双酚A类似物雌激素干扰效应的定量结构-活性关系模型

由于双酚A(BPA)具有内分泌干扰等毒性效应,有些国家已经开始限制其在部分工业品生产中使用。一些双酚A类似物因用于替代BPA而被大量使用。因其与双酚A具有相似的分子结构,双酚A类似物是否也具有内分泌干扰等毒性效应受到越来越多的关注。采用逐步多元线性回归(MLR)方法,构建了可预测双酚A类似物雌激素效应的定量结构-活性关系模型。模型的决定系数R~2=0.899,去一法交叉验证系数Q_(LOO)~2=0.868,Bootstrapping验证系数Q_(BOOT)~2=0.755,均方根误差RMSE=0.339,表明模型具有较好的拟合优度、稳健性;验证集决定系数Q_(EXT)~2=0.921,外部验证系数Q_(EXT)~2=0.810,均方根误差RMSE=0.638,表明模型具有较好的预测能力。采用欧几里德距离方法和Wil iams图表征了模型应用域,依据分子描述符对模型进行了机理解释,并用所建模型,填补了22种其他双酚A类似物缺失的雌激素干扰效应数据。     

In vitro toxic effects of heavy metals on fungal growth and phosphate-solubilising abilities of isolates obtained from Phragmites australis rhizosphere

In this research, we evaluated the toxic effect of metal ions on mycelial growth and phosphate-solubilising activity of soil-borne micromycetes isolated from the Phragmites australis rhizosphere using Pikovskaya-agar plates supplemented with four metal concentrations. The diameter growth rate (DGR) decreased as the metal concentration rise for all tested fungi. Trichoderma atroviride had the fastest growth rate (1.48?cm²?day^?1) and was the least susceptible to Al³⁺, Cd²⁺, Cr³⁺, Cu²⁺ and Pb²⁺ with a median effective concentration (MEC₅₀) of 12.19, 0.48, 4.51, 11.44 and 50.05?mM, respectively. Aspergillus japonicus was the most tolerant to Co²⁺, Ni²⁺ and Zn²⁺, with MEC₅₀ values of 3.36, 1.095 and 2.34?mM, respectively. Penicillium italicum was the most tolerant to Cr6⁺ (MEC₅₀?=?0.677?mM). The ability to solubilise phosphate remained, despite the decrease in the DGR, and P. italicum and Penicillium dipodomyicola had the highest Phosphate Solubilisation Indexes (PSIs) at 1.97 and 2.12, respectively. In particular, P. italicum recorded the highest PSI of all the studied isolates at 0.62?mM Cr³⁺ (PSI?=?4.74). A. japonicus and T. atroviride were the most tolerant isolates to all tested metals, which suggests that these isolates are promising candidates for further study with regard to mycoremediation and biofertilisation of metal-polluted soils.     

有机污染物的被动采样材料-水分配系数的QSAR研究

污染物的被动采样材料-水分配系数(K_(PW))是衡量被动采样器性能和进行优化的一个重要指标,由于实验方法难以逐个测定众多污染物的K_(PW)值,有必要发展其KP W预测方法。本研究选取聚乙烯(PE)、聚丙烯酸酯(PA)和硅橡胶(SR)3类常用的被动采样材料共7种,采用多元线性回归分析方法构建可用于K_(PW)预测的定量构效关系(QSAR)模型。所构建的QSAR模型具有良好的拟合优度(R2a dj介于0.806~0.989)、稳健性(Q2L O O和Q2B O O T分别介于0.786~0.988和0.773~0.801)和预测能力(R_(ext)~2和Q_(ext)~2分别介于0.769~0.989和0.757~0.982),可以用于预测烷烃、烯烃、芳香类、醇类、酮类、酯类、醚类等多种有机污染物的log KP W值。有机污染物的log KP W与分子Mc Gowan体积(Vx)、氯原子个数(n Cl)、环周长(Rperim)、多重键个数(n BM)、N,O极性贡献的拓扑极性表面积(TPSA(NO))、[-N(=)=]结构个数(Ndds N)和羟基个数(nROH)等参数有关。     

乙腈溶剂中单壁碳纳米管与常见有机化合物的相互作用

以单壁碳纳米管(SWCNTs)为固定相,采用高压匀浆法,制备HPLC色谱柱.测定乙腈相中18种有机化合物在SWCNTs色谱柱上的保留因子,研究SWCNTs与化合物的相互作用.结果表明,有机化合物取代基的种类和个数、杂原子的个数影响乙腈相中有机化合物与SWCNTs的相互作用.采用线性溶解能关系(LSER)定量表征SWCNTs与有机化合物的相互作用,所构建的LSER模型具有较强的拟合能力(R2=0.844)和稳健性(Q2LOO=0.768),发现π-/n-电子对作用和空穴/弥散作用是控制SWCNTs与有机化合物相互作用的主要因素.     

