Automated derivatization for on-line solid-phase extraction-gas chromatography; phenolic compounds

An automated system for derivaatization was coupled on-line with solid-phase extraction-gas-chromatography (SPE-GC). The system was optimized for the determination of phenol and chlorinated phenols in aqueous samples. The test analytes were acetylated with acetic anhydride; proper buffering of the sample was a critical factor. Next, the phenol acetates were enriched on a SPE cartridge and transferred to a GC; two appraoaches were studied. In the first approach, the derivatives were enriched on disposable C18 cartridges (ASPEC type) and desorbed with methylacetate. Aan aliquot of the final eluate was injected on-line the GC by means of a loop-type interface. In the second approach, trace enrichment was performed on 10 × 2 mm i.d. LC-type precolumn packed with polystyrenedivinylbenzene copolymer (PLRP-S) this precolumn was dried with a mitrogen purge and the phenol acetates were desorbed with ethyl acetate which was injectedon-line into the retention gap of the GC under partially concurrent solvent evaporation (PCSE) conditions. The Derivatization-SPE-GC system which was based on the loop-type interface has the advantage of simplicity and easy operation, the main drawback is the impossibility to determine phenol acetates which elute prior to trichlorophenol acetates. With the derivatization-SPE-GC approach using PCSE-based desorption, even the most volatile analyte of the test series, phenol acetate, can be determined successfully. The entire procedure, including the derivatization step, was fully automated and integrated in one set-up. The precision data for the integrated on-line derivatization-SP-FID system were fully satisfactory, with RSD values of 1–12 % at the 1 μg/1 level. When a sample volume of 2.2 ml was analyzed, The detection limits for the chlorinated phenol acetates were in the 0.1–0.3 μg/1 range.     

Thermodynamic and surface properties of Sb-Sn and In-Sn liquid alloys

The thermodynamic properties of Sb-Sn and In-Sn liquid alloys have been studied using the quasi-chemical model for compound forming binary alloys and that for simple regular alloys. The concentration fluctuation S _cc(0) and the Warren-Cowley short-range order parameter (α ₁) were determined for the whole concentration range at a temperature of 770 K. The surface tensions of these liquid alloys were determined for the whole concentration range by using energetics determined from thermodynamic calculations. In all calculations, In-Sn manifested properties very close to alloys of ideal mixing, while Sb-Sn showed properties that are asymmetric about equiatomic composition. Our results suggest that a weak complex of the form SbSn₂ could be present in the Sb-Sn alloy at a temperature of about 770 K.     

基于界面跟踪方法的汽蚀模型和算法的有效性验证

针对两相附着汽蚀流动机理,基于界面跟踪方法发展了新的汽蚀模型和算法。所发展的汽蚀模型和算法不仅考虑了液相／气相界面处的压力差,而且考虑了耦合Reynolds-Averaged Navier-Stokes方程求解技术得到的流场压力梯度信息来迭代计算附着汽蚀形状。采用具有试验数据的半球形头部圆柱体汽蚀绕流作为算例来验证所提出的汽蚀模型和算法的有效性。采用不同的网格数和松弛因子数值验证了发展的汽蚀模型和算法的有效性。三种汽蚀数下的数值计算结果得到的压力系数分布与试验数据完全吻合。结果表明所提出的汽蚀模型和算法能够准确模拟出汽蚀发生点和汽蚀长度。     

Metal components analysis of metallothionein-III in the brain sections of metallothionein-I and metallothionein-II null mice exposed to mercury vapor with HPLC/ICP-MS

