均匀设计用于研究硝基苯衍生物对青海弧菌Q67的联合毒性

实验设计在混合物毒性评估与预测中起着非常重要的作用. 应用微板毒性测试方法测定了7种硝基苯衍生物对青海弧菌Q67的发光抑制毒性,硝基苯、邻氯硝基苯、间氯硝基苯、对氯硝基苯、间硝基苯胺、对硝基苯胺和对硝基甲苯的-lg EC₅₀值(EC50的单位为mol/L)分别为2.66,3.22,3.30,3.29,2.94,4.22和3.39;引入均匀实验设计方法,在单个硝基苯衍生物剂量-效应关系基础上构建不同效应浓度下的10个混合物,同样应用微板毒性测试方法测定其对Q67的毒性,应用剂量加和(DA)与独立作用(IA)原理建立了混合物毒性的评估与预测模型. 结果表明:与等效应浓度比法相比,均匀实验设计构建的混合物浓度配比,具有三维浓度分布特征,可在更大范围内考察各种可能的混合物类型,更加接近于实际环境体系.      

烃类及其衍生物闪点、沸点的定量构效关系

基于定量结构一性质相关性（QSPR）原理,研究了烃类及其衍生物闪点、沸点与其分子结构间的内在定量关系。应用CODESSA软件计算384种烃类及其衍生物的分子结构描述符,建立了闪点和沸点的QSPR模型。用最佳多元线性回归（B．MLR）方法筛选得到的分子描述符建立了线性回归模型。用B-MLR方法所选择的5个描述符作为支持向量机（SVM）的输入建立了非线性模型。所有的化合物被分为训练集和测试集,对每个模型的训练集和测试集的复相关系数、交互验证系数、均方根误差等进行了计算,并用测试集对模型的预测能力进行检验,预测结果表明：预测值与实验值均符合良好,所建立的闪点模型稳健,泛化能力强,预测误差小,预测的效果令人满意,但沸点的模型预测效果有待加强。相比烃类物质的模型,加了衍生物的模型性能均有所下降。     

Novel synthetic approach to the potent germination stimulant strigol and its analogues

Abstract

Strigol (1) is a natural product that triggers suicidal germination of parasitic Striga species. Here we present an improved annulation sequence for the synthesis of the tricyclic moieties of strigol and its analogues. Our approach makes use of the one‐pot cyclization of 5‐nitro‐2‐pentanone and cyclopent‐2‐enone diesters to afford 7‐methyl‐4‐nitro‐l‐oxo‐hydrindene derivatives. Functional group elaboration of these intermediates leads to a series of hydrindene‐2‐acetic and propionic acids.     

Relative influence of the dissolved humic material on the solid-phase extraction efficiency of pesticides from environmental water

The effect of organic matter on the solid-phase extraction (SPE) efficiency for pesticides belonging to different chemical groups (urea-derivatives, carbamates and triazines) and having different polarities, was simultaneously studied for the first time in pure and simulated water samples. SPE was carried out in precolumns packed with C18 silica or styrene-divinylbenzene copolymer PLRP-S phases on-line coupled to high performance liquid chromatography (HPLC) analysis. Retention factors in water (k'_W) were estimated for 25 compounds and used for the calculation of the theoretical breakthrough volume (Vb_T) in pure water. Experimental breakthrough volumes (Vb_E) were first determined using purified and deionized water as the matrix for selected compounds having Vb_T < 500 mL; then, the same water with an added humic acid sodium salt (HA) at 0.4–5.6 mg/L of dissolved organic carbon (DOC) content, was used as the matrix for compounds having VbE < 500 mL in pure water. Several polar pesticides showed negative linear or logarithmic Vb_E curves depending on HA content; their recoveries were also determined in environmental samples having low dissolved organic carbon values, between 0.5–6.4 mg/L. A similar behavior was observed for these compounds in simulated and natural water samples, where DOC concentration and the percolated volume (Vp) mainly determine the solute recoveries values. However, the variation of recoveries as a function of DOC content could be negative or null depending on the two examined conditions (Vp lower or larger than Vb_E in pure water). Results demonstrated that breakthrough volume must always be considered to correctly interpret the participation of dissolved humic material on the SPE efficiency of organic micropollutants in water.     

