4－（6－甲基－2－苯并噻唑偶氮）间苯三酚反相高效液相色谱分离测定钒钴镍铬

作者以新研制的４－（６－甲基－２－苯并噻唑偶氨）间苯三酚为柱前衍生试剂，用含１０ｍｍｏｌ／Ｌ的ｐＨ６．８０的ＨＡｃ－ＮａＡｃ缓冲溶液，１０ｍｍｏｌ／ＬＴＢＡ·Ｂｒ和１×１０￣（－４）ｍｏｌ／ＬＥＤＴＡ的甲醇－水溶液（７８：２２，Ｖ／Ｖ）作流动相，在Ｃ＿（１８）柱上，１１ｍｉｎ内反相ＨＰＬＣ分离测定了Ｃｒ（Ⅵ），Ｖ（Ⅴ）Ｃｏ（Ⅱ），Ｎｉ（Ⅲ）。当Ｓ／Ｎ＝３时，其检出限分别是Ｖ（Ⅴ）５．４５ｎｇ，Ｃｏ（Ⅱ）１．０９ｎｇ，Ｎｉ（Ⅱ）１．５０ｎｇ，Ｃｒ（Ⅵ）１．７０ｎｇ。     

4—（6—甲基—2—苯并噻唑偶氮）间苯三酚反相高效液相色谱分离测定钒钴镍铬

作以新研制的４－（６－甲基－２－苯并噻唑偶氮）间苯三酚为柱前衍生试剂，用含１０ｍｍｏｌ／Ｌ的ｐＨ６．８０的ＨＡｃ－ＮａＡｃ缓冲溶液，１０ｍｍｏｌ／Ｌ ＴＢＡ．Ｂｒ和１×１０＾－４ｍｏｌ／ＬＥＤＴＡ的甲醇－水溶液（７８：２２，Ｖ／Ｖ）作流动相，在Ｃ１８柱上，１１ｍｉｎ内反相ＨＰＬＣ分离测定了Ｃｒ（Ⅵ），Ｖ（Ⅴ），Ｃｏ（Ⅱ），Ｎｉ（Ⅱ）。当Ｓ／Ｎ＝３时，其检出限分别是Ｖ（Ⅴ）５．４５ｎｇ，Ｃｏ（Ⅱ）     

铁（Ⅱ、Ⅲ）、钴（Ⅱ）、镍（Ⅱ）、铜（Ⅱ）－MBTAE配合物的反相高效液相色谱分离和测定

本文报道了以２－（６－甲基－２－苯并噻唑偶氮）－５－二乙氨基酚（ＭＢＴＡＥ）作柱前衍生化试剂，在ＳｐｈｅｒｉｓｏｒｂＣ＿８柱上，以甲醇：水＝８０：２０（Ｖ／Ｖ），含２ｍｍｏｌ／ＬＬｉ＿２ＳＯ＿４和１０ｍｍｏｌ／ＬｐＨ５．０醋酸盐缓冲溶液作流动相，反相高效液相色谱分离和测定了Ｆｅ￣（２＋）、Ｃｏ￣（２＋）、Ｎｉ￣（２＋）和Ｃｕ￣（２＋）。各金属离子的检出限（Ｓ／Ｎ＝３）分别为（ｐｇ）：Ｆｅ￣（２＋）６．４０，Ｃｏ￣（２－）１．３８，Ｎｉ￣（２＋）４．４７，Ｃｕ￣（２＋）７．２８。方法用于欧洲标准局，黑麦草标样的分析，所得结果与标准值相符。     

5,10,15,20—四（3—溴—4—磺酸苯基）卟啉高效液相色谱法测定河水中微量…

研究了新合成的显色剂５，１０，１５，２０－四（３－溴－４－磺酸苯基）卟啉与Ｃｏ（Ⅱ）、Ｚｎ（Ⅱ）、Ｃｕ（Ⅱ）形成配合物离子的反应，在ＺＯＲＢＡＸ ＯＤＳ柱上，用含２０ｍｍｏｌ／Ｌ乙酸－乙酸钠（ｐＨ６．０）和１０ｍｍｏｌ／Ｌ四乙基碘化铵的乙腈－水（２７：７３，Ｖ／Ｖ）流动相洗脱，在４２０ｎｍ波长下检测。Ｃｏ（Ⅱ）、Ｚｎ（Ⅱ）、Ｃｕ（Ⅱ）螯合物在９ｍｉｎ内获得完全分离，检测限分别为０．２ｎｇ，０．０５     

