Chemische Reaktionen von chlorvinylarsinverbindungen (Lewisite)

2-Chlorovinylarsine dichloride (Lewisite I) and 2,2′-dichlorodivinylarsine chloride (Lewisite II) react by room temperature rapidly and quantitatively with dithiols in a substitution reaction. The derivatives were identified with mass spectrometry. They can be detected with GC/ECD. This reactions can be used for the gas chromatographic detection of Lewisites in water and soil samples.     

Chemische Reaktionen von Chlorvinylarsinverbindungen (Lewisit)

2,2′-Dichlorodivinylarsine chloride (Lewisite II) react by room temperature quickly with alcohols in an equilibrium reaction to yield 2,2′-Dichlorodivinylarsine ether. The reactions are not quantitative. The methyl-, ethyl-and propylether are not stable.     

交联壳聚糖乙酸酯冠醚对金属离子的吸附性能研究

本文合成了二苯并-16-冠-5-氯代乙酸酯冠醚和3,5-二叔丁基-二苯并-14-冠-4-双氯代乙酸酯冠醚,然后分别将之与交联壳聚糖(简称CCTS)反应,制备了交联壳聚糖二苯并-16-冠-5-乙酸酯冠醚(简称CCTS-1)和交联壳聚糖3,5-二叔丁基-二苯并-14-冠-4-双乙酸酯冠醚(简称CCTS-2),并研究了它们对Pb~(2+),Cu~(2+),Cr~(3+),Ni~(2+),Cd~(2+)的吸附性能。结果表明:这两种吸附剂对pb~(2+),Cu~(2+)有较高的吸附选择性。     

Chemische Reaktionen von Phenylarsinverbindungen

In an equilibrium reaction, phenylarsine dichloride (PFIFFIKUS) reacts rapidly with alcohols at room temperature to yield phenylarsine bisether and phenylarsine chloride ether. The reactions, however, are not quantitative. The derivatives were identified using mass spectrometry.     

不同类型表面活性剂对1，2，4-三氯苯的增溶作用

研究了阴离子表面活性剂十二烷基硫酸钠、阳离子表面活性剂十六烷基三甲基溴化铵和非离子表面活性剂脂肪醇聚氧乙烯醚LAE对1,2,4-三氯苯（TCB）的增溶作用。讨论了表面活性剂类型对增溶作用的影响。比较发现,非离子型表面活性剂的增溶能力高于离子型表面活性剂。其原因主要是疏水有机物在非离子表面活性剂胶束中的增溶方式不同造成的。3种表面活性剂对TCB的增溶数据还表明,增港作用不仅在临界胶束浓度（MC）以上发生,而且在表面活性剂浓度低于CMC时亦有明显的增溶作用。     

溴阻燃剂对肝细胞的毒性

为评价四溴联苯醚(2,2,4,4-tetrabromodipheny lether,PBDE-47)、五溴联苯醚(2,2',4,4',5-pentabromodiphenylether,PBDE-99)、九溴联苯醚(polybrominated dipheny lethers206,PBDE-206)、六溴环十二烷(hexabromocyclododecane,HBCD)、四溴双酚A(tetrabromobisphenol A,TBBPA)对人肝细胞(LO2)的体外细胞毒性。将5种溴阻燃剂与人肝细胞LO2共同培养,采用四甲基偶氮噻唑蓝比色法(MTT法)检测5种溴阻燃剂对LO2细胞的相对增殖率,并按照GB/T16886.5-2003/ISO10993-5:1999标准评价5种溴阻燃剂对LO2的细胞毒性。体外实验表明,5种溴阻燃剂对LO2细胞均具有抑制作用,其中PBDE-47、PBDE-99和HBCD呈现剂量依赖关系。     

Photocatalytic degradation of polybrominated diphenyl ethers in pure water system

