一种有机硫类絮凝剂DTC的合成及性能评价

讨论了由有机伯胺或仲胺和CS2合成二硫代氨基甲酸盐DTC的反应及副反应,简介了合成工艺。根据红外光谱确认了由三乙烯四胺合成的二硫代氨基甲酸盐（以下简称DTC）的结构。以含原油350 mg/L、含悬浮固体55.1 mg/L,含Fe^2＋10.0 mg/L的模拟污水为实验水样,考察了该DTC的絮凝性能,在40℃、pH=6-7、沉降时间30分钟条件下DTC的适宜加量为20 mg/L,此时污水含油量为9.0 mg/L;使用DTC的适宜pH范围在4-8,pH=6为最佳值,适宜温度范围为10-45℃,温度高于45℃时DTC可发生热分解;DTC的除油效果随污水中Fe^2＋浓度增大而改善。在含油89.1 mg/L、含悬浮固体55.1 mg/L、含Fe^2＋13.2 mg/L的油田污水中,DTC的除油率最高,远高于常用絮凝剂PFS,PAC,CPAM,HPAM和PAM。当污水中不含Fe^2＋时,DTC无絮凝除油效果。讨论了DTC在Fe^2＋参与下的絮凝过程。图5表1参8。     

氨荒酸盐抑制铜在NaCl溶液中腐蚀的电化学研究

通过电化学极化曲线和失重实验,研究了氨荒酸盐对铜在氯化钠溶液中的缓蚀性能,并与相应胺的缓蚀性能进行了对比。结果表明:氨荒酸盐对铜具有较好的缓蚀性能。     

Cyclic ammonium salts of dithiocarbamic acid: stable alternative reagents for the synthesis of S-alkyl carbodithioates from organyl thiocyanates in water

Carbodithioate esters are important functional organosulfur compounds widely used in diverse fields such as pharmaceuticals, agrochemicals and material sciences. Common preparative methods include reaction of alkyl halides, carbon disulfide and bases under both metal-free and metal-catalyzed conditions. However, organyl thiocyanates have not been previously explored, possibly because of their conversion to organyl disulfides under basic conditions. Here, we report an efficient and practical method for the preparation of libraries of carbodithioate esters from organyl thiocyanates by reacting with cyclic amine-based dithiocarbamic acid salts in water. The protocol is found to be applicable in general to various thiocyanates such as benzyl/aroyl methyl/cinnamyl and so on. Other notable features include no by-products such as disulfides, metal- and alkali-free, aqueous conditions, and finally easy and near-quantitative formation of cyclic amine-based dithiocarbamic acid salt as a stable alternative reagent.     

Dietary exposure of Hong Kong adults to pesticide residues: results of the first Hong Kong total diet study

The use of pesticides and other chemicals has become a common practice in modern agriculture to enhance and stabilise crop yield, protect the nutritional integrity of food, facilitate food storage to assure year-round supplies, and provide attractive and appealing food products. With the adoption of strict good agricultural practice (GAP), only minimal amounts of pesticide residues should remain on the crops or in connected foods of animal origin up the food chain. To assess their associated health risk to local people, the dietary exposure of Hong Kong adults to residues of four groups of pesticides or their metabolites – organophosphorus pesticides (OPPs), carbamates, pyrethrins and pyrethroids, and dithiocarbamate (DTC) metabolites – is estimated in the first Hong Kong Total Diet Study (TDS). A total of 150 commonly consumed food items were collected and prepared “as consumed”. A total of 600 composite food samples were analysed for 85 pesticides or their metabolites by liquid chromatography-tandem mass spectrometry (LC-MS/MS). These pesticides were primarily found at low levels (highest mean = 350 μg kg^?1) in food samples of plant origin such as vegetables and fruits. Dietary exposures to pesticide residues were estimated based on the analytical results and the food consumption data of the local residents. The estimated dietary exposures of Hong Kong adults to all individual pesticides were well below their respective acceptable daily intakes (ADIs). The percentage contributions of the estimated mean and 95th percentile dietary exposures to the ADIs of individual pesticides were <6% and <24% for the OPPs, <1% for the carbamates and pyrethrins and pyrethroids, and <1% and <4% for the DTC metabolites, respectively. The findings indicate that dietary exposures to all the pesticide residues analysed in this study were unlikely to pose unacceptable health risks to the Hong Kong population.     

