Photopolyaddition of dithiols to bis(alkoxyallene)s

Polyadditions of 1,4-benzenedithiol (BDT) to bis(alkoxyallene)s, such as 1,4-bis(allenyloxy)xylene (3) and 1,4-bis(allenyloxy) benzene (4) , were carried out in benzene at 25°C by irradiation with a high pressure mercury lamp. Thiol groups were added to the terminal double bonds of the allenyloxy groups selectively to afford polymers containing reactive carbon–carbon double bonds in the main chain, similar to the radical polyadditions using azobis(isobutyronitrile) (AIBN). The molecular weight of the polymer obtained from BDT and 3 was 10 times higher than that of the polymer produced in the radical polyaddition with AIBN; whereas the molecular weight of the polymer from BDT and 4 was similar to that in the radical polyaddition, probably because of poor solubility of 4 and the polymer toward benzene. The geometrical structure of carbon–carbon double bonds in the polymer isomerized from an E to Z structure with reaction time by virtue of both the addition elimination of thiyl radical to the double bonds and the UV irradiation. © 1996 John Wiley & Sons, Inc.     

微波消解-氢化物发生原子荧光法测定塑料原料及其制品中的砷、汞

采用微波消解进行样品前处理，以硫脲为预还原剂，用氢化物发生原子荧光法测定塑料原料及其制品中的砷、汞。测定砷和汞的线性范围均为0～8μg／L，砷、汞的检出限分别为0．005、0．076μg／L，测定结果的相对标准偏差分别为4.96％～7．38％、2．94％～7．20％(n=6)，回收率分别为92．0％～103．2％、92．0％～98.0％。     

铅、汞、镉离子的荧光传感器研究进展

化学传感器提供了方便、快捷、廉价的分析检测有毒重金属离子的方法,并具有很高的灵敏度和选择性.它在环境科学、分析化学以及生命科学等领域有广泛的应用前景.本文分别综述了pb²⁺、Hg²⁺、Cd²⁺几种有毒重离子化学传感器的最新研究进展,并展望了该领域的发展趋势.     

The application of (199)Hg NMR and (199m)Hg perturbed angular correlation (PAC) spectroscopy to define the biological chemistry of Hg(II): a case study with designed two- and three-stranded coiled coils

The use of de novo designed peptides is a powerful strategy to elucidate Hg(II)-protein interactions and to gain insight into the chemistry of Hg(II) in biological systems. Cysteine derivatives of the designed alpha-helical peptides of the TRI family [Ac-G-(L(a)K(b)A(c)L(d)E(e)E(f)K(g))(4)-G-NH(2)] bind Hg(II) at high pH values and at peptide/Hg(II) ratios of 3:1 with an unusual trigonal thiolate coordination mode. The resulting Hg(II) complexes are good water-soluble models for Hg(II) binding to the protein MerR. We have carried out a parallel study using (199)Hg NMR and (199m)Hg perturbed angular correlation (PAC) spectroscopy to characterize the distinct species that are generated under different pH conditions and peptide TRI L9C/Hg(II) ratios. These studies prove for the first time the formation of [Hg{(TRI L9C)(2)-(TRI L9C-H)}], a dithiolate-Hg(II) complex in the hydrophobic interior of the three-stranded coiled coil (TRI L9C)(3). (199)Hg NMR and (199m)Hg PAC data demonstrate that this dithiolate-Hg(II) complex is different from the dithiolate [Hg(TRI L9C)(2)], and that the presence of third alpha-helix, containing a protonated cysteine, breaks the symmetry of the coordination environment present in the complex [Hg(TRI L9C)(2)]. As the pH is raised, the deprotonation of this third cysteine generates the trigonal thiolate-Hg(II) complex Hg(TRI L9C)(3)(-) on a timescale that is slower than the NMR timescale (0.01-10 ms). The formation of the species [Hg{(TRI L9C)(2)(TRI L9C-H)}] is the result of a compromise between the high affinity of Hg(II) to form dithiolate complexes and the preference of the peptide to form a three-stranded coiled coil.     

