Robust core-shell supramolecular assemblies based on cationic vesicles and ring-shaped [Mo154] polyoxomolybdate nanoclusters: template-directed synthesis and characterizations

Substantial progress has been made recently in extending the supramolecular assembly of biomimetic structures to vesicle-based sophisticated nanocomposites and mesostructures. We report herein the successful preparation of unilamellar surfactant vesicles coated with a monolayer of ring-shaped [Mo(154)] polyoxometalate (POM) nanoclusters, (NH(4))(28)[Mo(154)(NO)(14)O(448)H(14)(H(2)O)(70)]. approximately 350 H(2)O, by coulomb attractions using preformed didodecyldimethylammonium bromide (DDAB) surfactant vesicles as templates. The resultant vesicle-templated supramolecular assemblies are robust (they do not disintegrate upon dehydration) both at room-temperature ambient and vacuum conditions, as characterized by conventional transmission electron microscopy (TEM) and atomic force microscopy (AFM). The flexibility of the complex soft assemblies was also revealed by AFM measurements. The effect of POM-vesicle coulomb attractions on the dimensions of the templating vesicles was also investigated by using dynamic light scattering (DLS). Although origins of the structure stability of the as-prepared supramolecular assemblies are not clear yet, the nanometer scale cavities and the related properties of macroions of the POM clusters may play an important role in it.     

细胞色素C的电化学行为研究

本文评述了细胞色素Ｃ电化学研究的发展概况，重点介绍了细胞色素Ｃ在促进剂作用下的电化学行为，促进剂种类，影响促进作用的因素及促进机理。     

N-(1-异丙基-2-羧基-4-甲基二环[2.2.2]-5-辛烯-3-羰基)-N′-芳基(硫)脲的合成

在无溶剂绿色化学条件下,将α-萜品烯-马来酸酐加成物(1)与取代苯(硫)脲发生N-酰化反应,合成了4个N-(1-异丙基-2-羧基-4-甲基二环[2.2.2]-5-辛烯-3-羰基)-N′-芳基(硫)脲化合物(3a~3d),并由IR、UV-Vis、MS、1HNMR、13C NMR和元素分析确认了目标产物的结构。生物活性测试表明,其中3个化合物(3a、3b和3c)具有植物激素作用。     

Heterogeneous catalytic aerobic oxidation behavior of Co–Na heterodinuclear polymeric complex of Salen-crown ether

A new kind of Co–Na heterodinuclear polymer complex based on Salen Schiff base and crown ether has been successfully prepared by condensation polymerization. Its catalytic behavior for aerobic oxidation of cyclohexene, alkylbenzenes and linear aliphatic olefins was studied in the absence of any solvents or reducing agents under mild conditions. The oxidation of cyclohexene catalyzed by the above catalyst proved to be a simple and efficient method for obtaining 2-cyclohexen-1-one (CO) and 2-cyclohexen-ol (OH) in a high selectivity. Kinetics of the oxidation was also investigated. The results showed that the aerobic oxidation of cyclohexene catalyzed by Salen-crown ether heterodinuclear polymer complex follows a radical chain aerobic oxidation mechanism. This oxidation system is also efficient in the oxidation of alkylbenzenes and linear aliphatic olefins, which afforded corresponding benzylic oxidation products and epoxides, respectively.     

Designed nanostructured pt film for electrocatalytic activities by underpotential deposition combined chemical replacement techniques

Multiple-deposited Pt overlayer modified Pt nanoparticle (MD-Pt overlayer/PtNPs) films were deliberately constructed on glassy carbon electrodes through alternately multiple underpotential deposition (UPD) of Ag followed redox replacement reaction by Pt (II) cations. The linear and regular growth of the films characterized by cyclic voltammetry was observed. Atomic force spectroscopy (AFM) provides the surface morphology of the nanostructured Pt films. Rotating disk electrode (RDE) voltammetry and rotating ring-disk electrode (RRDE) voltammetry demonstrate that the MD-Pt overlayer/PtNPs films can catalyze an almost four-electron reduction of O(2) to H(2)O in air-saturated 0.1 M H(2)SO(4). Thus-prepared Pt films behave as novel nanostructured electrocatalysts for dioxygen reduction and hydrogen evolution reaction (HER) with enhanced electrocatalytic activities, in terms of both reduction peak potential and peak current, when compared to that of the bulk polycrystalline Pt electrode. Additionally, it is noted that after multiple replacement cycles, the electrocatalytic activities improved remarkably, although the increased amount of Pt is very low in comparison to that of pre-modified PtNPs due to the intrinsic feature of the UPD-redox replacement technique. In other words, the electrocatalytic activities could be improved markedly without using very much Pt by the technique of tailoring the catalytic surface. These features may provide an interesting way to produce Pt catalysts with a reliable catalytic performance as well as a reduction in cost.     

