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1.
分离与鉴定柴油基体中的微量芥子气类化合物 总被引:2,自引:0,他引:2
本文叙述了制备和分析柴油和芳香烃混合溶剂基体中痕量芥子气及芥子气二硫醚样品的方法。样品用硅胶色谱柱预分离及正已烷洗脱除去大量的基体;并用制备薄层色谱分离得到纯样。样品经GC-MS,质子NMR法等作结构鉴定。分析结果与标准样品相一致。 相似文献
2.
A sensitive and specific capillary gas chromatographic method has been developed to measure trace amounts of 2,2'-dichlorodiethyl sulphide (sulphur mustard) in environmental or biological samples. Sulphur mustard was isolated from water or plasma by a solid-phase extraction procedure and from blood by liquid-liquid extraction. The accuracy and precision of the methods were demonstrated using replicate analyses of spiked water, plasma or blood: within-run and between-run variabilities were less than 20%. These analytical methods were used to evaluate the rate of sulphur mustard degradation in water or plasma. Good linear calibration curves, with a detection limit of 45 ng/ml, were obtained for quantitation and determination of sulphur mustard in blood following its intravenous administration to rats. Initial toxicokinetic data were obtained. 相似文献
3.
K. A. M. Creber P. V. Samuleev W. S. Andrews 《Journal of Radioanalytical and Nuclear Chemistry》2009,282(2):597-600
Chemical warfare agents have been stockpiled for almost a decade and their destruction has become an environmental issue that
will continue to require attention for many years. There are hundreds of thousands of tonnes yet to be destroyed, and the
current chemical or incineration techniques are not without problems. While many researchers are seeking better chemical techniques,
we decided to try ionizing radiation to destroy sulphur mustard with the goal of producing non-toxic products. We irradiated
a variety of sulphur mustard samples by both a mixed field source (β, γ and neutrons) and a pure gamma source. The mixed field
irradiation of wet sulphur mustard for long irradiation times was the most successful at destroying the chemical agent. 相似文献
4.
Methods for the analysis of thiodiglycol sulphoxide, a metabolite of sulphur mustard, in urine using gas chromatography-mass spectrometry. 总被引:1,自引:0,他引:1
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. 相似文献
5.
Stable solid adducts of silicon tetrafluoride with the following thiazoles have been prepared: 2-aminothiazole, 2-amino-5-methylthiazole, 2-amino-6-methylbenzothiazole, 2-amino-7-nitrobenzothiazole and 2,4-dimethylthiazole. These adducts have been charactertsed by chemical and infrared spectral analysis. In all the cases except that of 2,4-dimethylthiazole (SiF4·2L) the composition is 1:1. Both exocyclic and endocyclic nitrogen atoms are the coordinating centres in all the four cases while only endocyclic participates in coordination in the case of 2,4-dimethylthiazole. No indication has been found for the involvement of sulphur in coordination. Probable structures of these adducts have been proposed in which silicon is hexacoordinate. 相似文献
6.
Angelo Albert Francesco Paolo Colonna Maurizio Guerra Bianca F. Bonini Germana Mazzanti Zoltàn Dinya Gian Franco Pedulli 《Journal of organometallic chemistry》1981,221(1):47-55
The radical adducts resulting from the reaction between group IVB organometallic radicals MR3 (M = Si, Ge, Sn; R = alkyl or aryl) and a number of thioketones of the chromone and flavone series have been investigated by ESR spectroscopy. The spectral parameters obtained for these species have been compared with those of similar adducts of the corresponding ketones. Both classes of radicals adopt an orthogonal conformation, and the differences between the former and the latter paramagnetic species can be accounted for by the different electronegativity of oxygen and sulphur. the effects of substitution of the heterocyclic oxygen with a sulphur or selenium atom on the spin density distribution are likewise explained. INDO calculations have been carried out on the model systems CH2XSiH3 (X = O, S). 相似文献
7.