用钼酸盐和罗丹明B光度法测定铂

本文研究了在聚乙烯醇（ＰＶＡ）存在下用钼酸盐和罗丹明Ｂ（ＲＢ）光度法测定铂，铂（Ⅳ）与相酸铵和罗丹明Ｂ形成离子缔合物，它的最大吸收波长位于５７０ｎｍ处；摩尔吸光系数６值为６．８３×１０￣５Ｌ·ｍｏｌ￣（－１）·ｃｍ￣（－１），铂量在０～３．５μｇ／２５ｍＬ范围内服从比耳定律，缔合物至少稳定１月。报告了４１种共存离子的影响，除生成杂多酸元素和Ａｕ（Ⅲ）、Ｏｓ（Ⅷ）、Ｒｕ（Ⅲ）外，大多数元素不干扰。测定铂（Ⅳ）的适宜条件为［ＨＣｌＯ＿４］＝０．９３ｍｏｌ／Ｌ，［ＲＢ］＝４．２×１０￣（－５）ｍｏｌ／Ｌ，ＰＶＡ０．８ｇ／Ｌ，本法已用于催化剂和某些铂矿中铂的测定，结果满意。缔合物的摩尔比为Ｐｔ（Ⅳ）：ＲＢ＝１：２，初步探讨了反应机理。     

1─（2─吡啶偶氮）─2─萘酚─6─磺酸衍生化反相高效液相色谱法测定铁、钴、镍

本文研究了水溶性试剂１－（２－吡啶偶氮）－２－萘酚－６－磺酸（ＰＡＮ－Ｓ）与铁（Ⅱ）、钴（Ⅱ）和镍（Ⅱ）之螯合物的衍生和液相色谱分离条件。在Ｎｏｖａ－ＰａｋＴＭＣ１８柱上，用含１０ｍｍｏｌ／Ｌ的ｐＨ５．０的醋酸－醋酸钠缓冲溶液的甲醇－水溶液（５０：５０，Ｖ／Ｖ）作流动相，溴化四丁基铵（ＴＢＡ·Ｂｒ）作离子对试剂，流动相流速为１．０ｍＬ／ｍｉｎ，在５５０ｎｍ波长处进行光度检测。在Ⅱｍｉｎ内用高效液相色谱分离测定了Ｆｅ（Ⅱ）、Ｃｏ（Ⅱ）和Ｎｉ（Ⅱ）与ＰＡＮ—Ｓ的螯合物，提出了离子对反相高效液相色谱快速分离测定痕量铁、钴、镍的新方法。信噪比（ＳＮＲ）为２时，检测下限分别为０．０４３、０．００７和０．０１２ｍｇ／Ｌ。     

双（取代环戊二烯基）二氯化锆的晶体结构分析

用Ｘ－射线晶体结构衍射法测定了双［１－苄基－１－乙基丙基环戊二烯基］二氯化锆［η５－Ｃ５Ｈ４Ｃ（Ｃ２Ｈ５）２ＣＨ２Ｃ６Ｈ５］２ＺｒＣｌ２（Ｉ）及（１，２－二异丁基－１，２－甲基－乙基桥联）双环戊二烯基二氯化锆［η５－Ｃ５Ｈ４Ｃ（ＣＨ３）（Ｃ４Ｈ９－ｉ）Ｃ（ＣＨ３）（Ｃ４Ｈ９－ｉ）Ｃ５Ｈ４－η５］ＺｒＣｌ２（Ⅱ）的结构。二者皆为单斜晶系，（Ｉ）的空间群为Ｐ２／ｎ，ａ＝１２．５８２（３），ｂ＝７．９９２（２），ｃ＝１４．９７９（３）Ａ，β＝１０１．６８（１）°，Ｖ＝１４７４．９（９）Ａ３，Ｍｒ＝６１２．８４，Ｚ＝２，Ｄｘ＝１．３８ｇ／ｃｍ３，μ＝５．６９ｃｍ（－１），Ｆ（０００）＝６４０，Ｒ＝０．０３３，Ｒω＝０．０３６。（Ⅱ）的空间群为Ｃｃ，ａ＝１３．３０９（３），ｂ＝９．５９１（１），ｃ＝１６．４４９（８）Ａ。β＝４．８３（３）°，Ｖ＝２０９．２（２）Ａ３，Ｍｒ＝４５８．６３，Ｚ＝４，Ｄｘ＝１．４５６ｇ／ｃｍ３，μ＝７．７７ｃｍ（－１），Ｆ（０００）＝９５２，Ｒ＝０．０５１，Ｒω＝０．０６１。化合物（Ｉ）以重叠式存在，两个苄基处于反式。晶体（Ⅱ）以交叉式存在，甲基、异丁基以反式构象存在。     