Adsorptive removal of direct dyes by PEI-treated peanut husk biomass: Box–Behnken experimental design

This paper reports the application of Box-Behnken experimental design to illustrate the adsorption of direct dyes (Indosol Black NF and Indosol Orange RSN) using polyethyleneimine (PEI)-treated peanut husk biomass. The effect of three independent variables (initial dyes concentration, biosorbent dose and pH) was investigated during the study. Maximum biosorption capacity (141 and 98.2 mg/g) of PEI-pretreated biomass was achieved with 200 mg/L initial dye concentration and 0.05 g/50 mL biomass dose for Indosol Black NF and Indosol Orange RSN, respectively. Acidic pH was found to be favourable for maximum dyes removal. Characterisation of biosorbent was carried out through Fourier transform-infrared spectroscopy (FT-IR), scanning electron microscopy, thermogravimetric analysis (TGA) and point of zero charge determination. FT-IR analyses confirmed the involvement of carboxylic and carbonyl groups. The desorption study was also conducted to check out the possibility of regeneration of dyes and adsorbent and it was found that 51.58 and 76.6% of Indosol Black NF and Indosol Orange RSN, respectively, can be desorbed from the loaded biosorbent by using 1 M NaOH solution. The results indicated that PEI-treated peanut husk biomass can be used as an efficient biosorbent for the removal of Indosol Black NF and Indosol Orange RSN dyes from aqueous solutions.     

Evaluation of the performance of rural wastewater treatment plants using chemical measurements in combination with statistical techniques: a case study

The performance of a wastewater treatment plant was assessed statistically using multivariate cluster and principle component analysis. This was after measuring some physico-chemical properties in the influent, effluent, downstream, and upstream waters over a 4-month period. The cluster analysis grouped the sampling sites into three clusters: relatively non-polluted (upstream), medium polluted (downstream), and polluted (influent and effluent). The polluted water was further subdivided into very highly (influent) and highly (effluent) polluted. The grouping of influent and effluent into one cluster was due to some water quality parameters such as amount of copper, lead, and phosphates that are not efficiently removed by the plant. Using principal component analysis, samples from the same site taken over a period of 4 months were scattered, indicating inconsistencies in the performance of the plant. This was more pronounced during the rainy season, suggesting that increased water volumes from open sewers make the already poorly performing plant worse. The major loading factors found by principle component analysis were phosphate, lead, iron, zinc, copper, pH, and conductivity. Generally, the wastewater treatment system was found to be efficient in removing heavy metals and these were found in the sludge, but not anions. The mean percentage metal removal could be arranged in the following decreasing order: iron (85%)?>?zinc (57%)?>?copper (40%) and lead (38%) following the concentrations (mg?kg^?1) found in the sludge: iron (11,300)?>?zinc (820)?>?copper (180)?>?lead (20)?>?cadmium (3). Phosphate and iron concentrations in the effluent were found to be above the South African Bureau of Standards (SABS) recommendations. The major cause of poor performance is the high volume of the wastewater, exceeding the capacity of the plant 10 times.     

Dispersive liquid–liquid microextraction of cadmium(II) for preconcentration prior to flame atomic absorption spectrometric detection in water

A dispersive liquid–liquid microextraction procedure for cadmium(II) as its 2-(5-bromo-2-pyridylazo)-5-diethylamino-phenol chelate is presented. Carbon tetrachloride and methanol were used as extraction and dispersive solvents, respectively. After phase separation, the preconcentrated-separated cadmium(II) is determined by flame atomic absorption spectrometry with a microinjection technique. The factors which affected the extraction efficiency, i.e. the pH of the sample solution and the volumes of reagent and sample were investigated. The effects of some alkali, alkali earth, and transition metal ions, and of some anions on the recovery of cadmium were also studied. A preconcentration factor of 250 was obtained for a sample volume of 50?mL under optimum conditions. The method was validated by analysis of certified reference materials and applied to some water samples from Turkey.     