Due to the low water solubility of polybrominated diphenyl ethers, organic solvent is usually added into the oxidation system to enhance the removal efficiency. In this study the photocatalytic degradation of decabromodiphenyl ether (BDE209), a type of polybrominated diphenyl ether used throughout the world, in pure water without the addition of organic solvent was investigated. In the pure water system, BDE209 was not dissolved but dispersed as nano-scale particles with a mean diameter of 166 nm. Most of BDE209 (>98%) were removed within 4 h and the final debromination ratio was greater than 80%. Although the addition of organic solvent (tetrahydrofuran, THF) could lead to a relatively high BDE209 degradation rate, the final debromination ratio (<50%) was much lower than that in pure water system. Major oxidation intermediates of tetrahydrofuran, including tetrahydro-2-furanol and γ-butyrolactone, were detected indicating the engagement of THF in the BDE209 degradation process. The photocatalytic degradation of BDE209 in the pure water system followed first-order kinetics. The BDE209 degradation rate constant increased from 0.0011 to 0.0023 min⁻¹ as the pH increased from 3 to 9.     

Comparative larvicidal potential of different plant parts of Withania somnifera against vector mosquitoes in the semi-arid region of Rajasthan

Larvicidal potential of the extracts from different parts viz. green and red fruits, seeds, fruit without seeds, leaves and roots of Withania somnifera in different solvents was evaluated against larvae of Anopheles stephensi, Aedes aegypti and Culex quinquefasciatus, the important disease vectors prevalent in the semi-arid region. Experiments were carried out on late 3rd or early 4th instar larvae of these mosquitoes using standard WHO technique. 24 and 48 hr LC50 values along with their 95% confidence limits, regression equation, chi-square (chi2)/heterogeneity of the response have been determined by log probit regression analysis. The 24 hr LC50 values as observed for whole green fruits in water, methanol and petroleum ether were 350.9, 372.4, 576.9; 115.0, 197.1, 554.6; 154.9, 312.0, 1085.0 while corresponding values for red fruits were 473.5, 406.4,445.2; 94.7, 94.5, 1013.0; 241.8, 535.0, 893.3 mg l(-1) for An. stephensi, Ae. aegypti and Cx. quinquefasciatus respectively showing that methanol extracts were more effective against anophelines as compared to culicines when whole fruits were taken. The 24 hr LC50 values as observed for seeds in acetone, methanol and petroleum ether were 188.1, 777.5, 822.5; 245.5, 769.0, 1169.0; 140.3, 822.9, 778.4 and for fruit without seeds were 80.2, 97.6, 146.6; 88.4, 404.4, 1030.0; 30.0, 44.5, 54.2 mg l(-1) for the above mosquito species respectively showing that extract of fruit without seeds were most effective in petroleum ether followed by acetone and methanol extracts. However, experiments conducted with methanol extracts of leaves and roots of this plant species did not show any appreciable larvicidal activity and a 20-40% mortality was observed up to 500 mg l(-1) of the extracts. Overall larvae of anophelines were found more susceptible as compared to culicines to all the extracts tested. Petroleum ether extract of fruit without seeds was found most effective against all the mosquito species showing that active ingredient might be present in this part of the plant species. The study would be of great importance while planning vector control strategy based on alternative plant derived insecticides.     

4-苯基-2-丁酮微型化合成研究

运用微型化的方法对以乙酸和乙醇为基本原料合成4-苯基-2-丁酮的反应物用量、技术要点与操作步骤进行实验研究,其产率约为61%,研究结果表明此方法可行.表1,参5.     

Environmentally benign NiAlCe-hydrotalcite for efficient synthesis of benzoin ethyl ether

Benzoin ethyl ether is traditionally synthesized in two steps of initial condensation followed by etherification, using toxic cyanide catalysts and enzymes. Here, we show that an environmentally benign NiAlCe-hydrotalcite catalyst is highly efficient for one-step synthesis of benzoin ethyl ether. We synthesized NiAlCe-hydrotalcite catalysts by a modified coprecipitation method. 99.3 % selectivity was achieved at 63.7 % conversion of benzaldehyde on the NiAlCe-hydrotalcite catalyst with a Ni²⁺/Al³⁺/Ce³⁺ ratio of 22:10:1. Moreover, NiAlCe-hydrotalcite catalysts maintained stable activities over three consecutive runs.     