Karolin K. Kroening Douglas D. Richardson Scott Afton Joseph A. Caruso 《Analytical and bioanalytical chemistry》2009,393(8):1949-1956
Sulfur mustard (HD), bis(2-chloroethyl)sulfide, is one of a class of mustard agents which are chemical warfare agents. The
main chemical warfare hydrolysis degradation products of sulfur mustards are: thiodiglycol, bis(2-hydroxyethylthio)methane,
1,2-bis(2-hydroxyethylthio)ethane, 1,3-bis(2-hydroxyethylthio)propane, and 1,4-bis(2-hydroxyethylthio)butane. The aim of this
study is to identify these five hydrolysis degradation products utilizing reversed-phase high-performance liquid chromatography
coupled with inductively coupled plasma mass spectrometry (ICP-MS) for element-specific sulfur detection using a collision/reaction
cell and electrospray ionization mass spectrometry to confirm the identification. To date, this is the first study utilizing
ICP-MS with 32S element-specific detection for the analysis of vesicant chemical warfare agent degradation products. 相似文献
8.
Reactions of the sulphonium ion of sulphur mustard (SM+1) at the N7, N3 and O6 sites of guanine, N7, N3 and N1 sites of adenine, O2 and N3 sites of cytosine and O2 and O4 sites of thymine were studied theoretically in gas phase and aqueous media employing density functional theory (DFT) and second order Møller–Plesset perturbation (MP2) theory. The B3LYP, B3PW91 and B1B95 functionals of DFT and the 6-31+G* and AUG-cc-pVDZ basis sets were used in the calculations. Basis set superposition error was treated using the counterpoise method by single point energy calculations at the B3LYP/6-31+G* level in gas phase. The present study explains the mechanism of alkylation of the DNA bases and shows that SM+1 would form stable adducts at the endocyclic nitrogen sites of the DNA bases, and at the O6 site of guanine and the O2 site of cytosine. Formation of adducts at the N7 site of guanine and N3 site of adenine are found to be most favored and next most favored respectively, which agrees with experimental observations. 相似文献
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10.
Collision-induced dissociation experiment demonstrated that under the same collision energy, different fragmentation pattern could help distinguish the accurate location of amino acids-NL adducts. 相似文献
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12.
Skubal LR Biedron SG Newville M Schneider JF Milton SV Pianetta P O'Neill HJ 《Talanta》2005,67(4):730-735
Chemical analyses of U.S. stockpiled mustard chemical warfare agent show some agent destined for destruction contains mercury [L. Ember, Chem. Eng. News 82 (2004) 8]. Because of its toxicity, mercury must be removed from agent prior to incineration or be scrubbed from incineration exhaust to prevent release into the atmosphere. Understanding mercury/agent interactions is critical if either atmospheric or aqueous treatment processes are used. We investigate and compare the state of mercury in water to that in thiodiglycol, a mustard simulant, as co-contaminants are introduced. The effects of sodium hypochlorite and sodium hydroxide, common neutralization chemicals, on mercury in water and simulant with and without co-contaminants present are examined using X-ray absorption fine spectroscopy (XAFS). 相似文献
13.
Van den Driessche B Lemière F Witters E Van Dongen W Esmans EL 《Rapid communications in mass spectrometry : RCM》2005,19(4):449-454
Calf thymus DNA was treated with melphalan, a nitrogen mustard, and the formation of melphalan cross-linked DNA adducts was investigated. These cross-linked adducts could not be detected either in the enzymatically or in the thermally generated DNA hydrolysates. However, a search for DNA cross-linked adducts in the hydrolysates obtained under acidic conditions revealed the presence of different types of cross-links, mainly containing an adenine moiety. These results are very important because they show that the detection of cross-links is dependent on the hydrolytic procedure used and that these cross-linked adducts are formed under totally different reaction conditions from those in in vivo situations. This can explain the very low abundance or even the absence of cross-linked adducts in nitrogen mustard treated animals. The generally accepted theory that the anti-cancer activity of bifunctional mustards such as melphalan is due to cross-linking of DNA strands remains therefore from our point of view questionable. 相似文献
14.
