脂肪醇对环氧乙烷环氧丙烷嵌段共聚物破乳效果的影响—Ⅰ.W/O型乳状液的破坏

现时国内外的原油破乳剂品种繁多,但就其组成而言,主体都是环氧乙烷(EO)和环氧丙烷(PO)的嵌段共聚物。我们曾对这类破乳剂的破乳规律进行过较系统的研究。为了进一步寻找提高破乳效果的途径,本文研究了正构脂肪醇对EO-PO共聚物破乳效果的影响。结果表明,加入适量的脂肪醇能大幅度提高破乳效率,效果最好的是正戊醇。     

Iron‐Catalyzed Aminomethyloxygenative Cyclization of Hydroxy‐α‐diazoesters with N,O‐Aminals

A new and efficient cyclization reaction has been developed to synthesize cyclic α,α‐disubstituted β‐amino esters via iron‐catalyzed intramolecular aminomethyloxygenative cyclization of diazo compounds with N,O‐aminal under mild reaction conditions. A broad range of hydroxy‐α‐diazoesters with different substituents and various N,O‐aminals were compatible with this protocol, affording the corresponding α,α‐disubstituted β‐amino esters bearing a five‐ to eight‐membered oxacycle in good yields.     

三聚氰胺基螯合树脂/碳纳米管修饰充蜡石墨电极阳极溶出伏安法测定铅和镉

采用超声法合成了三聚氰胺-甲醛-硫脲螯合树脂（MFT）,基于碳纳米管优良的光电性能,制备了MFT/纳米碳管复合物修饰充蜡石墨电极（MFT/MWCNTs/WGE）。 采用场发射扫描电子显微镜及电化学技术表征了该修饰电极的特性。 该电极被成功地用于水溶液中重金属离子Pb(Ⅱ)和Cd(Ⅱ)的同时测定,Pb(Ⅱ)和Cd(Ⅱ)的溶出峰电流与浓度分别在3×10-8～9×10-7 mol/L和5×10-8～7×10-7 mol/L的浓度范围内,呈良好的线性增长关系,Pd(Ⅱ)和Cd(Ⅱ)的检测限分别为2×10-9和3×10-9 mol/L（3σ）。     

Performance of a Flow-Through Enzyme Reactor Prepared from a Silica Monolith and an α-Poly(D-Lysine)-Enzyme Conjugate

Horseradish peroxidase (HRP) is covalently bound in aqueous solution to polycationic α-poly(D-lysine) chains of ≈1000 repeating units length, PDL, via a bis-aryl hydrazone bond (BAH). Under the experimental conditions used, about 15 HRP molecules are bound along the PDL chain. The purified PDL-BAH-HRP conjugate is very stable when stored at micromolar HRP concentration in a pH 7.2 phosphate buffer solution at 4 °C. When a defined volume of such a conjugate solution of desired HRP concentration (i.e., HRP activity) is added to a macro- and mesoporous silica monolith with pore sizes of 20–30 µm as well as below 30 nm, quantitative and stable noncovalent conjugate immobilization is achieved. The HRP-containing monolith can be used as flow-through enzyme reactor for bioanalytical applications at neutral or slightly alkaline pH, as demonstrated for the determination of hydrogen peroxide in diluted honey. The conjugate can be detached from the monolith by simple enzyme reactor washing with an aqueous solution of pH 5.0, enabling reloading with fresh conjugate solution at pH 7.2. Compared to previously investigated polycationic dendronized polymer-enzyme conjugates with approximately the same average polymer chain length, the PDL-BAH-HRP conjugate appears to be equally suitable for HRP immobilization on silica surfaces.     

机械载荷作用下单边裂纹载流薄板的应力场

采用坐标变换的方式，将单边裂纹载流薄板通电瞬间由温度产生的应力场表达式中的各应力分量分离，并用极坐标进行表示．给出了Ⅰ型穿透裂纹尖端附近的应力场的表达式．最后将温度产生的应力场与单向拉伸载荷作用产生的应力场相叠加，推导出用极坐标表示的机械载荷作用下单边裂纹载流薄板的应力场的表达式，并给出算例．     

生物可降解高聚物P3HB4HB热性能、结晶性能和力学性能研究

P3HB4HB是3β-羟基丁酸酯(3HB)和4β-羟基丁酸酯(4HB)的共聚物。由微生物合成的P3HB4HB具有良好的生物相容性和生物降解性。本研究通过示差扫描热分析(DSC)研究了P3HB4HB的热性能;通过广角X-射线衍射(WAXD)分析了材料的结晶度;通过拉伸力学试验研究了材料的力学性能。结果表明,4HB含量越高,玻璃化转变温度越低,结晶温度越高,结晶度越低;P3HB4HB是一类力学性能接近于PCL或PLGA的生物高分子,通过调节4HB的含量,可以制备出具有不同力学性能的生物材料。     

Synthesis,characterization and cytotoxicity of Pt(II), Pd(II), Cu(II) and Zn(II) complexes with 4’‐substituted terpyridine

Eight novel Pt(II), Pd(II), Cu(II) and Zn(II) complexes with 4’‐substituted terpyridine were synthesized and characterized by elemental analysis, UV, IR, NMR, electron paramagnetic resonance, high‐resolution mass spectrometry and molar conductivity measurements. The cytotoxicity of these complexes against HL‐60, BGC‐823, KB and Bel‐7402 cell lines was evaluated by MTT assay. All the complexes displayed cytotoxicity with low IC₅₀ values (<20 μm ) and showed selectivity. Complexes 3 , 5 , 7 and 8 exerted 9‐, 5‐, 12‐ and 7‐fold higher cytotoxicity than cisplatin against Bel‐7402 cell line. The cytotoxicity of complexes 3 , 5 , 6 , 7 and 8 was higher than that of cisplatin against BGC‐823 cell line. Complexes 3 , 7 and 8 showed similar cytotoxicity to cisplatin against KB cell line. Complex 7 exhibited higher cytotoxicity than cisplatin against HL‐60 cell line. Among these complexes, complex 7 demonstrated the highest in vitro cytotoxicity, with IC₅₀ values of 1.62, 3.59, 2.28 and 0.63 μm against HL‐60, BGC‐823, Bel‐7402 and KB cells lines, respectively. The results suggest that the cytotoxicity of these complexes is related to the nature of the terminal group of the ligand, the metal center and the leaving groups. Copyright © 2013 John Wiley & Sons, Ltd.     

一类三对角矩阵的特征值和特征向量的研究

讨论了一种三对角矩阵的特征值和特征向量.按矩阵右下角对角元素的参数分为两类,得出特征值和特征向量的结论或数值算法.举例说明了算法的有效性.     

Enantioselective total synthesis of a natural hydrocarbazolone alkaloid,identification of its stereochemistry,and revision of its spectroscopic data

The natural hydrocarbazolone alkaloid (1R,2R,3R)-3-hydroxy-1,2-dimethyl-1,2,3,9-tetrahydro-4H-carbazol-4-one has been synthesized in a catalytic and enantioselective manner. A key hydrocarbazole derivative was constructed by the holmium-catalyzed Diels-Alder reaction of (silyloxyvinyl)indole as the diene. Total synthesis of the natural product clarified the ambiguity in the spectroscopic data reported for natural products.