B2O3/TiO2-ZrO2催化环己酮肟气相Beckmann重排反应研究 Ⅰ.B2O3含量的影响

 制备了不同B2O3含量（0～20％）的B2O3／TiO2－ZrO2固体酸催\r\n化剂，用XRD，FT－IR，N2吸附及NH3－TPD等方法测定了其结构、比表\r\n面积、孔分布和表面酸性．结果表明，当B2O3含量较低（≤5％）时，\r\n催化剂呈无定形态，样品中的B2O3主要以BO4结构存在．当B2O3含量较\r\n高（≥8％）时，催化剂中的TiO2－ZrO2以ZrTiO4晶相存在，分散于Ti\r\nO2－ZrO2表面的B2O3主要以玻璃体形式和BO3结构存在．随着B2O3含量\r\n的增加，催化剂的比表面积减小，孔径增大．300℃下的环己酮肟气相\r\nBeck－mann重排反应结果表明，随着B2O3含量的增加，己内酰胺的选择\r\n性逐渐增大，而己内酰胺的收率在B2O3含量为12％时达到最大值．讨论\r\n了B2O3／TiO2－ZrO2的催化性能与其表面酸性及孔径大小的关系．     

二茂钛苄氧基衍生物的合成及性质研究

Ｃｐ２ＴｉＣｌ２及（ＭｅＣｐ）２ＴｉＣｌ２在Ｅｔ３Ｎ或ＮａＮＨ２存在下与苄醇类化合物反应，高产率地合成了６个未见文献报道的二茂钛（Ⅳ）苄氧基衍生物，甲基二茂钛（Ⅳ）苄氧基化合物，经元素分析，ＨＮＭＲ和ＩＲ光谱确定了化合物的结构，并对其部分性质进行了讨论。     

季铵盐固相催化使聚氯乙烯脱HCl

通过将季铵盐与聚氯乙烯(PVC)混溶成膜,使其在固相脱HCl,研究了催化剂对PVC脱HCl反应速度和产物结构的影响以及固相反应与温度、时间的关系.发现在催化性能上下基铵盐比乙基铵盐好得多,根据实验结果提出了季铵盐通过分解成叔胺实现催化的机理.     

Biosorption of copper(II) and zinc(II) from aqueous solution by Pseudomonas putida CZ1

To study Pseudomonas putida CZ1, having high tolerance to copper and zinc on the removal of toxic metals from aqueous solutions, the biosorption of Cu(II) and Zn(II) by living and nonliving P. putida CZ1 were studied as functions of reaction time, initial pH of the solution and metal concentration. It was found that the optimum pH for Zn(II) removal by living and nonliving cells was 5.0, while it was 5.0 and 4.5, respectively, for Cu(II) removal. At the optimal conditions, metal ion biosorption was increased as the initial metal concentration increased. The adsorption data with respect to both metals provide an excellent fit to the Langmuir isotherm. The binding capacity of living cells is significantly higher than that of nonliving cells at tested conditions. It demonstrated that about 40-50% of the metals were actively taken up by P. putida CZ1, with the remainder being passively bound to the bacterium. Moreover, desorption efficiency of Cu(II) and Zn(II) by living cells was 72.5 and 45.6% under 0.1M HCl and it was 95.3 and 83.8% by nonliving cells, respectively. It may be due to Cu(II) and Zn(II) uptake by the living cells enhanced by intracellular accumulation.     

Energetic preferences for alpha,beta versus beta,gamma unsaturation

Density functional theory has been applied at the B3LYP/6-311+G(d,p)//B3LYP/6-31G(d) level to examine the energetics of alpha,beta- versus beta,gamma-unsaturation for some common organic functional groups. Specifically, the relative stabilities of allyl-X (H2C=CHCH2X) and 1-propenyl-X (H3CCH=CHX) isomers have been computed for X = methyl, vinyl, phenyl, formyl, acetyl, methoxy, methylthio, methylsulfinyl, methylsulfonyl, sulfamoyl, and methoxysulfonyl, and the results are compared to available experimental data. The intrinsic preference of 3 kcal/mol for the 1-propenyl isomer when X = CH3 is exceeded by 2-4 kcal/mol for first-row conjugating groups, but it is not met for the sulfur-containing groups. In particular, alpha,beta-unsaturation is favored by less than 1 kcal/mol for the sulfone and sulfonamide analogues, while it is preferred by 8 kcal/mol for the vinyl-substituted case. Detailed structural results and torsional energy profiles are also reported.     