Summary Platinum(IV)/platinum(II) chloride and bromide form 1 : 1, 1 : 2 or 3 : 2 (metal: ligand) addition compounds with 1,2-ethylene-, 1,3-propylene-and 1,4-butylene-bisdiphenyl-phosphine sulphide or selenide and 1,6-hexamethylene-bisdiphenylphosphine selenide. The adducts have been characterized by elemental analysis, i.r. and reflectance spectra, and molar conductance data. All adducts have been assigned bridged square planar or octahedral arrangements around platinum(II) or platinum(IV) ions respectively. Both oxidation states of platinum conform to class b behaviour with respect to the soft donor sulphur and selenium atoms of the ligands.Reprints of this article are not available. 相似文献
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Marie-Caroline Aoust de Rouvèze Veronique Gilard Robert Martino Myriam Malet-Martino Ulf Niemeyer 《Phosphorus, sulfur, and silicon and the related elements》2013,188(6-7):1735-1738
31 P NMR was used to demonstrate that glufosfamide is hydrolyzed into isophosphoramide mustard (IPM) with a half-life of about 25 h at 37;C and pH 7.4 in buffer as well as in human plasma. Through a cascade of reactions, IPM gives rise to three final products, dihydroxyIPM, phosphate ion, and phosphorylethanolamine, which is by far the major compound. 相似文献
18.
MacDonald C Smith C Michopoulos F Weaver R Wilson ID 《Rapid communications in mass spectrometry : RCM》2011,25(13):1787-1793
The application of sulphur-specific detection via ultra-performance liquid chromatography coupled to inductively coupled plasma mass spectrometry (UPLC/ICPMS) to detect and quantify the glutathione (GSH)-adducts produced via the in vitro formation of reactive metabolites is demonstrated. The adducts were formed in human liver microsomes supplemented with unlabelled GSH for clozapine. The calculation of adduct concentration was performed via comparison of the peak areas to calibration curves constructed from omeprazole, a sulphur-containing compound over the range of 0.156 to 15.62 μM of sulphur with a detection limit of 1.02 ng of sulphur on-column. Identification of the adducts was performed using conventional UPLC/time-of-flight (TOF)-MS with the calculation of clozapine intrinsic clearance carried out by high-performance liquid chromatography/tandem mass spectrometry (HPLC/MS/MS). The use of ICPMS in this way appears to offer a novel, rapid and sensitive means of determining the quantity of GSH conjugates with the combined adducts producing 0.9 μM of reactive metabolite out of a total of 3.5 μM of metabolites. The GSH adduct therefore represents 26% of this total produced as a result of the metabolism of drug to reactive species. 相似文献
19.
Bent T. Røen Erik Unneberg John Aa. Tørnes Elsa Lundanes 《Journal of chromatography. A》2010,1217(14):2171-2178
Methods for trace determination of sulphur mustard (HD) and some related cyclic sulphur compounds in soil samples have been developed using headspace-trap in combination with gas chromatography–mass spectrometry (GC–MS). Two quite different types of soil were employed in the method optimisation (sandy loam and silty clay loam). Prior to analysis, water saturated with sodium chloride was added to the samples, at a water to soil ratio of 1:1. A detection limit of 3 ng/g was achieved for HD, while the cyclic sulphur compounds 1,4-thioxane, 1,3-dithiolane and 1,4-dithiane could be detected at 0.2–0.7 ng/g. The methods were validated in the concentration range from the limit of quantification (LOQ) to hundred times LOQ. The within assay precision at fifty times LOQ was 6.9–7.3% relative standard deviation (RSD) for determination of the cyclic sulphur compounds, and 15% RSD for determination of HD. Recoveries were in the range of 43–60% from the two soil types. As the technique requires very little sample preparation, the total time for sample handling and analysis was less than 1 h. The technique was successfully employed for the determination of cyclic sulphur compounds in a sediment sample from an old dumping site for chemical munitions, known to contain HD degradation products. 相似文献
20.
含氮芥和亲脂基团的聚磷酸酯的合成及其抗肿瘤活性的初步研究 总被引:1,自引:1,他引:0
本文通过3-烷氧基1,2-丙二醇与N,N'-双(2-氯乙基)二氯磷酰胺的缩合反应,制得11种新的含氮芥和亲脂基团的聚磷酸酯.用核磁、红外光谱以及元素分析确定了聚合物的结构.部分聚合物抗肿瘤初步试验结果表明.这类聚磷酸酯对小鼠肉瘤180有一定的抑制作用.在本研究中还改进了3-烷氧基-1,2-丙二醇的合成方法. 相似文献