Synthesis of a novel C2-symmetric thiourea and its application in the Pd-catalyzed cross-coupling reactions with arenediazonium salts under aerobic conditions

[reaction: see text] A novel thiourea-based C2-symmetric ligand was synthesized, and its application in the palladium-catalyzed Heck and Suzuki coupling reactions of arenediazonium salts was evaluated. The reactions, which were performed at room temperature, without added base, and under aerobic conditions, produced product in 4 h with good yield. The corresponding arenediazonium salts were easily generated in one step from anilines.     

蟹,虾壳微观形貌与结构研究

用Ｘ射线衍射与扫描电镜研究了蟹壳，虾壳的形貌与微观结构，蟹壳中以方解石晶型存在的碳酸钙分布在网状结构的有机质中，网孔的尺寸约５～２５μｍ有机基质脱去蛋白后留下的甲壳质呈片层状结构，它的重复距离为０．９６ｎｍ。     

基于纳米金探针和基因芯片的DNA检测新方法

运用荧光纳米金探针和基因芯片杂交建立一种新的DNA检测方法. 荧光纳米金探针表面标记有两种DNA探针: 一种为带有Cy5荧光分子的信号探针BP1, 起信号放大作用; 另一种为与靶DNA一部分互补的检测探针P532, 两种探针比例为5∶1. 当靶DNA存在时, 芯片上捕捉探针(与靶DNA的另一部分互补)通过碱基互补配对结合靶DNA, 将靶DNA固定于芯片上; 荧光纳米金探针通过检测探针与靶DNA及芯片结合, 在芯片上形成“三明治”复合结构, 最后通过检测信号探针上荧光分子的信号强度来确定靶DNA的量. 新方法检测灵敏度高, 可以检测浓度为1 pmol/L的靶DNA, 操作简单, 检测时间短. 通过改进纳米金探针的标记和优化杂交条件, 可进一步提高核酸检测的灵敏度, 这将在核酸检测方面具有重要的应用价值.     

3-甲基环状乙撑磷酸二酯醇解的反应途径的理论研究

采用密度泛函理论和MP2方法研究了3-甲基环状乙撑磷酸二酯(MEP)与甲醇的反应途径:(Ⅰ)CH3O-+MEP;(Ⅱ)CH3OH+MEP;(Ⅲ)CH3O-+HMEP(MEP的质子化形式);(Ⅳ)CH3OH+HMEP.在B3LYP/6-31++G(d,p)水平上优化了四条反应途径的反应物、中间体、过渡态及产物的几何构型,并在同水平上进行了自然电荷分析,然后在MP2/6-311++G(3df,2p)水平上计算了各驻点的单点能.采用极化连续介质模型(PCM)研究了各途径在苯、甲醇和水溶液中的溶剂化效应.计算结果表明,溶剂效应使途径(Ⅰ)的自由能垒降低,而使途径(Ⅱ)和(Ⅳ)的决速步骤的自由能垒升高.在气相和苯溶剂中途径(Ⅳ)是反应的优势途径,在甲醇和水溶剂中途径(Ⅰ)则成为最优.研究结果进一步表明实验条件下途径(Ⅱ)与(Ⅳ)对总醇解反应的贡献相当.     

Side-by-side comparison of disposable microchips with commercial capillary cartridges for application in capillary isoelectric focusing with whole column imaging detection

Simple-structured, well-functioned disposable poly(dimethylsiloxane) (PDMS) microchips were developed for capillary isoelectric focusing with whole column imaging detection (CIEF-WCID). Side-by-side comparison of the developed microchips with well-established commercial capillary cartridges demonstrated that the disposable microchips have comparable performance as well as advantages such as absence of lens effect and possibility of high-aspect-ratio accompanied with a dramatic reduction in cost.     

