Asymmetric cyclopropanation of styrene catalyzed by Cu-(chiral Schiff-base) complexes

Asymmetric cyclopropanation of olefins was carried out with chiral copper-Schiff base complexes derived from copper acetate monohydrate, substituted salicylaldehydes and a chiral amino alcohol. Substituents on salicylaldehyde framework demonstrate a significant effect on the steroselectivities. Those with electron-withdrawing properties enhance the selectivities, whereas bulky sustituents in ortho position to the phenol hydroxy group decrease the selectivities. An ee of more than 98% was achieved for the reaction of styrene with diazoacetate. (C) 2000 Elsevier Science Ltd. All rights reserved.

On-line voltammetric monitoring of dissolved Cu and Ni in the Gulf of Cadiz, south-west Spain

Geochemical processes in estuarine and coastal waters often occur on temporally and spatially small scales, resulting in variability of metal speciation and dissolved concentrations. Thus, surveys, which are aimed to improve our understanding of metal behaviour in such systems, benefit from high-resolution, interactive sampling campaigns. The present paper discusses a high-resolution approach to coastal monitoring, with the application of an automated voltammetric metal analyser for on-line measurements of dissolved trace metals in the Gulf of Cadiz, south-west Spain. This coastal sea receives metal-rich inputs from a metalliferous mining area, mainly via the Huelva estuary. On-line measurements of dissolved Cu, Zn, Ni and Co were carried out on-board ship during an eight-day sampling campaign in the study area in June 1997. A pumping system operated continuously underway and provided sampled water from a depth of ca. 4 m. Total dissolved metal concentrations measured on-line in the Gulf of Cadiz ranged between <5 nM Cu (<3 nM Ni) ca. 50 km off-shore and 60–90 nM Cu (5–13 nM Ni) in the vicinity of the Huelva estuary. The survey revealed steep gradients and strong tidal variability in the dissolved metal plume extending from the Huelva estuary into the Gulf of Cadiz. Further on-line measurements were carried out with the automatic metal monitor from the bank of the Odiel estuary over a full tidal cycle, at dissolved metal concentrations in the μM range. The application confirmed the suitability of the automated metal monitor for coastal sampling, and demonstrated its adaptability to a wide range of environmental conditions in the dynamic waters of estuaries and coastal seas. The near-real time acquisition of dissolved metal concentrations at high resolution enabled an interactive sampling campaign and therefore the close investigation of tidal variability in the development of the Huelva estuary metal plume.

山杏种皮黑色素与Cu~(2+)和Zn~(2+)络合性质的研究

【目的】研究山杏种皮黑色素与Cu2+和Zn2+络合的相关性质,为山杏种皮黑色素以及其他植物黑色素的开发利用提供依据。【方法】采用电位滴定、紫外-可见光差示吸收光谱和红外光谱对山杏种皮黑色素与Cu2+和Zn2+的络合物进行分析。【结果】Cu2+和Zn2+与山杏种皮黑色素络合后,均能促进山杏种皮黑色素酸性位点的去质子化作用,但Cu2+的促进作用更强,结合更为牢固;随pH值升高,山杏种皮黑色素中解离出的络合位点增多,络合Cu2+能力增强。【结论】Cu2+和Zn2+主要与山杏种皮黑色素中羰基发生络合作用,氨基和羟基参与了络合。

石油烃、Cu~(2+)单一与复合污染对沙蚕的毒性效应

在实验室模拟条件下研究了石油烃、Cu2+单一与复合污染对沙蚕的毒性效应.试验的结果表明,沙蚕的死亡率与石油烃、Cu2+的浓度呈显著相关关系.其半数致死浓度LC50分别为:30.2～116.26μg/L(石油烃);449.52～1130.34μg/L(Cu2+).沙蚕体内Cu2+的积累量随着暴露溶液中Cu2+浓度的上升而增加,当Cu2+的浓度>500μg/L时,这一变化十分显著;而沙蚕体内石油烃的含量随着暴露溶液中石油烃浓度的升高无显著变化.而Cu2+和石油烃复合污染对沙蚕的毒性作用较为复杂,在不同的处理中,表现出了协同和拮抗两种作用方式.同时,在Cu2+与石油烃复合污染条件下,沙蚕体内Cu2+的积累量也有显著变化.在复合处理组中,当Cu2+的浓度达到500μg/L时,Cu2+在沙蚕体内的积累量与Cu2+单一污染相比,Cu2+在沙蚕体内积累量相比显著降低.

有机质对Cu~(2+)在棕壤及其各粒级微团聚体中吸附解吸特性的影响

采用平衡液吸附法和NH4AC、EDTA溶液解吸法,研究了有机质对Cu2+在棕壤及其各粒级微团聚体中(<10μm,10～50μm,50～250μm)的吸附解吸过程中的影响,为寻求有效控制土壤中Cu2+环境行为的对策措施提供理论支撑。研究结果表明,各粒级微团聚体中有机质对Cu2+的吸附能力随粒级的减小而增强,原土仅次于<10μm微团聚体。就吸附机制而言,去除有机质后的原土及其各粒级微团聚体在不同吸附机制控制下的吸附能力也有所变化,表现为:去除有机质后,棕壤及各粒级微团聚体对Cu2+的静电吸附能力增强,络合吸附能力和专性吸附的能力均有所降低。分析表明,原土及其不同粒级微团聚体对Cu2+的吸附能力及稳定性的差异,与其重要组成成分有机质有关。

Synthesis of Cu-In-S ternary nanocrystals with tunable structure and composition

Nearly monodisperse Cu-In-S ternary nanocrystals with tunable composition, crystalline structure, and size were synthesized by a hot-injection method using mixed generic precursors. Such ternary nanocrystals with zincblende and wurtzite structure were reported for the first time.

Silver nanocluster-based fluorescent sensors for sensitive detection of Cu(II)

In this work, we report the first application of water-soluble fluorescent Ag nanoclusters in fluorescent sensors. The fluorescence of poly(methacrylic acid) (PMAA)-templated Ag nanoclusters was found to be quenched effectively by Cu2+, but not when other common metal ions were present. By virtue of the specific response toward the analyte, a new, simple, and sensitive fluorescent method for detecting Cu2+ has been developed based on Ag nanoclusters.

Constructing channel structures based on the assembly of p-sulfonatocalix[4]arene nanocapsules and [M(bpdo)(3)](2+)(M = Cu, Zn)

Novel channel structures based on [M(bpdo)(3)](2+) and p-sulfonatocalix[4]arene nanocapsules have been established; these are sustained exclusively by charge-assisted pi...pi interactions and sorption experiments show the porous materials have selective guest sorption properties.

A copper/p-sulfonatocalix[6]arene/phenanthroline supramolecular compound with 1D [Cu-2-calixarene](n) coordination chains

A supramolecular complex [Cu(phen)(2)H2O]{[Cu(phen)(H2O)](2)[C6AS]}center dot 2.5H(2)O (phen = 1,10'-phenanthroline and C6AS = p-sulfonatocalix[6]arene) has been synthesized under hydrothermal condition, and characterized by IR spectroscopy, TG analysis and single crystal X-ray diffraction. In the structure, unprecedented 1D ({[Cu(phen)(H2O)](2)[C(6)AS]}(2-))(n) coordination chains (exactly being belts) are stacked into some 2D layers by the pi center dot center dot center dot pi stacking interactions, which are further interconnected into a 3D extended structure by hydrogen bonding.