Determination of endocrine disrupting compounds using temperature-dependent inclusion chromatography: I. Optimization of separation protocol

In the present work we optimised the separation of battery of key UV non-transparent low-molecular-mass compounds having possible endocrine disrupting compounds (EDCs) activity or which may be used as the endocrine effect biomarkers. Simple optimization strategy was based on strong temperature effect that is driven by electrostatic interactions between macrocyclic mobile phase additives like cyclodextrins and eluted components of interest under C18 stationary phase and acetonitrile/water mobile phase conditions. Particularly, the effect of temperature involving native β-cyclodextrin and its hydroxypropyl derivative to improve separation of number of natural (d-equilenin, equilin, estetrol, estriol, estrone, 17β-estradiol, 17α-hydroxyprogesterone, 20α-hydroxyprogesterone, cortisol, cortisone, progesterone, testosterone, tetrahydrocortisol and tetrahydrocortisone) and artificial steroids (ethynylestradiol, norgestrel isomers, medroxyprogesterone, mestranol, methyltestosterone, norethindrone, 17α-estradiol) as well as non-steroidal compounds (diethylstilbesterol, bisphenol A, 4-tert-butylphenol, dimethyl phthalate, dibutyl phthalate and dioctyl phthalate) was investigated. It has been found that successful isocratic separation of 27 chemicals can be achieved using acetonitrile/water eluents modified with β-cyclodextrin or hydroxypropyl-β-cyclodextrin at concentration of 10 mM and temperature of 47 °C. Separation protocol is simple, reliable, direct and non-radioactive and may be easily adapted for rapid separation and quantification of wide range of given steroids and related EDCs in environmental samples, particularly those that are characterised by unstable biological matrix and components of interest load.     

The analysis of a group of acidic pharmaceuticals, carbamazepine, and potential endocrine disrupting compounds in wastewater irrigated soils by gas chromatography-mass spectrometry

The analysis of pharmaceuticals and potential endocrine disruptors in the environment has rightly concentrated on their presence in wastewaters and possible contamination of receiving bodies, such as groundwaters. However, wastewater is increasingly being reused for irrigation and in order to fully understand the environmental fate of these compounds, reliable methods for their analysis in soil are required, of which there are relatively few available. This article reports a method for a range of acidic pharmaceuticals, carbamazepine, and endocrine disrupting compounds in soils with final analysis by gas chromatography-mass spectrometry. Two soil types (Phaeozom and Leptosol) and three fortification levels were used to validate the method. Recoveries of acidic pharmaceuticals varied between 62 and 102%, carbamazepine from 75 to 118%, and potential endocrine disruptors between 54 and 109%; most recoveries were between 75 and 95% and relative standard deviations were generally less than 10%. Detection limits were between 0.25 and 2.5 ng/g except for phthalates and 4-nonylphenols (25 ng/g). The method was used to analyze soils where untreated wastewaters have been used to irrigate crops for approximately 90 years. Concentrations of acidic pharmaceuticals in the soil were <1 ng/g and potential endocrine disruptors varied from below the limit of detection (estrone, 17β-estradiol, and 17α-ethinylestradiol) to 2079 ng/L (bis-diethylhexyl phthalate). This data indicated that despite the continuous application of the contaminants over many years, concentrations were generally lower than those expected to be contributed by a single irrigation event. Only carbamazepine, at concentrations of 6.48 ng/g (in Phaeozem) and 5.14 ng/g (in Leptosol), showed any evidence of persistence in the soils analyzed.     

双渠道销售差别定价闭环供应链协调应对生产成本扰动研究

针对一个新产品和再造品存在差别定价,且两类产品通过不同销售渠道进行销售的闭环供应链,构建了一个基本的两部收费契约协调模型。随后,考虑突发事件同时干扰新产品和再造品生产成本的情况下,集中式决策闭环供应链的最优决策问题,并设计了可协调成本扰动下双渠道销售差别定价闭环供应链的两部收费契约。研究表明:在集中式决策闭环供应链中,相比于稳定环境下新产品和再造品的最优决策,生产成本扰动下两类产品最优产量的调整方式不仅与生产成本扰动的程度相关,还与两类产品之间的相互替代系数相关,且改进的两部收费契约以系统各成员共担风险的方式实现了闭环供应链协调的目的。     

多因素扰动下同价双渠道供应链协调应对突发事件

一条双渠道供应链存在一个传统零售商和一个拥有电子渠道的制造商,制造商采用了跟随零售商线上线下同价的定价策略。通过建立市场需求模型,求出供应链的最优价格、生产数量,利用博弈论和合同理论的原理设计收益共享契约。研究表明,当供应链处于稳定状态时,收益共享契约可以用来实现同价双渠道供应链的协调。当突发事件导致市场规模和制造成本发生扰动时,同价双渠道供应链存在鲁棒性,而收益共享契约也能够很好地协调同价机制下的双渠道分权供应链,最后给出一个算例验证了结论。     