3，19－二羟基－1－硫杂－5，8，11，14，17－五氧杂环二十烷的醚化与缩聚反应

３，１９－二羟基－１－硫杂－５，８，１１，１４，１７－五氧杂环二十烷（简称二羟基硫杂２０－冠－６）在一缩二乙二醇二甲醚和氢化钠存在下可与卤代烷顺利地进行醚化反应，得到双己氧基、双十二烷氧基、双十六烷氧基、双节氧基和双烯丙氧基硫杂２０－冠－６，同时也得到了单己氧基、单十二烷氧基、单十六烷氧基和单辛氧基单羟基疏杂２０－冠－６副产物。二羟基硫杂冠醚可顺利地与丁二酰氯缩聚，得到主链含硫杂冠醚基团的聚酯     

Studies on the Spectral Behavior between Protein with Poniacyl Carmine 2B and its Analytical Application

In this paper, the spectral behavior of protein and Poniacyl Carmine 2B (PC 2B) has been studied by spectrophotometric method. The conditional constants, apparent combination constant K and maximum binding number n, were used to express the combination ability of the reactions between PC 2B and protein under a set of given conditions. The Sandell index s was used to express the sensitivity of the determination of protein. The factors, acidity, PC 2B concentration and the ionic strength, were discussed by the change of apparent combination constant and maximum binding number. It was found that acidity of the solution, PC 2B concentration and ionic strength had a significant effect on the sensitivity of the assay of protein. Under the optimal conditions, the apparent combination constant K and the maximum binding number n were 2.36 × 10⁶ L mol^?1 and 95, respectively. With further investigation, it was found that the Scatchard model was suitable in treating the data obtained in the experiments. In the buffer medium of HCl‐KCl at 1.87, the addition of protein made the maximum absorption of the system move from 527 nm to 513 nm. Its apparent molar absorptivity is 4.46 × 10⁵ Lmol^?1 cm^?1 at 513 nm. Beer's law is obeyed in the range of 0 ? 55 μg mL^?1. The system developed in this paper has been used for the determination of protein in milk powder successfully.     

水热法合成Ce0.67Zr0.33O0.2固溶体研究

采用两种不同前驱体通过水热法合成了Ce0.67Zr0.33O0.2固溶体,并通过XRD,BET,TPR等手段考察了样品的相结构,比表面及还原特性.结果表明,在180℃,12 h的水热条件下,以共沉淀产物为前驱体所制得的Ce0.67Zr0.33O0.2固溶体比表面积较高,但存在一定程度的相分离;以凝胶产物为前驱体制得的Ce0.67Zr0.33O0.2固溶体结构更完整,具有良好的还原特性及热稳定性.     

[Ni(dien)_2]_2[Mn(NCS)_6]·H_2O的合成、晶体结构

硫氰酸根的结构为N≡C－S－，其两端的N原子和S原子分别有一对和三对孤对电子，因此，硫氰酸根可采用多种不同的配位模式与金属离子发生配位。硫氰酸根可作为单齿配体与一个金属离子配位，形成M－SCN或M－NCS的单核配合物，也可以作为桥联配体同时与两个、三个甚至四个金属离子配位形成多核配合物犤１～３犦；另一方面，硫氰酸根是一个具有一定共轭性的偶极子，可传递磁相作用。因此，选择硫氰酸根作为桥联配体，将多个顺磁金属离子桥联形成一维、二维或三维结构的多核金属配合物分子，并研究它们的磁性已成为分子磁学的一个研究领域…     

偏氟乙烯的聚合反应

本文研究了用有机引发剂引发偏氟乙烯的水相聚合,并对制得的聚偏氟乙烯的性质进行了研究。有机引发剂引发聚合的聚偏氟乙烯的热稳定性、强度、结晶度和熔点均比用过硫酸盐引发聚合的聚偏氟乙烯高。