Two noncentrosymmetric complexes: [W(CO)4(bipy)] and [W(CO)4(phen)](bipy = 2,2′-bipyridine, phen = 1,10-phenanthroline) obtained through solvothermal synthesis and their optical properties

Solvothermal treatments of W(CO)₆ with 2,2′-bipyridine and 1,10-phenanthroline give [W(CO)₄(bipy)] (1) and [W(CO)₄(phen)] (2), respectively, which both crystallize in noncentrosymmetric space groups, suggesting that they meet the requirement of second harmonic generation (SHG) investigations. The preliminary experiment indicates that they are SHG active, and approximately estimated to be that of urea.     

DNA-modified electrodes; part 4: optimization of covalent immobilization of DNA on self-assembled monolayers

The covalent immobilization of DNA onto self-assembled monolayer (SAM) modified gold electrodes (SAM/Au) was studied by X-ray photoelectron spectrometry and electrochemical method so as to optimize its covalent immobilization on SAMs. Three types of SAMs with hydroxyl, amino, and carboxyl terminal groups, respectively, were examined. Results obtained by both X-ray photoelectron spectrometry and cyclic voltammetry show that the largest covalent immobilization amount of dsDNA could be gained on hydroxyl-terminated SAM/Au. The ratio of amount of dsDNA immobilized on hydroxyl-terminated SAMs to that on carboxyl-terminated SAMs and to that on amino-terminated SAMs is (3-3.5): (1-1.5): 1. The dsDNA immobilized covalently on hydroxyl-terminated SAMs accounts for 82.8-87.6% of its total surface amount (including small amount of dsDNA adsorbed). So the hydroxyl-terminated SAM is a good substrate for the covalent immobilization of dsDNA on gold surfaces.     

PBA@POM Hybrids as Efficient Electrocatalysts for the Oxygen Evolution Reaction

To realize the effective conversion of renewable energy through water decomposition, efficient electrocatalysts for the oxygen evolution reaction (OER) are essential. In this article, PBA@POM was successfully prepared with a Prussian blue analogue (PBA) as the initial structure. A facile hydrothermal process is reported for obtaining PBA@POM by etching the cubic PBA with a strong Brønsted acid, H₃PMo₁₂O₄₀ (HPMo). The hollow cube structure not only exposes more active sites but also promotes electron transport, which results in excellent electrocatalytic activity for the OER. Compared with the PBA, which initially simply adhered to POM, the optimum PBA@POM hybrids display remarkably enhanced OER catalytic activity, with an almost constant overpotential of 440 mV at a current density of 10 mA cm^?2 and a small Tafel slope (23.45 mV dec^?1). The facilely prepared PBA@POM with good electrochemical activity and stability promises great potential for the OER.     

Single nanocrystal arrays on patterned poly(ethylene glycol) copolymer microstructures using selective wetting and drying

Single nanocrystal arrays were fabricated on sub-microwells of poly(ethylene glycol) (PEG) copolymer using selective wetting on the hydrophilic regions of the exposed substrate surface and subsequent drying. Templates were produced by molding a thin film of a PEG-based random copolymer on hydrophilic substrates such as glass or silicon dioxide. The polymeric microstructures provide a topographical barrier around the well, which makes it possible to create nanocrystal arrays with controlled geometrical features. The size of the nanocrystal was found to decrease with decreasing well size and also decrease with decreasing topological height. A simple empirical equation was derived to predict the size of the crystal as a function of the pattern size and height, which is in good agreement with the experimental data.     

Electrocatalysis of Metalloporphyrins(Ⅷ)——Electrocatalytic Reduction of Molecular Oxygen with Water-Soluble Cobalt (Ⅱ) Tetrakis(4-Trimethyl Ammonium Phenyl) Porphyrin Catalyst

Reported here is the electrocatalytic reduction of molecular oxygen in the presence of water-soluble cobalt(Ⅱ) tetrakis(4-trimethyl ammonium phenyl) porphyrin (Co(Ⅱ)TTAPP) as catalyst in solutions of various pH values. The overpotential of molecular oxygen reduction is reduced by ca. 200-400 mV in acidic and neutral solutions compared with several decades of millivolts in alkaline solutions, indicating that Co(Ⅱ)TTAPP possesses much higher catalytic activity in acidic and neutral solutions than in alkaline. H2TTAPP in solutions of various pH exhibits no significant catalytic activity for oxygen reduction. The significant difference in the electrocatalytic activity of Co(Ⅱ)TTAPP from that of H2TTAPP for oxygen reduction indicates that the electrocatalytic activity of Co(Ⅱ)TTAPP should be attributed to the central cobalt atom (Co(Ⅱ)) coordinated by N4 internal ring in Co(Ⅱ)TTAPP. The total number of electrons involved in oxygen reduction electrocatalyzed by Co (Ⅱ)TTAPP is 2, and the product of suc     

