毒气之王——芥子气

芥子气,一种重要的军用毒剂,被称为“经过战争考验”的最有效的军用战剂之一。本文将从芥子气的发现及利用、理化性质、毒性、中毒机理、中毒症状、预防及治疗等方面予以简单介绍,其中渗透结构决定性能的科学思想,让读者对芥子气有所了解。     

Application of high performance liquid chromatography coupled to on-line solid-phase extraction-nuclear magnetic resonance spectroscopy for the analysis of degradation products of V-class nerve agents and nitrogen mustard

The detection and identification of the degradation products of nitrogen mustard and nerve agent VX by high performance liquid chromatography coupled to on-line solid-phase extraction-nuclear magnetic resonance spectroscopy (HPLC-UV-SPE-NMR) were demonstrated. The analytes selected for the study were N,N-dimethylaminoethanol (DMAE), N,N-diethylaminoethanol (DEAE), N,N-diisopropylaminoethanol (DIAE) and triethanolamine (TEA). Offline solid-phase extraction (SPE) followed by derivatization was applied to eliminate the interferents and make the analytes amenable for UV detection. Thereafter, chromatographically separated derivatives were trapped on on-line SPE cartridges. They were subsequently eluted and ¹H NMR and COSY spectra were obtained. The overall detection limits of the LC-UV-SPE-NMR method for the mentioned analytes were found to be 18, 23, 25, and 32 mg/L respectively. Applicability of the method to real samples was demonstrated by the analysis of samples provided during the 22nd OPCW official proficiency test. The method gave reproducible NMR spectra devoid of intense background signals.     

Efficient Oxidation of Sulfur Mustard and Its Simulants using N‐tert‐Butyl‐N‐chlorocyanamide

N‐tert‐Butyl‐N‐chlorocyanamide reacts with sulfur mustard instantaneously to give a corresponding nontoxic sulfoxide in quantitative yield. The transformation is selective and takes place in semi‐aqueous medium (CH₃CN/H₂O, 1∶1), even at subzero temperatures.     

31P NMR and HPLC Investigations of the Cyclophosphamide Metabolite,Phosphoramide Mustard

Abstract

Phosphoramide mustard (PM), a key active metabolite of the widely used anticancer drug cyclophosphamide (CP), can exist in several closely-related ionized, cyclized and substituted forms. We have developed a high pressure liquid chromatographic (HPLC) method for analysing serum concentrations of PM in order to relate these serum concentrations to toxicity and efficacy of treatment of CP. ³¹p NMR spectroscopy is used to verify the HPLC peak homology of the proposed PM peak.     

Synthesis and Characterization of Thiophene‐derived Amido Bis‐nitrogen Mustard and Its Antimicrobial and Anticancer Activities

The thiophene‐derived amido bis‐nitrogen mustard N²,N²,N⁵,N⁵‐tetrakis(2‐chloroethyl)‐3,4‐dimethylthiophene‐2,5‐dicarboxamide was designed and synthesized via five‐step reactions from commercially available 2‐chloroacetonitrile. This target compound was confirmed by ¹H NMR, ¹³C NMR, MS, IR spectra and elemental analyses, and its structure was further characterized by X‐ray single‐crystal analysis. The biological activities for the title compound and some intermediates were evaluated in vitro for their antibacterial, antifungal and cytotoxic activities. The preliminary results showed that the title compound could inhibit efficiently the growth of the tested microorganisms including drug‐resistant bacteria MRSA to some extent. Moreover, the target compound was found to be effective against prostatic carcinoma cell line (PC‐3), breast carcinoma cell line (MCF‐7), colon carcinoma (LoVo) and lung cancer (A549). Especially, it gave selective antitumor efficacy against prostatic carcinoma cell line (PC‐3) at a low dose.     

The influence of sunflower and mustard leaf extracts on the germination of mustard seeds

The extracts from sunflower and mustard leaves were separated using SPE-Columns. The mustard seeds were germinated on water (24 h) and subsequently on crude extracts or separate fractions. The heat production rate was measured by isothermal calorimetry at 21°C and changes in seed cotyledons by FT-Raman spectroscopy. Crude extracts strongly inhibited seed germination. The water and ‘methanol’ fractions of mustard and sunflower extracts have a similar influence on the pattern of heat efflux. FT-Raman spectroscopy showed that extracts caused changes in cotyledons mainly in the content of fatty acids, carotenoids and flavonoids. Isothermal calorimetry and Raman spectroscopy are useful for the study of allelopathic interactions.     

Headspace-trap gas chromatography–mass spectrometry for determination of sulphur mustard and related compounds in soil

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.     

2-硫代-4-噻唑啉酮衍生物的合成

2-硫代-4-噻唑啉酮(1)与醛反应, 再用甲醛和胺进行胺甲基化, 合成5-芳基亚甲基-3-确定胺甲基-2-硫代-4-噻唑啉酮.     

Electrocatalysis of Chemical Warfare Agent Sulfur Mustard in Room Temperature Ionic Liquid

Room temperature ionic liquids (RTILs) have the potential for being ideal alternatives for organic solvents in chemical warfare agent (CWA) electrochemical reactions. In this paper, electrocatalysis of CWA sulfur mustard (SM) was achieved by exploring the potential advantage of RTIL methyltrioctylammonium bis (trifluoromethylsulfonyl) imide and further this methodology was used for the detection of CWA. The hydrophobicity of this RTIL offers the opportunity to use this methodology in field condition without environmental humidity effect. The diffusion coefficient calculated for SM in RTIL was 0.196×10⁻⁹ cm²/s. The electrochemical parameters deduced from cyclic voltammetry such as electron transfer coefficient (α), electron transfer number (n) and heterogenous rate constant were estimated 0.11, 2 and 4.41 s⁻¹, respectively. The electrocatalytic activity of the RTIL toward the electrochemical reduction and oxidation of CWA is evidenced, showing the potential of this novel approach for the oxidation of other toxic CWAs. The new RTIL based strategy provides an opportunity to develop field deployable detection of CWA and could provide a new paradigm shift in CWA detection approach, addressing the escalating threat of CWA.     

速食鲐鱼软罐头的研制

研究了速食鲐鱼软罐头的制作工艺。根据鲐鱼加工特性,采用去皮,复合盐液漂洗、压榨、雪菜汁浸渍等工序连续脱脂。对主要工艺参数的研究表明:复合漂洗液中NaHCO3最佳浓度为2%;用6.0°Bé雪菜汁浸渍1h可得最佳效果;鱼片40℃干燥5.5h。121℃、25min杀菌后得最终制品。