铜（Ⅰ）—苯骈三氮唑络合吸附波的极谱研究与应用

本文在０．６ｍｏｌ／Ｌ ＮＨ３－ＮＨ４Ｃｌ缓冲溶液（ｐＨ＝９．８）中，Ｃｕ（Ⅱ）在滴汞电极上还原生成Ｃｕ（Ⅰ），可与苯骈三氮唑（ＢＴＡ）络合，产生一灵敏的络合吸附波，Ｅｐ＝－０．７３Ｖ（ｕｓ，ＳＣＥ）。苯骈三氮唑的浓度在０．４０－１０．０ｍｇ／Ｌ范围内与极谱波峰高呈线性关系，检测下限为０．４０ｍｇ／Ｌ，相对标准偏差为１．４％－３．２％；回收率为９７．５％－１０１．５％。     

反相HPLC测定钒,铌,钽的2—（2—吡啶偶氮）—5—二乙氨基苯酚配合物

以２－（２－吡啶偶氮０－５－二乙氨基苯酚（ＰＡＤＡＰ）为柱前衍生试剂，在含０．１％酒石酸的１０ｍｍｏｌ／Ｌ（ｐＨ３．５）ＨＡｃ－ＮａＡｃ缓冲溶液的甲醇／水（５０∶５０，Ｖ／Ｖ）中（５８０ｎｍ检测），在Ｃ１８柱上于１１ｍｉｎ内实现了Ｖ、Ｎｂ、Ｔａ的同时分离及测定，检出限（Ｓ／Ｎ＝３）杰０．３４、０．２９、７．３０ｎｇ／ｍＬ．该法灵敏度高，用于矿样分析所得民推荐值相行，标准加入回收率为９９．０％～１０     

2-溴代对苯二甲酸根桥联双核钴(Ⅱ)配合物的合成、磁性及抗癌活性

合成了三种以２－溴代对苯二甲酸根为桥联配体的新型双核钴（Ⅱ）的配合物，即［Ｃｏ２（ＢＴＰ）（ｐｈｅｎ）４］（ＣｌＯ４）２·Ｈ２Ｏ（配合物１）、［Ｃｏ２（ＢＴＰ）（Ｎｐｈｅｎ）４］（ＣｌＯ４）２·２Ｈ２Ｏ（配合物２）和［Ｃｏ２（ＢＴＰ）（Ｂｐｙ）４］（ＣｌＯ４）２·２Ｈ２Ｏ（配合物３）（ＢＴＰ＝２－溴代对苯二甲酸根，ｐｈｅｎ＝１，１０－菲罗啉，Ｎｐｈｅｎ＝５－硝基－１，１０－菲罗啉，Ｂｐｙ＝２，２′－联吡啶）。使用元素分析、ＩＲ、ＵＶ－Ｖｉｓ光谱和电导测定方法对该配合物进行了表征。测定了配合物的变温磁化率，并对所得数据进行了理论分析，求得了配合物１、配合物２和配合物３的自旋磁交换积分分别为：２Ｊ＝－６．５ｃｍ－１，２Ｊ＝－７．８ｃｍ－１和２Ｊ＝－８．９ｃｍ－１。对该三配合物进行了体外抗人白血病癌细胞的实验。发现该三配合物均具有一定的抑制癌细胞的活性     

Metals and other elements

This is the 13th report of the General Referee covering developments during the past year, presenting selected reports, and concluding with recommendations for consideration by the Methods Committee on Residues and Related Topics.     

