高效液相色谱手性固定相法拆分金属簇合物

在正相条件下,ChiralcelR○OD手性色谱柱上,首次直接拆分了3种外消旋过渡金属簇合物,考察了手性化合物结构以及流动相中的醇在手性识别过程中对手性拆分的影响。     

Interactions between Cytochrome c and DNA Strands Self-Assembled at Gold Electrode

In this work, we reported the investigation on the interaction between DNA strands self-assembled at gold electrodes and an electron transfer protein, cytochrome c. We observed that cytochrome c exhibited well-defined electrochemistry in both double-stranded and single-stranded DNA films. This suggested that the electron transfer reaction of cytochrome c arose possibly due to the electron hopping along DNA strands rather than wiring along the double helix. We also compared the heterogeneous electron transfer rate of cytochrome c with that of a ruthenium complex, which further confirmed this mechanism.     

Preparation of Vanadium and Vanadium Oxide Clusters by Means of Inert Gas Aggregation

Vanadium clusters were prepared by the inert gas aggregation technique by evaporating V of high purity. Structural characterization was performed by high-resolution transmission electron microscopy. Apart from vanadium clusters of bcc structures in different orientations, crystalline VO clusters of NaCl structures were observed, which was attributed to the reaction with free oxygen present on the amorphous carbon substrates. The latter could be detected by electron energy-loss spectroscopy. The exposure of the samples to air caused a change to amorphous structures, which re-crystallized under the electron beam. This effect was interpreted as a reaction with water present in the air.     

New Preparation Method of CdS Clusters Encapsulated in Y-Type Zeolites

CdS clusters encapsulated in Y-type zeolite were prepared by a novel technique with non-aqueous systems. The mechanical mixture of CdCl₂· 2.5H₂O crystal with Y-type zeolite was heated at 773 K, followed by the H₂S treatment at 373 K, resulting in the formation of CdS clusters with the size <2.3 nm.     

Gold nanoparticles on ceria: importance of O vacancies in the activation of gold

Synchrotron-based techniques (high-resolution photoemission, in-situ X-ray absorption spectroscopy, and time-resolved X-ray diffraction) have been used to study the destruction of SO₂ and the water-gas shift (WGS, CO + H₂O → H₂ + CO₂) reaction on a series of gold/ceria systems. The adsorption and chemistry of SO₂ was investigated on Au/CeO₂(111) and AuO _x /CeO₂ surfaces. The heat of adsorption of the molecule on Au nanoparticles supported on stoichiometric CeO₂(111) was 4–7 kcal/mol larger than on Au(111). However, there was negligible dissociation of SO₂ on the Au/CeO₂(111) surfaces. The full decomposition of SO₂ was observed only after introducing O vacancies in the ceria support. AuO _x /CeO₂ surfaces were found to be much less chemically active than Au/CeO₂(111) or Au/CeO_2−x (111) surfaces. In a separate set of experiments, in-situ time-resolved X-ray diffraction and X-ray absorption spectroscopy were used to monitor the behavior of nanostructured {Au + AuO _x }–CeO₂ catalysts under the WGS reaction. At temperatures above 250 °C, a complete AuO _x → Au transformation was observed with high catalytic activity. Photoemission results for the oxidation and reduction of Au nanoparticles supported on rough ceria films or a CeO₂(111) single crystal corroborate that cationic Au^δ+ species cannot be the key sites responsible for the WGS activity at high temperatures. The active sites in {Au + AuO _x }/ceria catalysts should involve pure gold nanoparticles in contact with O vacancies of the oxide.     

基于金纳米-植酸胶束混合组装的过氧化氢传感器的电化学研究

采用混合组装技术,利用植酸胶束(IP6micelles)的磷酸酯键络合辣根过氧化物酶(HRP)和金纳米粒子(GNPs),形成了具有生物亲和性的纳米复合材料,保持了辣根过氧化物酶的生物活性,并利用金纳米粒子的高电子密度、介电特性和催化性能,实现了HRP与玻碳电极(GCE)表面的直接电子转移。Nafion膜的滴加能提高电极的选择性和稳定性。实验过程中借助紫外-可见吸收光谱和透射电子显微镜进行表征,实验结果证明:GNPs的高导电和高催化性能,结合植酸胶束的优良生物相容性和对酶的高负载量的特点,使得吸附在其上的HRP保持活性,制备的生物传感器能对H2O2进行电催化还原。Nafion/HRP-IP6micelles-GNPs/GCE对H2O2的线性浓度范围为5×10-7～1.15×10-5mol/L(线性相关系数r=0.993,n=9),最低检测限为0.1μmol/L(信噪比S/N=3),米氏常数为0.002 4 mmol/L。     

到达数据中时空异常聚簇发现

在时空数据中有一类表示用户在某一时间到达某一地点的数据——到达数据,到达数据可以是社交网站的签到数据、轨迹数据中的停留点及公共交通中乘客抵达的位置数据,这些数据的聚簇可以反映用户的聚集行为.基于到达数据,提出一类新的时空数据查询——时空异常聚簇发现.将到达数据进行周期性划分,通过时空聚类算法对一个时间段的数据进行聚类,比较不同时间段内聚簇的差异度,发现具有最大簇异常度的前k个簇.通过该查询发现的时空异常聚簇可以应用于城市安全管理、基于位置的服务和交通调度等方面.定义了异常簇查询模型,提出了针对任意形状聚簇的簇差异度度量,将异常簇查询转化为二分图最大匹配问题,对二分图构建与匹配进行了优化并提出了高效的查询算法.利用真实数据集进行了充分实验,验证了查询结果的实际意义,评估了所提出的各查询算法在不同参数设置下的查询效率.     

An electrochemical study of the dissolution of gold in thiosulfate solutions. Part II. Effect of Copper

Thiosulfate has been considered as one of the most promising of the non-toxic alternatives to cyanide for the leaching of gold and much work has been carried out with the aim of understanding and improving the ammoniacal thiosulfate leaching process. In particular the behaviour of gold in thiosulfate solutions containing copper in the absence of ammonia has received little attention. It has been shown in this study involving electrochemical and leaching tests that copper ions catalyze not only the oxidation of thiosulfate but also the dissolution of gold in alkaline thiosulfate solutions. Electrochemical studies have shown that copper has a positive effect on the anodic dissolution of gold with increasing concentrations of copper resulting in higher dissolution rates of gold at a potential of 0.3V. Studies on the dissolution of gold powder in alkaline oxygenated thiosulfate solutions containing low concentrations of copper have shown that the role of copper in enhancing the dissolution rate of gold is possibly associated with the formation of a copper–thiosulfate–oxygen intermediate which is more reactive in terms of cathodic reduction than dissolved oxygen. The electrochemical experiments have been complemented by a leaching study which has shown that milling of gold powder in the presence of copper (added as ions, metal, or oxide) assists with the dissolution of gold in thiosulfate solutions.     

铜及其合金电解仿金着色工艺

详细介绍了一种铜及铜合金阴极还原着仿金色工艺及其配方。探讨了该工艺的着色原理、电流密度的影响及所得着色膜层的性能。结果表明，该工艺所得的膜层呈金黄色，结晶致密，耐蚀性好。     

自含砷合碳难处理金矿中提取金的研究─Ⅰ.氨水脱砷-石灰加压氧化-氰化

针对甘肃省坪定金矿含金、砷高、金部分地赋存于脉石、脉石为碱性、属于难选难冶矿的特点，提出了氨水脱砷－石灰加压氧化－氰化新工艺．当原矿含金8．7g／t及13．0％砷时，砷可脱除95％，金可浸出85％．技术及经济指标预计均较满意．