Reduced texaphyrin: A ratiometric optical sensor for heavy metals in aqueous solution

We report here a water-soluble metal cation sensor system based on the as-prepared or reduced form of an expanded porphyrin, texaphyrin. Upon metal complexation, a change in the redox state of the ligand occurs that is accompanied by a color change from red to green. Although long employed for synthesis in organic media, we have now found that this complexation-driven redox behavior may be used to achieve the naked eye detectable colorimetric sensing of several number of less-common metal ions in aqueous media. Exposure to In(III), Hg(II), Cd(II), Mn(II), Bi(III), Co(II), and Pb(II) cations leads to a colorimetric response within 10 min. This process is selective for Hg(II) under conditions of competitive analysis. Furthermore, among the subset of response-producing cations, In(III) proved unique in giving rise to a ratiometric change in the ligand-based fluorescence features, including an overall increase in intensity. The cation selectivity observed in aqueous media stands in contrast to what is seen in organic solvents, where a wide range of texaphyrin metal complexes may be prepared. The formation of metal cation complexes under the present aqueous conditions was confirmed by reversed phase high-performance liquid chromatography, ultra-violet-visible absorption and fluorescence spectroscopies, and high-resolution mass spectrometry.     

不同煤阶煤孔隙特征及其吸附能力响应

我国是煤炭资源大国，煤层气储量规模相当可观，但煤储层又具有低孔、低渗的不足，照搬国外或常规石油天然气的开采程序和方法已被证实是走不通的。应结合实际，根据不同地质条件、不同煤阶的开采程序，进行孔隙特征研究。煤孔隙特征、连通性和吸附能力对煤层气开采影响尤为重要，为研究煤孔隙结构特征随煤变质程度的变化关系及其吸附能力的响应特点，采取不同地区不同变质程度煤样，进行压汞测试和等温吸附实验。实验结果表明，煤孔隙度和平均孔径均随变质程度增加呈现降低—升高—降低的趋势；煤中孔隙连通性随煤变质程度增加逐渐变差；随煤变质程度增加，其最大吸附能力也呈现降低—升高—降低的总体趋势。     

Using bald eagles to indicate the health of the Great Lakes' environment

The bald eagle (Haliaeetus leucocephalus) is one of the most studied birds of North America, and a great amount of natural life‐history information, including the response of various stressors on the eagles' ability to reproduce, are well known. In Michigan, the eagle has been chosen to track the trends of bioaccumulative compounds of concern across watersheds in the state. The state has been divided into major watersheds, and 20% of these are surveyed each year. A control area in northern Minnesota, Voyageurs National Park, is also sampled annually. We report here on the methods used, the preliminary results of the 1999 field season, and how differences in mercury concentrations varied over a 10‐year period. Mercury in feathers of nestling eagles declined over time only in Lakes Michigan and Huron, but have not decreased among other subpopulations in Michigan. Concentrations of polychlorinated biphenyls (PCBs) and 4,4′‐DDE in blood plasma from nestling eagles have declined over time for most subpopulations; however, they remain greater for breeding areas associated with the Great Lakes' food web. Sea eagles of the genus Haliaeetus are a good sentinel species to track trends in bioaccumulative compounds in aquatic systems.     

Single and matrix HgCdTe photovoltaic detectors

The recent researches and technological developments of middle and long wavelength infrared HgCdTe photovoltaic detectors are presented. Structure, topology, design and performance of HgCdTe photodiodes, silicon readout electronics, Focal Plane Arrays both staring and time delay and integration types, thermal imagers are discussed. Negative differential conductance, bistability and high frequency oscillations under background infrared radiation in HgCdTe photodiodes are reported.     

核磁共振谱的岩石孔喉结构分析

刘堂宴 ,王绍民 ,傅容珊 ,周明顺 ,李艳华 ,罗曼 .核磁共振谱的岩石孔喉结构分析 .石油地球物理勘探 ,2 0 0 3,38(3) :32 8～ 333岩心核磁共振 T2 谱和压汞分析数据均在一定程度上反映了岩石的孔喉结构 ,理论分析表明 ,这两组数据具有相关性。应用岩心核磁共振 T2 谱研究岩石孔喉结构 ,关键是确定 T2 与 Pc的转换系数。但以前的方法在 T2与 Pc 的转换过程中 ,需要涉及某些岩石特性参数 ,实用中有一定困难。本文直接利用岩心核磁共振 T2 谱和压汞分析数据之间的相关性 ,客观地确定 T2 与 Pc之间的转换系数 ,避免了确定岩石特性参数的困难。应用本文方法 ,对 6块岩心的多种核磁共振分析数据进行了对比分析 ,做出了 NMR (Nuclear Magnetic Resonance,简称NMR) T2 毛管力曲线和孔喉半径分布 ,并将这些结果与压汞分析的结果进行了对比。结果表明 ,岩心 NMR T2谱在实用性和评价精度上均略显优势 ;至少是在饱含油的条件下 ,岩心的 NMR T2 谱可以用于研究孔喉结构分布 ,油气的弛豫特性作为影响背景值存在 ,对于评价结果没有明显的影响 ;在全部 6块岩心中 ,T2 与 Pc 的转换系数位于 2 5 0 0～ 4 0 0 0μs· MPa之间。     