Chameleon Metals: Autonomous Nano-Texturing and Composition Inversion on Liquid Metals Surfaces

Studies on passivating oxides on liquid metals are challenging, in part, due to plasticity, entropic, and technological limitations. In alloys, compositional complexity in the passivating oxide(s) and underlying metal interface exacerbates these challenges. This nanoscale complexity, however, offers an opportunity to engineer the surface of the liquid metal under felicitous choice of processing conditions. We inferred that difference in reactivity, coupled with inherent interface ordering, presages exploitable order and selectivity to autonomously present compositionally biased oxides on the surface of these metals. Besides compositional differences, sequential release of biased (enriched) components, via fractal-like paths, allows for patterned layered surface structures. We, therefore, present a simple thermal-oxidative compositional inversion (TOCI) method to introduce fractal-like structures on the surface of these metals in a controlled (tier, composition, and structure) manner by exploiting underlying stochastic fracturing process. Using a ternary alloy, a three-tiered (in structure and composition) surface structure is demonstrated.     

金属在生物和医学中的作用

金属元素在整个生命体系中起着重要的作用。金属离子与核酸、蛋白质等生物大分子的作用以及对神经系统的不正常的影响可以直接或间接地损伤DNA从而引起细胞的变异,进而导致各种疾病;同时我们可以根据这些特性研究金属离子的药物用于各种疾病的诊断和治疗。本文着重介绍了几种重要的金属和无机药物。     

Liquid Metals and Liquid Semiconductors

Numerous liquid systems have electrical properties which resemble those of crystalline and amorphous semiconductors. The existence of “semiconducting” behavior in these liquids is mostly related to a continuous transition from a metallic to a “semiconducting” state when a thermodynamic variable such as temperature, density or concentration is changed. Changes in the nature of the chemical interaction and the associated changes in the structure of the liquid are of fundamental importance for the transition to a “semiconducting” state. This will be demonstrated for the ionic liquid CsAu, for covalent liquid selenium, and for expanded liquid metals.     

Metals in Medicine

Not only the 24 or so essential elements , but also nonessential and even radioactive elements have enormous potential for applications in medicine. In the fight against cancer cisplatin, one of the world's best selling anticancer drugs, is being joined by other platinum, titanium, and ruthenium complexes. Gadolinium(III ) complexes can be safely injected as magnetic resonance imaging contrast agents, and ligand design allows targeting of paramagnetic ions as well as radiodiagnostic (e.g. ^99mTc) and radiotherapeutic isotopes (e.g. ¹⁸⁶Re). Manganese superoxide dismutase mimics, vanadium insulin mimics, ruthenium nitric oxide scavengers, lanthanide-based photosensitizers, and metal-targeted organic agents show exciting clinical potential.     

Metals in membranes

In this critical review we discuss recent advances in understanding the modes of interaction of metal ions with membrane proteins, including channels, pumps, transporters, ATP-binding cassette proteins, G-protein coupled receptors, kinases and respiratory enzymes. Such knowledge provides a basis for elucidating the mechanism of action of some classes of metallodrugs, and a stimulus for the further exploration of the coordination chemistry of metal ions in membranes. Such research offers promise for the discovery of new drugs with unusual modes of action. The article will be of interest to bioinorganic chemists, chemical biologists, biochemists, pharmacologists and medicinal chemists. (247 references).     

金属的生物甲基化作用和环境输送

讨论了生命体与重金属间的相互关系、重金属生物甲基化作用的环境输送及生物富集，评述了重金属的生态危害么及微生物在其环境输送过程中所起的作用。     

Clusters and Colloidal Metals in Catalysi

The review summarizes the results of works on the synthesis, structure, and magnetic and catalytic properties of giant palladium clusters, specifically, nanosized palladium complexes stabilized by o-phenanthroline and acetate ligands, which are objects of the colloid chemistry of palladium.     

Speciation Dynamics and Bioavailability of Metals

The dynamic features of metal ion speciation in complex aqueous systems are defined in terms of the pertaining association/dissociation rate parameters. Subsequently, the role of complex species in the supply of free-metal towards a consuming interface is analysed. Limiting cases are those of inert and labile complexes. For each category the steady-state metal uptake by organisms can be described by a basic two-parameter flux equation. This allows a detailed interpretation of experimentally observed bioconversion rates. As an example, the uptake of radiocobalt(II) by carp from various types of complex media is reconstructed on the basis of the flux characteristics.