内分泌干扰物三苯基锡的激光拉曼光谱分析

三苯基锡(TPhT)是目前已知的内分泌干扰物中唯一的两种金属化合物之一,被广泛应用于工业、农业和交通领域,其大量使用会对土壤、海洋和内陆淡水环境造成不同程度的影响。本实验采用激光共聚焦拉曼光谱采集固体TPhT的拉曼光谱信号,尝试将该方法用于TPhT检测,探索该方法的可行性,并进行检测参数的优化选择。将拉曼光谱分析检测方法与TPhT的物性研究相结合,根据TPhT分子中不同官能团振动模式的不同,将拉曼谱图分为高、中、低3个波数区(1 500～3 200,900～1 500和100～900 cm-1)进行拉曼谱峰的归属与分析,得到了TPhT的特征振动模式和拉曼特征峰,并建立一套TPhT的标准拉曼图谱库,光谱范围在100～3 200 cm-1之间。结果表明,当激光功率选择为衰减到原激光功率(500 mW)的0.5%、曝光10 s、累积2次时,得到的拉曼谱图信噪比高且检测时间短。在212,332,657,997和1 577 cm-1处出现的信号强度较高的拉曼峰,可作为固体TPhT拉曼检测的特征峰,657和997 cm-1处拉曼特征峰的同时出现即可认为复杂的环境样品中存在TPhT。实验结果给出了辨别TPhT存在的标志,这些结果将为拉曼光谱用于实际环境样品中TPhT的残留检测提供理论依据和数据基础。     

供应链网络竞争背景下的重组应对需求干扰

本文以生产并销售同质产品,且以制造企业为核心的供应链网络为研究对象,在供应链网络与供应链网络竞争的经济背景下,利用变分不等式理论和纳什非合作博弈理论,建立了需求干扰前和需求干扰后两个阶段下的供应链网络均衡模型,并利用所建模型比较了不同重组方式应对需求干扰的有效性。     

等离子体破裂时HL-2M真空室的结构应力分析

利用ANSYS有限元程序分析计算了等离子体线性大破裂时HL-2M真空室上的感应电流及电磁力,并对真空室进行了结构应力分析。结果表明,真空室上主要产生环向感应电流和径向电磁力,且主要集中在真空室壳体的柱状段;在破裂产生的电磁力及其他机械载荷的作用下,真空室的结构设计能较好地满足强度和刚度要求。     

不同区间下电流猝灭特性在等离子体破裂期间的对比研究

托卡马克装置上电磁负载大小值与破裂期间电流猝灭特征有密切的关系.电流猝灭特征包括电流猝灭波形以及电流猝灭率等,它将在一定程度上决定装置的寿命.本文选取100%-40%, 90%-10%, 80%-20%三个区间分析了HL-2A装置上等离子体破裂现象,得到三个不同区间下电流猝灭参数范围.对比分析结果表明：在相同定义下,利用100%-40%和80%-20%区间得到的平均电流猝灭时间以及电流猝灭率分布差异最小.除了80%-20%区间外,100%-40%区间也可作为提供最大线性平均等离子体电流猝灭速率近似的适合区间.     

Size-Dependent Impact of Magnetic Nanoparticles on Growth and Sporulation of Aspergillus niger

Magnetic nanoparticles (MNPs) are becoming important DNA nanocarriers for genetic engineering of industrial fungi. However, the biological effect of MNPs on industrial fungi remains unknown. In this study, we prepared three kinds of magnetic nanoparticles with different sizes (i.e., 10 nm, 20 nm, and 200 nm) to investigate their impact on the growth and sporulation of the important industrial fungus Aspergillus niger. Transmission electron microscopy, X-ray diffraction analysis and Zeta potential analysis revealed that the three kinds of MNPs, including MNP10, MNP20 and MNP200, had uniform size distribution, regular Fe₃O₄ X-ray diffraction (XRD) patterns and similar Zeta potentials. Interestingly, although the three kinds of MNPs did not obviously inhibit growth of the fungus, the MNP20 at 500 mg/L strongly attenuated sporulation, leading to a remarkable decrease in spore numbers on culturing plates. Further investigation showed that MNP20 at the high concentration led to drastic chitin accumulation in the cell wall, indicating cell wall disruption of the MNP20-treated fungal cells. Moreover, the MNPs did not cause unusual iron dissolution and reactive oxygen species (ROS) accumulation, and the addition of ferrous ion, ferric ion or the reactive oxygen species scavenger N-acetyl-L-cysteine (NAC) had no impact on the sporulation of the fungus, suggesting that both iron dissolution and ROS accumulation did not contribute to attenuated sporulation by MNP20. This study revealed the size-dependent effect of MNPs on fungal sporulation, which was associated with MNP-induced cell wall disruption.     

Use of reporter cell lines for detection of endocrine-disrupter activity

We have studied stable transformed human mammary cell lines with highly inducible steroid receptor-mediated luciferase reporter gene expression. Cells responding specifically to glucocorticoids, progestagens, androgens, or estrogens are described and characterized. The use of this high-throughput, cell-based assay for analysis of steroid (ant)agonists is reported. Systematic characterization of endocrine-disrupting activity on human receptors and in a human-cell system is interpreted for a selection of xenobiotics. We show that the phytoestrogens apigenin and genistin have progestagenic and androgenic activity, respectively. Finally, application of cell-based assays to the analysis of environmental samples is discussed.