八氯二丙醚的研究现状与展望

八氯二丙醚是一种农药增效剂,多用于农药喷雾剂、蚊香等。八氯二丙醚在环境中滞留时间长,属于类持久性有机污染物,可能具有致畸、致癌、致突变作用。近10年来国内外学者对环境中的八氯二丙醚进行了比较多的调查和研究。首先对八氯二丙醚的性质、应用情况进行了阐述,然后分析八氯二丙醚的研究现状及可能来源,最后对未来八氯二丙醚的研究的重点和发展趋势进行了展望。文献分析表明：（1）目前国内外的研究集中报道八氯二丙醚在环境中的含量（如农药、蚊香、茶叶、大米、蔬菜、水果等）,缺乏八氯二丙醚的环境行为及其在环境中的迁移、转化及降解机理的研究,更缺乏农产品中八氯二丙醚残留的快速检测研究。（2）报道八氯二丙醚对动物及昆虫的毒性及毒理学试验、杀虫活性研究,缺乏八氯二丙醚对人体暴露风险的研究。     

代谢活化作用对多溴代联苯类污染物类/抗甲状腺激素活性的影响

选用大鼠肝匀浆(S9)和鼠肝癌细胞(H4ⅡE)两种体系代谢活化多溴代联苯醚混标(BDEs)和十溴联苯醚(BDE209),采用重组甲状腺激素受体基因酵母检测BDEs和BDE209母体及其代谢产物的类/抗甲状腺激素效应.结果表明,BDEs和BDE209母体均不表现甲状腺激素效应(p>0.05);但是经S9和H4ⅡE细胞代谢活化后,其代谢产物表现出明显的类甲状腺激素活性和抗甲状腺激素活性(p<0.05),BDEs和BDE209的干扰甲状腺激素效应需要经过代谢活化步骤.比较不同代谢活化体系,重组酵母细胞本身的代谢活化作用并不显著,而H4ⅡE细胞和S9代谢活化体系均能够导致活性中间体.     

Products of laccase catalyzed reaction of 1-hydroxypyrene

The formation of residues in soils and sediments which are not readily extractable is an important fate for hydrophobic organic contaminants. Reaction of 1-hydroxypyrene, a known fungal and terrestrial invertebrate metabolite and photo-oxidation product of pyrene, with a commercially prepared laccase (an oxidoreductive enzyme) in solution provides a test system to study the fate of residues in nature. The reaction of dissolved 1-hydroxypyrene with laccase produced a distinct color change and caused a precipitate to form. At least six products were shown by HPLC analysis with photodiode array detection. The most prominent peak was composed of 1,6- and 1,8-pyrene-dione as confirmed by proton NMR analysis. LC/MS data on remaining peaks indicate that radical coupling produces acetonitrile soluble dimers and at least one trimer. Proposed structures consistent with MS and photodiode array data indicate that pyrene subunits are linked predominantly by ether bonds. Additional products, insoluble in acetonitrile, were also formed. The formation of complex products in vitro, indicates that the same mechanisms could produce bound residues in soil.     