示波极谱滴定法测定工业氯化钙主要成份

在氯化铵-氨水(pH=11)支持电解质中用微银汞膜电极进行试验,锰、铁不干扰测定,用EDTA滴定氯化钙获得令人满意的结果。对三种样品进行分析,变异系数为0.08％—0.11％。该法快速准确,适用于氯化钙主要成份的测定。     

Analysis of trace mercury in water by solid phase extraction using dithizone modified nanometer titanium dioxide and cold vapor atomic absorption spectrometry

A new method for analysis of trace mercury in water samples was developed, based on the combination of preconcentration/separation using dithizone-modified nanometer titanium dioxide (TiO2) as a solid phase extractant and determination by cold vapor atomic adsorption spectrometry (CVAAS). Dithizone was dissolved with alcohol and loaded on the surface of nano-sized TiO2 powders by stirring. The static adsorption behavior of Hg2 on the dithizone-modified nanoparticles was investigated in detail. It was found that excellent adsorption ratio for Hg2 could be obtained in the pH range of 7-8 with an oscillation time of 15 min, and a 5 mL of 3.5 mol·L-1 HCl solution could quantitatively elute Hg2 from nanometer TiO2 powder. Common coexisting ions caused no obvious influence on the determination of mercury. The mechanisms for the adsorption and desorption were discussed. The detection limit (3σ) for Hg2 was calculated to be 5 ng·L-1. The proposed method was applied to the determination of Hg2 in a mineral water sample and a Zhujiang River water sample. By the standard addition method, the average recoveries were found to be 94.4%-108.3% with RSD (n = 5) of 2.9%-3.5%.     

巯基棉预浓集—中子活化法测定水泥及其浸出水中的微量汞

在不同酸度下巯基棉可以从溶液中富集和分离Au、As、Ag、Br、Cu、Ca Co、InHg、Ni、Se、Sb、Sn、Pb、W、Fe和In等30多种元素。由于用巯基棉吸附待测元素后不必洗脱,因此大大提高了富集能力,可用于海水、地下水、地表水及工业废水中一些元素的测量。本文用巯基棉富集后进行中子活化分析测定水泥及其浸出水中的汞。     

VCM生产过程中汞污染的防治

介绍了引进VCM生产技术中，有关含汞污水的处理方法及在生产工艺上所采取的减少汞污染的措施，解决了催化剂的汞污染问题。     

Dental amalgam – the effect of the technology of alloy powder preparation on the corrosion behaviour and the release of mercury

Dental amalgams are based on a broad spectrum of materials differing in their chemical composition, metallurgical treatment, and in the way the initial alloys powders are prepared. In addition to their chemical composition, amalgams based on various powders differ in both their microstructure and the amount of mercury needed for preparation. All these facts may affect electrochemical processes occurring during their interaction with oral fluids, and also mercury release. While verifying the effect of the technology used for the preparation of the high‐copper ternary alloy powder on the properties of resulting amalgams, this study aimed at the mechanism of their interaction with a model saliva solution as well as mercury release was included. Measurements were done in a model saliva solution using standard electrochemical methods and exposition measurements. The interaction of individual types of amalgams with artificial saliva did not reveal any significant differences. The free corrosion potential of all these amalgams in an aerated solution settled in the range of values in which tin oxidation, resulting in a layer of insoluble corrosion producsts, turned out to be the dominant anodic process. The rate of mercury release was the lowest for amalgams based on a gas‐atomized alloy. The highest rate of mercury release, and also its dependence on time, was exhibited by lathe‐cut powder based amalgam. In addition to different volume fraction of the Ag‐Hg phase and the level of its tin alloying, this different behaviour may be explained by differences in the rate at which a layer of tin corrosion products acting as a barrier to mercury release is formed.