砷的代谢机制、毒性和生物监测

砷化合物是备受关注的一类污染物,特别是饮用水中的砷污染引发了全球性的健康问题.本文综述了近年来人们对砷的代谢机制、毒性和生物监测的研究进展.砷在生物体内的代谢过程十分复杂,在氧化还原酶和甲基转移酶的参与下,产生一系列的代谢产物和中间产物.其中,砷的原始摄入形态、代谢产物及中间产物由于不同的物理化学性质,体现了不同的毒性.人类和不同的动物由于不同的砷代谢机理和甲基化能力,也表现了对砷毒性抵抗能力的差异.在生物体内,一些砷化合物与生物蛋白相互作用,影响它们的存在形式、分布和传输,是砷的生物代谢和毒理研究中不可或缺的内容.生物监测是一种直接有效的污染物健康风险评估方法.在尿液、血液、唾液、头发和指甲中砷化合物直接反映了暴露主体的砷暴露程度,这5种生物介质作为砷暴露的生物标志物各有优缺点.在砷的研究中,代谢机制和毒性的研究可以帮助选择合适的生物监测方法,做出合理准确的健康风险评估.生物监测也可促进对砷的代谢机制和毒性的理解,推断可能的代谢途径,定量毒性剂量效应,两者相互依赖相互促进.     

绿色氧化合成苯乙酮的研究

研究了以氧气为氧化剂、液相氧化乙苯合成苯乙酮反应的各种影响因素,在优化的反应条件(冰乙酸20mL、乙苯5mL、醋酸钴用量为乙苯的4.2%(物质的量)、Br/Co=2.5(物质的量)、氧气流速为100mL/min、常压、温度80℃和反应时间4h)下,乙苯转化率达到99.94%,苯乙酮收率达到98.49%.     

Spectroscopic study on the interaction between[Hg（SCN）4]2- and hemoglobin

The interaction between[Hg（SCN）₄]^2- and hemoglobin（Hb） under conditions that simulate a physiological environment was investigated by UV-vis spectroscopy,fluorescence spectroscopy,resonance Rayleigh scattering（RRS） spectroscopy and circular dichroism（CD） spectroscopy.The results obtained from the change of UV-vis and CD spectra,the quenching of Hb fluorescence and the enhancement of RRS intensity proved that a 10:1 type complex was formed between[Hg（SCN）₄]^2- and Hb.The possible mechanism suggested for the interaction was that ten Hg（SCN）₄]^2- anions entered the four subunits of a Hb molecule to react with some residues to form an adduct by coordination and electrostatic forces.The coordination of[Hg（SCN）₄]^2- with Trp was the major cause of the fluorescence quenching of Hb.     

乙酰胺-氯化锌新型离子液体的合成及物化性质

合成了CH3CONH2-ZnCl2体系离子液体;利用红外光谱仪分析了CH3CONH2-ZnCl2离子液体的化学特征,采用步冷曲线法绘制了CH3CONH2-ZnCl2二元体系熔点图,测定了其物化性质.结果表明,CH3CONH2-ZnCl2二元体系的最低熔点为8℃;当CH3CONH2与ZnCl2的摩尔比为3:1时,Zn2+...     

Highly oxidized graphene with enhanced fluorescence and its direct fluorescence visualization

We prepared hyper-oxidized graphene (HOG) as a form of graphene derivative by additional oxidation of graphene oxide (GO) sheets. HOG, which formed more functional groups and isolated conjugated clusters on the sheets, accordingly showed high solubility in water and alcohols, high transmittance and film transparence, longer fluorescence decay constant time, and enhanced fluorescence in states of solution and solid. By contrast, GO has much weaker fluorescence in solution and its fluorescence is totally quenched in solid. The influences of concentration, metallic ions, and pH on HOG fluorescence in aqueous solution were also investigated in detail. Due to HOG’s strong fluorescence, direct visualization was realized on substrates and in solution. In addition, direct 3D fluorescence visualizations of HOG phase in polymer composites were achieved. These results show the great potential of HOG in a broad range of applications, from biological labeling, probes, and drug carriers to high-performance composites and nanomanipulation.