树脂D001负载纳米Pd/Fe双金属脱溴2,2’,4,4’-四溴联苯醚(BDE-47)的研究

采用大孔树脂D001交换吸附Pd2+、Fe2+并在厌氧条件下以硼氢化钠溶液还原吸附的钯铁离子制备成负载纳米Pd/Fe双金属树脂。利用该树脂对2,2’,4,4’-四溴联苯醚(BDE-47)进行脱溴反应,探讨了该法的可行性和特性。结果表明:当大孔树脂D001、氯化钯、硫酸亚铁用量分别为0.75 g、2μg和0.2 g时所制备的双金属树脂脱溴水-乙醇溶液中的BDE-47效果最佳,反应遵循准一级动力学,速率常数k约为0.161 d-1,半减期为1.21 d。负载Pd/Fe的D001连续3次脱溴反应都有较好的效果,水-乙醇溶液中超过90%以上的BDE-47在反应6 d后被降解。负载Pd/Fe双金属的树脂可以重复活化再生,但再生2次后其脱溴效率变差,反应6 d只有47.3%的BDE-47被降解。用气相色谱-质谱联用仪和离子色谱仪跟踪Pd/Fe双金属树脂脱溴BDE-47反应,可知产物包括溴离子、三溴联苯醚、二溴联苯醚、一溴联苯醚和联苯醚。     

4种具有α-季碳结构的对位壬基酚异构体的合成和表征

不同来源工业壬基酚混合物(t-NP)中对位壬基酚(p-NP)异构体的组成各不相同,各异构体之间在环境行为等方面也存在着较大差异,因此在壬基酚的环境归趋、生态毒性以及雌激素活性等研究中迫切需要t-NP中不同单个异构体作为模型化合物,然而目前市场上能购买到的直链壬基酚(4-n-NP)异构体不能作为代表.以苯酚和4种含分支结构的壬醇为原料(苯酚与壬醇摩尔比为4:1),以BF3为催化剂,按照Friedel-Crafts烷基化方法合成了t-NP中常见的4种烷基链具有α-季碳结构的对位壬基酚的异构体,即4(3′,5′-二甲基-3′-庚基)-苯酚(p353NP),4(3′,6′-二甲基-3′-庚基)-苯酚(p363NP),4(2′,6′-二甲基-2′-庚基)-苯酚(p262NP)和4(3′-甲基-3′-辛基)-苯酚(p33NP).合成的壬基酚粗产物用硅胶柱色谱法提纯后的纯度达99%,并经紫外可见分光光度计、荧光分光光度计、HPLC、GC-MS、1H-和13C-NMR进行了表征.合成的4种p-NP异构体可被用于壬基酚的雌激素活性、毒理、代谢和环境归趋等研究.     

树脂D001负载纳米Pd/Fe双金属脱溴2,2＇,4,4＇-四溴联苯醚（BDE-47）的研究

采用大孔树脂D001交换吸附Pd2＋、Fe2＋并在厌氧条件下以硼氢化钠溶液还原吸附的钯铁离子制备成负载纳米Pd/Fe双金属树脂。利用该树脂对2,2＇,4,4＇-四溴联苯醚（BDE-47）进行脱溴反应,探讨了该法的可行性和特性。结果表明：当大孔树脂D001、氯化钯、硫酸亚铁用量分别为0.75 g、2μg和0.2 g时所制备的双金属树脂脱溴水-乙醇溶液中的BDE-47效果最佳,反应遵循准一级动力学,速率常数k约为0.161 d-1,半减期为1.21 d。负载Pd/Fe的D001连续3次脱溴反应都有较好的效果,水-乙醇溶液中超过90%以上的BDE-47在反应6 d后被降解。负载Pd/Fe双金属的树脂可以重复活化再生,但再生2次后其脱溴效率变差,反应6 d只有47.3%的BDE-47被降解。用气相色谱-质谱联用仪和离子色谱仪跟踪Pd/Fe双金属树脂脱溴BDE-47反应,可知产物包括溴离子、三溴联苯醚、二溴联苯醚、一溴联苯醚和联苯醚。     

Anthranilic acid: a free amino‐acid pheromone in the black chafer, <Emphasis Type="Italic">Holotrichia loochooana loochooana</Emphasis>