基于双氨基三唑硫醚为中性载体的汞离子选择性电极的研究

研制了基于双氨基三唑硫醚为中性载体的阳离子选择性电极。实验表明,该电极对Hg2 具有良好的电位响应特性,在pH 2.0硝酸盐缓冲液中,电极电位呈近能斯特响应,线性响应范围为4.0 mg/L~20 g/L,斜率为33.4 mV/dec.(25℃),检出限为1.7 mg/L。该电极响应时间短(<10 s),pH范围较宽(1.3~3.3)。将该电极用于实际水样和二元混合溶液中Hg2 的检测,其结果令人满意。     

球形汞膜电极倒导数恒电流溶出分析法研究

本文推导并验证了球形汞膜电极倒导数恒电流溶出分析法理论。确定其理论的应用条件为汞膜厚度不超过4.6×10~(-4)cm,探讨了噪音对灵敏度的影响。     

Flotation-spectrophotometric method for the determination of mercury using iodide and brilliant green

This paper describes a sensitive spectrophotometric method for the determination of mercury, based on the flotation of a mercury iodide-brilliant green complex with cyclohexane at pH 5 and dissolution of the complex in acetone. The absorbance of the complex is measured at 625 nm. Beer's law is obeyed from 4–500 g/l of mercury. The method is highly sensitive ( = 5.96 × 10⁵ 1 mol^–1 cm^–1) and selective, as it is free from interferences by almost all cations and anions in the presence of EDTA. Furthermore, a two-level orthogonal array design as a chemometric method has been used for optimization of the various parameters involved. The method has been successfully applied to paper industry effluents.     

抗坏血酸对等离子体质谱法测定汞的增敏作用研究

研究了将抗坏血酸加入到样品中作为增敏剂,以电感耦合等离子体质谱测定汞的增敏效应。考察了硝酸浓度、抗坏血酸浓度、水浴温度和时间等实验条件对增敏作用的影响。结果表明,在5%硝酸,500 mg·L~(-1)的抗坏血酸,水浴温度50℃,时间为20 min的条件下,汞的灵敏度最高,此时,汞的灵敏度增强近30倍,其检出限低至1 ng·L~(-1)。在汞浓度为0.005~10.0μg·L~(-1)范围内线性关系良好,相关系数为0.999,相对标准偏差为5.6%(0.1μg·L~(-1),n=7)。该文还进一步探讨了抗坏血酸产生增敏作用的机理。     

Elemental Analysis of Stone Fruits by Inductively Coupled Plasma Mass Spectrometry and Direct Mercury Analysis

This study reports the concentrations of eight trace essential (Zn, Mn, Cu, Ni, Cr, Co, V, and Se) and four toxic elements (Pb, As, Cd, and Hg) in commonly consumed stone fruits from South Korea. The samples were digested by microwave-induced combustion and analyzed by inductively coupled plasma mass spectrometry (ICP-MS). The concentrations of mercury were analyzed by direct mercury analysis (DMA). The analytical techniques were validated by linearity, limits of detection and quantification, precision, recovery, and for accuracy by analyzing a spinach leave-certified reference material; satisfactory results were obtained in all cases. The concentrations of essential trace elements varied considerably among the stone fruits. Generally stone fruits contained comparatively high concentrations of Zn (0.946 to 7.86?µg/g) and Mn (below the limit of detection to 1.66?µg/g), while lower contents of Cu (0.214 to 1.24?µg/g), Cr (0.032 to 0.114?µg/g), Ni (0.006 to 0.091?µg/g), Co (0.004 to 0.016?µg/g), V (below the limit of detection to 0.023?µg/g), and Se (0.0002 to 0.005?µg/g) were obtained. The concentrations (µg/g) of toxic metals were 0.007 (peach) to 0.016 (cherry) for Pb, 0.001 (plum) to 0.007 (cherry) for As, 0.002 (apricot and cherry) to 0.003 (peach) for Cd, and 0.0003 (peach) to 0.0016 (jujube) for Hg. The values for the estimated dietary intakes, target hazard quotients, and hazard indices were lower than the recommended safety limits by World Health Organization. Therefore, the analyzed stone fruits were deemed to be safe for human consumption.