Mercury vapor is effectively absorbed via inhalation and easily passes through the blood–brain barrier; therefore, mercury poisoning with primarily central nervous system symptoms occurs. Metallothionein (MT) is a cysteine-rich metal-binding protein and plays a protective role in heavy-metal poisoning and it is associated with the metabolism of trace elements. Two MT isoforms, MT-I and MT-II, are expressed coordinately in all mammalian tissues, whereas MT-III is a brain-specific member of the MT family. MT-III binds zinc and copper physiologically and is seemed to have important neurophysiological and neuromodulatory functions. The MT functions and metal components of MTs in the brain after mercury vapor exposure are of much interest; however, until now they have not been fully examined. In this study, the influences of the lack of MT-I and MT-II on mercury accumulation in the brain and the changes of zinc and copper concentrations and metal components of MTs were examined after mercury vapor exposure by using MT-I, II null mice and 129/Sv (wild-type) mice as experimental animals. MT-I, II null mice and wild-type mice were exposed to mercury vapor or an air stream for 2 h and were killed 24 h later. The brain was dissected into the cerebral cortex, the cerebellum, and the hippocampus. The concentrations of mercury in each brain section were determined by cold vapor atomic absorption spectrometry. The concentrations of mercury, copper, and zinc in each brain section were determined by inductively coupled plasma mass spectrometry (ICP-MS). The mercury accumulated in brains after mercury vapor exposure for MT-I, II null mice and wild-type mice. The mercury levels of MT-I, II null mice in each brain section were significantly higher than those of wild-type mice after mercury vapor exposure. A significant change of zinc concentrations with the following mercury vapor exposure for MT-I, II null mice was observed only in the cerebellum analyzed by two-way analysis of variance. As for zinc, the copper concentrations only changed significantly in the cerebellum. Metal components of metal-binding proteins of soluble fractions in the brain sections were analyzed by size-exclusion high-performance liquid chromatography (HPLC) connected with ICP-MS. From the results of HPLC/ICP-MS analyses, it was concluded that the mercury components of MT-III and high molecular weight metal-binding proteins in the cerebellum of MT-I, II null mice were much higher than those of wild-type mice. It was suggested that MT-III is associated with the storage of mercury in conditions lacking MT-I, and MT-II. It was also suggested that the physiological role of MT-III and some kind of high molecular weight proteins might be impaired by exposure to mercury vapor and lack of MT-I and MT-II.     

Determination of anions in rainwater by capillary electrophoresis with conductivity detection

A routine method for the determination of chloride, nitrate and sulfate anions in rainwater by capillary electrophoresis was developed. The system uses an end-column non-suppressed conductivity detector. Linear calibration plots were generated from 0.050 to 20 mg/l, which is the range generally found in wet depositions. Accuracy and precision were evaluated by analyzing certified standards of simulated rainwater and environmental samples, or by comparing CE results with those obtained by IC, the reference technique for anion analysis in wet deposition. The reproducibility of the method was satisfactory except at the lower and upper limits of the analytical range. Sensitivity lay in the range of few μg/l.     

一种自制的蒸馏水器保护装置

本装置由检测、控制、执行、报警和电源五部分组成。检测部分采用了靠正常水位导通的两根信号线。当蒸馏水器在正常运行时遇停水,本装置可立即实现断电保护,同时发出声光报警,有效防止干烧,杜绝事故发生。本装置制作简便,元器件均为市售,成本低廉,性能可靠。     

Water bridges are essential to neonicotinoids: Insights from synthesis,bioassay and molecular modelling studies

To identify the detailed roles of water bridges in neonicotinoids recognition, twenty-four neonicotinoids compounds were designed, synthesized, bioassayed and modelled. Of all nine fragments mimicking water bridges, cyano group was the optimal one. The insecticidal activities indicated that the water bridge might be stable in the active site and was not suitable to be replaced by other groups, which highlighted the significance of water bridges for neonicotinoids.     

简便快速的硫化氢测定法

本文提出了有一种简易快速测定剂来测定水样中的硫化氢的方法。该法的检出限为０．１ｍｇ／Ｌ，对１．０１ｍｇ／Ｌ的Ｈ２Ｓ样品７次测定的相对标准偏差＜４．１％，１ｈ能测定１２个样品。用本测定了几种水样中的Ｈ２Ｓ含量，回收率为８４％－１０５％。应用它可上标准法的４ｈ左右缩短到５ｍｉｎ；使分析成本降低９／１０；不需配制一系列分析试剂和仪器，只需一支小型塑料管和几片药片，便于渔业水质和环境水质的野外现场监测。     

磁性微珠的制备及其在生物样品分离富集中的应用

磁性微珠作为一种新型的功能材料,广泛应用于磁性材料、生物医学、细胞学、生物工程及分离工程等诸多领域,并显示出强大的生命力。本文对磁性微珠的结构、性质、制备方法及其在生物样品的分离富集等方面的应用,进行了总结和评述,引用文献62篇。