Summary. Ether extract of the abdominal gland of female black chafers Holotrichia loochooana loochooana (Sawada) (Coleoptera: Scarabaeidae) induced a series of pre-mating behaviors that included short-distance orientation, mounting and abdominal bending toward females in the laboratory. When the extract was chromatographed on a silica gel column, the activity was eluted with 50% ether in hexane and ether fractions. GC-MS analyses revealed that both the active fractions contained anthranilic acid (2-aminobenzoic acid) as a major compound. When partitioned to basic, acidic and amphoteric fractions, pheromonal activity was observed with the latter two fractions and anthranilic acid was detected in these fractions by HPLC analyses. The amount of anthranilic acid in the female extract was estimated to be ca. 1.3 μg/female. Authentic anthranilic acid induced pre-mating behavior in males of at levels equal to that elicited by the compound in the extract. It also attracted male beetles to the traps in the field. Received 29 October 2002; accepted 9 January 2003. R1D=" Correspondence to:Hiroe Yasui, e-mail:yasui@affrc.go.jp     

Oviposition of carrot fly (Psila rosae) in response to foliage and leaf surface extracts of host plants

Summary. Foliage of twelve host and two non-host species and surrogate leaves treated with the respective leaf extracts were presented to laboratory populations of the carrot fly (Psila rosae) in oviposition choice assays. The stimulatory activity of dichloromethane surface extracts and the diethyl ether fraction of hot water extracts did not reflect accurately the differences in acceptability observed among intact leaves. A better correlation was found using hexane extracts prepared in a microwave oven. Two out of five fractions of this crude hexane extract obtained by silica gel column chromatography stimulated oviposition. The diethyl ether fraction, which contained the previously identified oviposition stimulants (propenylbenzenes, furanocoumarins, polyacetylenes), could account for only a minor part of the variation in the acceptability of host leaves. The preference hierarchy for intact leaves corresponded better to the ranking of species according to activity of the methanolic fraction, which apparently contains unknown stimulatory compounds.? The water fractions of the hot water extracts were shown to reduce egg-laying underneath surrogate leaves treated with a stimulatory extract. This oviposition-deterring effect was particularly strong with the non-preferred species Pimpinella major, which is also highly resistant in the field. Hence, unidentified inhibitory compounds may also contribute to differential accept ability of host plants. It is concluded that antixenotic (non-preference) resistance of host plants to carrot fly attack depends on complex mixtures of semiochemicals. Received 11 June 1997; accepted 26 November 1997.     

Regression models to estimate total concentrations of polybrominated diphenyl ethers: data from NHANES 2003–2004

The objective of this study was to develop regression models to estimate the total concentration of polybrominated diphenyl ethers in serum based on the known concentrations of a limited number of congeners. Because of the possible adverse health effects associated with the exposure to polybrominated diphenyl ethers, it is of interest to know their total concentrations. Data from the National Health and Nutrition Examination Survey for 2003–2004 (N = 1859) were used to develop regression models to estimate both wet weight and lipid-adjusted total concentrations. Only the knowledge of three congeners, namely, 2,2′,4,4′-tetrabromodiphenyl ether, 2,2′,4,4′,5-pentadibromodiphenyl ether, and 2,2′,4,4′,5,5′-hexabromodiphenyl ether was required to use these models. Other than the concentrations of these three congeners, age, gender, and smoking status were the only information needed to use these models. Optionally, models were developed that could also use the race/ethnicity of the participants. All models explained more than 98% of the known variability in the observed total concentration levels. Over 98% of the model generated, predicted values were found to be within 5% of the observed values.     

Visible light-assisted photocatalytic oxidation of organic pollutants using nitrogen-doped titania

An experimental research into the aqueous photocatalytic oxidation (PCO) of organic groundwater pollutants, methyl-tert-butyl ether (MTBE), tert-butyl alcohol, phenol, humic substances, 2-ethoxy ethanol and ethylene glycol was undertaken using visible light-sensitive nitrogen-doped titanium dioxide photocatalysts. Nitrogen-doped titania proved to be an effective photocatalyst for MTBE with its action comparable to and even surpassing that of Degussa P25. In contrast, with the other substances the photocatalysts showed negligible activity. This difference was explained by the poor adsorption properties of N-doped catalysts. The predominance of different PCO mechanisms dependent of the surface properties of N-TiO₂ catalysts was elucidated.