Facile solvent-free synthesis of pure-phased AlN nanowhiskers at a low temperature

Pure hexagonal aluminum nitride (AlN) nanowhiskers have been successfully synthesized by directly reacting AlCl₃ with NaN₃ in non-solvent system at the low temperature of 450 °C for 24 h. The obtained products are characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, high-resolution transmission electron microscopy and selected area electron diffraction, which show that the obtained products are hexagonal phase AlN nanowhiskers with width from 10 to 80 nm and length up to several micrometers. The influencing factors of the formation of AlN nanowhiskers were discussed and a possible growth mechanism for AlN nanowhiskers was proposed. Additionally, the study on the corresponding optical properties and catalytic properties is also carried out.     

LyP-1 peptide-functionalized gold nanoprisms for SERRS imaging and tumor growth suppressing by PTT induced-hyperthermia

The gold nanoprisms (GNPs) have exhibited special plasmonic properties for biomedical applications because of their unique shapes and dimensions. Based on their optical performance, the NIR dye IR780 not only enabled the GNPs-based nanosystem as SERRS nanoparticles for Raman-encoded molecular imaging, but also enhanced the plasmonic photothermal property by laser irradiation. Meanwhile, the GNPs/IR780-Lyp-1 by introduction of tumor-homing peptide segment LyP-1, which presents high affinity to p32 protein, demonstrated the increased enrichment in tumor region and enhanced photothermal therapy efficacy.     

水相中乙醇对胶体泡沫性质的影响

用不同比例的水-乙醇混合物作水相制备了胶体泡沫（CLA）,实验观察并测定了CLA的形态、粒径分布、半衰期、Zeta电位、水相溶液的粘度和水相/油相之间的界面张力等性质.结果表明，水相中加入乙醇会影响CLA的稳定性和粒径大小,但对CLA的Zeta电位影响不大.乙醇对CLA稳定性的影响主要是由于乙醇分子嵌入到界面膜中导致膜的强度变化以及水相粘度发生变化导致CLA粒子间隙的排液过程发生变化.     

星状四芳胺类空穴传输材料的合成

有机电致发光器件 (ＯＥＬＤ)是继阴极射线管平板显示器 (ＣＲＴ)和液晶显示器 (ＬＣＤ)之后的第三代平板显示器。它具有主动发光、驱动电压低(2伏左右 )、发光亮度高 (1 3 0 0 0ｃｄ ｍ2 以上 ) ,无软Ｘ 射线污染 ,响应速度快 (1 0 -6 ～ 1 0 -8秒 )等优点。从 1 987年美藉华人邓清云等提出多层结构的ＯＥＬＤ的器件结构以来的十多年间 ,ＯＥＬＤ以及其材料的研究已成为显示技术以及显示材料等方面的研究热点 ,发展很快[1～ 3] 。在 1 999年日本先锋公司已开发出了单色的汽车用ＯＥＬ平板显示器商品 ,今年东芝公司又开发出了 2 .7英寸的彩…     

Oxidative free radical reactions of enamino esters

Oxidative free radical reactions of enamino esters are described. Electrophilic carbon-centered radicals produced by the cerium(IV) ammonium nitrate (CAN) oxidation of β-dicarbonyl compounds undergo efficient addition to the C-C double bond of enamino esters. This CAN mediated free radical reaction between enamino esters and β-dicarbonyl compounds provides a novel method for the synthesis of highly substituted pyrroles. The direct CAN oxidation of β-enaminocinnamates gave the dimerization products effectively.