated, both in terms of the relative magnitude of the optimum average linear carrier gas velocity, and in terms of the significance of the sharpness of the curve.