Synthesis,structural and optical properties of ZnS,CdS and HgS nanoparticles from dithiocarbamato single molecule precursors

Dithiocarbamate complexes of Zn(II), Cd(II) and Hg(II) were synthesize and characterized by elemental analysis, thermogravimetric analysis, UV–Vis, FTIR, ¹H- and ¹³C-NMR spectroscopy. The complexes were thermolyzed at 180°C to prepare HDA-capped ZnS, CdS and HgS nanoparticles. The optical properties of the nanoparticles showed absorptions that are blue shifted with respect to the bulk and narrow emissions. The ZnS nanoparticles are in the cubic phase with average crystallite sizes of 3–5 nm. The CdS nanoparticles consist of a mixture of cubic and hexagonal phases with particle sizes of 8–22 nm, while the HgS nanoparticles are in the cubic phase with average crystallite sizes of 7–14 nm.     

A convenient solvent-free and one-pot synthesis of 4-hydroxythiazolidine-2-thiones

A highly efficient solvent-free and simple one-pot approach for the synthesis of 4-hydroxythiazolidine-2-thione is described. The reaction of primary amines and carbon disulfide in the presence of 2-chloroacetaldehyde afforded the title compounds in high yields.     

One step gold (bio)functionalisation based on CS2-amine reaction

Dithiocarbamates have been regarded as alternative anchor groups to thiols on gold surfaces, and claimed to be formed in situ through the reaction between secondary amines and carbon disulphide. In this paper, we further exploit this methodology for a convenient one step biomolecule immobilisation onto gold surfaces. First, the reactivity between CS₂ and electroactive compounds containing amines, primary (dopamine), secondary (epinephrine), and an amino acid (tryptophan) has been investigated by electrochemical methods. Cyclic voltammetric characterisation of the modified electrodes confirmed the immobilisation of all the target compounds, allowing the estimation of their surface concentration. The best result was obtained with epinephrine, a secondary amine, for which a typical quasi-reversible behaviour of surface confined electroactive species could be clearly depicted. Electrochemical reductive desorption studies enabled to infer on the extent of the reaction and on the relative stability of the generated monolayers. Bio-functionalisation studies have been accomplished through the reaction of CS₂ with glucose oxidase in aqueous medium, and the catalytic activity of the immobilised enzyme was evaluated towards glucose, by electrochemical methods in the presence of a redox mediator. Scanning tunnelling microscopy (STM) and Atomic force microscopy (AFM) were used respectively, to characterize the gold electrodes and Glucose Oxidase coverage and distribution on the modified surfaces.     

微波消解-分光光度法测定茶叶中铜的含量

采用微波消解法预处理茶叶样品,利用二乙基二硫代氨基甲酸钠(DDTC)分光光度法测定其中铜的含量,确定了最大吸收波长、显色剂用量、显色时间、pH值、消解工艺和掩蔽剂等条件,和干法灰化法测定的结果进行对比,本方法具有灵敏度高、精密度好、耗时少、操作简单等优点,相对标准偏差(n=6)在2.2%~5.1%,加标回收率在98.6%~101.3%,结果满意。     

含FeDBC光敏剂的低密度聚乙烯膜紫外光氧化降解的研究

合成了N,N-二正丁基二硫代氨基甲酸铁(FeDBC)光敏剂,通过元素分析、热谱分析、红外(IR)光谱和紫外(UV)光谱表征了它的组成和性质。进而研究了FeDBC对UV光氧化低密度聚乙烯(LDPE)膜的物理性能、羰基指数和粘均分子量的影响,并探讨了FeDBC在敏化LDPE膜光氧降解方面的作用机理。结果表明,在LDPE膜中加入0.1％～0.3％FeDBC,即成可控寿命的LDPE农膜。     

Studies on the Vilsmeier-haack reaction. Part XIII: Novel heterocyclo-substituted 4,4′-bi-pyrazolyl dithiocarbamate derivatives

5-Imino-3-methyl-l-phenyl-2-pyrazoline-4-dithiocarbamic acid (I) underwent simultaneous formylation and dimerization reactions with the Vilsmeier reagent giving 4-[5′-imino-3-(1″-formyl-2″-dimethylaminoethenyl)-3′-methyl-1′-phenyl-1′H-pyrazolo-4′-dithiocarbamyl-2,4-dihydro-3-imino-5-methyl-2-phenyl-1-pyrazoline]dithiocarbamate (II) which hydrolysed with sodium hydroxide to give 4-[3′-(1″-formyl-2″-hydroxyethenyl)-3′-methyl-1-phenyl-1′-H-pyrazolo-4′-dithiocarbamyl-1′-pyrazoline]dithiocarbamate-5,5′-dione (IV). Treatment of II and/or IV with morpholine, piperidine, piperazine, hydroxylamine, hydrazine hydrate or phenylhydrazine afforded the corresponding dipyrazolo-4,4′-dithiocarbamate derivatives with different heterocyclic systems at the 3-position. The structures of these compounds were confirmed by microanalysis data, IR and ¹H-NMR spectrometry. All synthesized compounds have been screened in vitro against Gram-positive and Gram-negative bacteria, and fungi.