Synthesis and characterization of monodisperse magnetic composite particles for magnetorheological fluid materials

Monodisperse magnetic composite particles (MCP) were prepared and characterized for a study of magnetic field-responsive fluids. Magnetic composite particles used are iron oxide-coated polymer composite particles, which were synthesized through in situ coating of iron oxide onto pre-existing polymer particles by the reduction of ferrous fluids. For a uniform and bulk coating of iron oxide, the porous structure was introduced into the substrate polymer particles through a two-step seeded polymerization method. Moreover, surface cyano-functionality was born from acrylonitrile unit of substrate polymer and it played an important role in obtaining successful uniform coating. The structure of the composite particle was analyzed by using a thermo gravimetric analysis (TGA) and a X-ray diffraction (XRD) analysis. The magnetization property of the particle was also observed. Then, the rheological properties of monodisperse magnetorheological (MR) suspensions of magnetic composite particles were examined under a magnetic field using a parallel-plate type commercial rheometer. From the rheological measurements, it was found that MR properties of the magnetic composite suspensions are dependent on the iron oxide content and the fluid composition.     

高硅沸石骨架结构及其稳定性的模拟计算(I)*

The lattice energy of a series of high-silica zeolites was determined using the lattice energy minimization method. The results were compared to the lattice energy of dense polymorphs of SiO2. All high-silica zeolites frameworks are only 30～67kJ•mol-1 less stable than α-quartz This may imply that there is little energy barrier to the formation of high-silica zeolites frame-works and explain the structural diversity observed for high-silica zeolites. The relationships of calculated lattice energies and framework Structures was disscussed. The results revealed a good linear relationship between framework density of these molecular sieves and all-silica framework lattice energies.     

Recovery of palladium from basic reprocessing waste of spent nuclear fuel

The methods including collection method, extraction-collection method, and special extraction-collection method have been investigated for high speed and efficient recovery of palladium from high pH reprocessing waste of spent nuclear fuel. The equilibrium of the reactions can be obtained is less than 1 minute. The maximum percent recovery of Pd is about 89%, 96% and 97% for collection, extraction-collection, and special extraction-collection methods, respectively. Nearly 100% of back extraction of Pd in the organic phase can be attained by using 7.4M ammonia solution, with a phase ratio of 1:1. The purity of the Pd product is high. The percent recovery of Pd is constant, up to 5·10³ Gy of irradiation dose.     

Lithium isotope separation by chemical exchange with polymer-bound azacrown compounds

The chromatographic separation of lithium isotopes was investigated by chemical exchange with the recently synthesized polymer-bound dibenzo pyridino diamide azacrown (DBPDA) and reduced dibenzo pyridino diamide azacrown (RDBPDA). Column chromatography was employed for the determination of the effect of solvents and ligand conformation on the separation coefficients. The maximum separation coefficients, , for the DBPDA and RDBPDA at 20.0±0.02°C with acetonitrile as eluent, were found to be 0.034±0.002 and 0.035±0.002, respectively. The isotope separation coefficient and adsorption capability of the lithium ion on the DBPDA and RDBPDA were only slightly dependent on ligand structure, but strongly dependent on the solvent. DBPDA and RDBPDA appeared to have almost the same value for the isotope separation coefficient of lithium.     

大鼠体内复方清开灵代谢物的分析

建立了复方中药清开灵代谢物的液相色谱-质谱/质谱分析方法。采用Phenomenex Luna C18色谱柱,以0.1%甲酸(A)及V(甲醇)∶和V(乙腈)=4∶1混合液(B)作流动相,采用梯度洗脱(0 min,B为0%;33min,B为60%;66 min,B为88%;75 min,B为100%),流速:0.5 mL/min,离子阱质谱负离子模式进行检测。通过差谱方法对可能的代谢物进行快速搜索。对发现的重要的代谢物根据分子量以及多级质谱的碎片离子数据,结合体内代谢反应规律,进行指认和结构鉴定。共鉴定了3个主要的代谢物,其中一个为黄芩苷的代谢物,另两个为绿原酸的代谢物,后两个代谢物未见文献报道。本实验为研究复方中药复杂体系体内的代谢产物提供了一个有效而且快捷的模式。