Formation of multiple trimethylsilyl derivatives in the derivatization of 17α-ethinylestradiol with BSTFA or MSTFA followed by gas chromatography-mass spectrometry determination

N,O-bis(trimethylsily)trifluoroacetamide (BSTFA) and N-methyl-N(trimethylsily) trifluoroacetamide (MSTFA) are common derivatization reagents used in the GC-MS analysis of estrogen steroids such as estrone (E1) and 17(-ethinylestradiol (EE2). In this study, three trimethylsilyl (TMS) steroid derivatives, mono-and di-trimethylsilyl EE2 and mono-trimethylsilyl E1, were observed during the derivatization of EE2 with BSTFA or MSTFA and/or GC separation. Factors influencing the production of multiple TMS derivatives and their relative abundance were examined. It was found that both methanol and bisphenol A competed with estrogenic esteroids when reacting with silylation reagents, and thus affected the formation of TMS derivatives and their relative abundance in the derivatization products. Methanol was found to be more reactive than bisphenol A with the BSTFA reagent. None of the three solvents tested in this study could prevent the generation of multiple TMS derivatives during the derivatization of EE2 with BSTFA, followed by GC analysis. A similar result was observed using MSTFA as the derivative reagent followed by GC analysis. Thus, the suitability of BSTFA or MSTFA as the derivatization reagent for the determination of E1 and EE2 by GC-MS, under the conditions reported here, is questionable. This problem can be solved by adding trimethylsilylimidaz (TMSI) in the BSTFA reagent as recommended, and the performance of the method has been proved in this study.     

单取代苯衍生物的QSAR研究——分子表面积和活性基团表面积的应用

本文对３０种单取代苯衍生物的结构和毒性关系进行了研究，由于取代基的多样性和性质的各不相同，用量子化学计算所得电子性质参数，拓扑指数和某些经验参数作描述参数，均不能得到好的与毒性的相关性，为此，引入了与取代基相关的取代基活性基团表面积，再加上反映分子总体性质和形状分子表面积及三阶形状指数，所得回归方程较好反映了结构和毒性关系，这也说明了对于单取代苯衍生物，取代基在致毒作用中可能起重要作用。     

酚取代微生物的QSAR研究

计算了带７种不同取代基的２９种酚取代衍生物的分子表面积。用分子表面积,ＯＨ基表面积,代基当量作为描述变量,对上述化合物的ＭｉｃｒｏｔｏｘＲ毒性进行了回归分析,得到有一定意义的回归方程,其相关系数为０．９０。如果氰取代酚作为局外化合物,则相关系数达０．９４。说明这些参数在预言毒性方面有重要意义。     

全氟和多氟烷基化合物微生物降解与转化研究进展

全氟和多氟烷基化合物(PFASs)因其持久性、长距离迁移性、生物积累性和生物毒性而受到广泛关注.目前世界上对环境中PFASs的监测和管控主要针对全氟烷基酸(PFAAs).而大部分多氟烷基化合物在环境中能够被微生物降解为PFAAs,也被称为前体物.因此,探究前体物在环境中的微生物转化行为有助于综合评价PFASs的环境风险,以及制定相关的管控和修复措施.虽然PFAAs一直被认为是环境中的“永久化合物”,但近年来,PFAAs的厌氧微生物还原脱氟作为一项极具潜力且充满挑战的修复技术,成为研究的一个前沿热点.系统总结了前体物(氟调化合物和全氟辛烷磺胺衍生物)、 PFAAs和新型PFASs在微生物作用下的降解规律和转化路径,并讨论了PFASs微生物降解的影响因素,最后提出未来的研究方向.     

Pb（II） biosorption using chitosan and chitosan derivatives beads： Equilibrium, ion exchange and mechanism studies

The study examined the adsorption of Pb(II) ions from aqueous solution onto chitosan, chitosan-GLA and chitosan-alginate beads. Several important parameters influencing the adsorption of Pb(II) ions such as initial pH, adsorbent dosage and di erent initial concentration of Pb(II) ions were evaluated. The mechanism involved during the adsorption process was explored based on ion exchange study and using spectroscopic techniques. The adsorption capacities obtained based on non–linear Langmuir isotherm for chitosan, chitosan-GLA and chitosan-alginate beads in single metal system were 34.98, 14.24 and 60.27 mg/g, respectively. However, the adsorption capacity of Pb(II) ions were reduced in the binary metal system due to the competitive adsorption between Pb(II) and Cu(II) ions. Based on the ion exchange study, the release of Ca2+, Mg2+, K+ and Na+ ions played an important role in the adsorption of Pb(II) ions by all three adsorbents but only at lower concentrations of Pb(II) ions. Infrared spectra showed that the binding between Pb(II) ions and the adsorbents involved mostly the nitrogen and oxygen atoms. All three adsorbents showed satisfactory adsorption capacities and can be considered as an e cient adsorbent for the removal of Pb(II) ions from aqueous solutions.     

紫外分光光法测定苯胺类化合物的注意事项及解决方法

对国标法(GB 11889-89)中的N-(1-萘基)乙二胺偶氮分光光度法测定水中苯胺类化合物进行了深入研究,同时指出了苯胺类化合物测定全过程中应注意的问题及解决方法。应用改进过的方法测定水中苯胺类化合物,方法快速、准确、简便,检出限为0.03 mg/L。应用该方法分别对金华市地表水及工业废水中的苯胺类化合物进行检测,加标回收率为93.1%~104%。