Cobalt speciation assay for human serum,Part II. Method validation in a study of human volunteers ingesting cobalt(II) chloride dietary supplement for 90 days

A new analytical method for determining cobalt (Co) species in human serum by size exclusion chromatography with inductively coupled plasma mass spectrometry (SEC-ICP-MS) was applied to serum samples collected from 12 human volunteers who participated in a Co(II) chloride supplement study involving ingestion of 1 mg Co/day for up to 90 consecutive days. The study protocol included determination of serum total Co by acid digestion followed by ICP-MS. Co speciation assay measurements were conducted for up to 13 time points per individual spanning from one to two weeks before dosing began to two weeks after dosing ceased. The Co speciation assay showed good recovery >91% relative to total Co measurements. Undiluted serum demonstrated uniform fractions of large molecular Co defined as Co bound to albumin and other proteins >50 kDa at 96% and the residual as small molecular Co defined as free Co(II) and <1 kDa Co-complexes for individual serum Co concentrations up to 146 μg/L. There were no dose-related changes in Co distribution. Analysis of the same serum samples with tenfold dilution in 0.1 M acetic acid led to a lower fraction of large molecular Co at 87%, with the difference between diluted and undiluted measurements being 8.4%. The difference noted between undiluted and diluted large molecular Co may be attributed to Co release from albumin. Data demonstrated that large molecular Co was the predominant Co species in both undiluted and diluted human serum over a broad range of in vivo Co concentrations, reflecting high albumin–Co binding capacity. These data validate the Co speciation assay and may be employed in understanding further the toxicokinetics and dose-response relationships for Co species.     

Solid phase extraction of trace metals from environmental samples using Amberlite XAD-7 loaded with 2-hydroxy-propiophenone-4-phenyl-3-thiosemicarbazone and determination by inductively coupled plasma–atomic emission spectrometry

A method for the solid phase extraction of trace metals, namely Co, Cu, Pb, Ni and Zn, from environmental and biological samples using column Amberlite XAD-7 loaded with 2-hydroxy-propiophenone-4-phenyl-3-thiosemicarbazone (HPPPTSC) and determination by inductively coupled spectrometry (ICP–AES) has been developed. The reagent has the capacity to form chelate complexes with the metals because of three binding sites in the reagent molecule. The optimum experimental conditions for the quantitative sorption of five metals, pH, effect of flow rate, concentration of eluent, sorption capacity and the effect of diverse ions on the preconcentration of analytes have been investigated. The sorption capacity of the resin has 83, 127, 35, 88 and 85?µmol?g^?1 for Co²⁺, Cu²⁺, Pb²⁺, Ni²⁺ and Zn²⁺, respectively. The preconcentration factors for Co²⁺, Cu²⁺, Pb²⁺, Ni²⁺ and Zn²⁺ were 100, 110, 120, 140 and 150, respectively. The accuracy of the proposed procedure was evaluated by standard reference materials. The achieved results were in good agreement with certified values. The proposed method was applied for the determination of trace metals in river water and plant leaves.     

三峡库区城市化与生态环境耦合关系定量辨识

受人文社会规律支配的城市化过程与受自然规律制约的生态环境演化过程之间,通过种种复杂的胁迫与约束机制,具有双指数倒U型曲线的耦合演化规律性。如果以区域内不同城镇构成的空间样本来测算城市化与生态环境之间的耦合关系,其耦合曲线通常有以下5种型式：下降、正U、上升、倒U和再下降。该演化序列符合否定之否定的发展规律。通过相关分析、主成分分析和层次分析等方法,对三峡库区15个区县的城市化水平和生态环境状况作了综合评价,并在综合和分组两个层面对二者耦合关系进行了定量辨识。结果表明：通过空间样本反映的重庆库区城市化与生态环境耦合关系曲线为正U型,揭示出库区城市化与生态环境耦合演化的二元性;城市化与生态环境沿长江自西向东具有基本一致的变化趋势,说明现阶段库区城市化对生态环境的依赖性大于其破坏性。