水热法合成多金属氧酸盐棒状超细晶体

以SrCl₂·6H₂O、(NH₄)₆P₂Mo₁₈O₆₂·nH₂O为原料，在PEG-600/H₂O微乳体系中于80～130 ℃温度下水热反应8～12 h，从而制得一种多金属氧酸盐棒状超细晶体，组成是Sr₃P₂Mo₁₈O₆₂·nH₂O。该超细晶体具有长棒状形貌、高结晶度且分散性能较好，长度范围在10.0～20.0 μm，径度在1.0～2.0 μm。对反应体系中的PEG-600/H₂O体积比(V_PEC-600∶V_H2O)、水热温度以及(NH₄)₆P₂Mo₁₈O₆₂·nH₂O/SrCl₂·6H₂O质量比(W_POMs∶W_SrCl2·6H2O)3个影响因素进行了探讨，结果表明：V_PEC-600∶V_H2O主要对棒状超细晶体的形貌、长径比以及晶体结晶度有着重要影响，体积比在范围V_PEC-600∶V_H2O=(1.50～2.00)∶1.00有利于大长径比的棒状超细晶体的形成；水热温度则优选80～130 ℃范围，过低则不发生反应，过高则发生了多金属氧酸盐与PEG-600的氧化-还原反应；W_POMs∶W_SrCl2·6H2O基本上不影响超细晶体的形成。还初步探讨了该棒状超细晶体的形成机理。     

5,7′-(亚甲胺基)-二-8-羟基喹啉的合成及其理论研究

以4-甲基苯磺酸作催化剂、用三乙胺调节pH值约为9的条件下, 由5-甲酰基-8-羟基喹啉和5-氨基-8-羟基喹啉合成了新的5,7′-(亚甲胺基)-二-8-羟基喹啉, 利用IR, UV, ¹H NMR, MS确认了分子结构, 比较研究了其光致发光特性, 运用Gaussian 98量子化学程序包, 采用B3LYP密度泛函(DFT)的方法, 在6-31G(d,p)水平上对分子的几何构型进行结构优化; 并对目标化合物的稳定结构通过计算预测其振动光谱, 计算结果与实验值基本相符.     

PREPARATION OF POLYSULFONAMIDE/TiO2 NANOCOMPOSITES BY SOL-GEL

Polysulfonamide (PSA) was synthesized at room temperature, the polymerization based on terephthaloyl chloride and 3,3 '-diaminodiphenylsulfone in the common solvent N,N -Dimethyl-acetamide (DMAc). Polysulfonamide/titanium oxide nanocomposites were prepared by sol-gel method. Tetrabutyl titanate(TBT) was added into the polysulfonamide solution, at the same time ,some water was mixed to make the TBT hydrolyze. In the process, hydrochloric acid was used to catalyze the reaction. The polysulfonamide chemistry structure was characterized by FT-IR spectrum. Atomic force microscopy (AFM) was employed to observe the microstructure of the composite film. The thermal property was investigated by TGA.The results show that we have succeeded to synthesize the polysulfonamide, TiO2particles were well distributed in the composite film and average size was about 20 nm on average, the heat-resistance of nanocomposite was batter than the pure polysulfonamide.     

Synthesis of Fullerene-end Functionalized Poly（methyl methacrylate） via Reverse Atom Transfer Radical Polymerization

The use of the reverse atom transfer radical polymerization （RATRP） to end-functionalize poly（methyl methacrylate） （PMMA） with fullerenes, e.g. C60 and C70 was described in this paper. The Cl-terrninated PMMA was prepared via RATRP with designed molecular weight and narrow molecular weight distributions, and then directly used to react with fullerenes to produce C60（C70） terminated PMMA polymers in the presence of CuBr/Cu/bipy or FeCl2/bipy catalysts. The resultant polymers exhibit good solubility in some common organic solvents, e.g. THF, CHCl3 and toluene, and were well structurally characterized by a variety of physical techniques.     

Hydrothermal synthesis of one-dimensional (1D) Na<Subscript>x</Subscript>TiO<Subscript>2</Subscript> nanostructures

Nanorods of sodium titanium dioxide bronze Na_xTiO₂ were synthesized by the hydrothermal treatment of the amorphous TiO₂·nH₂O gel with 10 M NaOH followed by ultrasonication in 0.1 M HCl and thermal treatment (500°C, 10 h). The thermal treatment of the nanorods does not change the morphology of the particles. According to the electron diffraction data, the Na_xTiO₂ nanorods grow along the c axis.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 71–73, January, 2005.     

Characterization of mesoporous nanocrystalline TiO2 photocatalysts synthesized via a sol-solvothermal process at a low temperature

Nanocrystalline TiO₂ samples with mesoporous structure were prepared via a solvothermal treatment of surfactant-stabilized TiO₂ sols. The samples were obtained from media of different acidities including nitric acid, deionized water, and ammonia (denoted as HT-1, HT-2 and HT-3, respectively). These samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), N₂-sorption (BET surface area), micro-Raman spectroscopy, infrared absorption spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS). The photocatalytic activities of the samples were tested by the self-photosensitized degradation of an azo dye, Mordant Yellow 10 (MY), in aqueous solution under visible light irradiation. The results reveal that all three samples have high surface area and are pure anatase phase. The sample prepared in nitric acid medium possesses the most ideal mesoporous structure and also exhibits a blue shift in the Raman spectrum. All three samples show much higher photocatalytic activity than the commercial P-25. The activity order of the three samples is HT-1>HT-2>HT-3.     

Synthesis of new axially dissymmetric ligand with large perfluoroalkyl groups

A new axially dissymmetric ligand with large perfluoroalkyl groups, 2,2′-bis(1-hydroxy-1H-perfluorooctyl)biphenyl (1c), which could not be obtained by the coupling reaction of the aryl bromide using copper powder, was synthesized successfully by the coupling reaction using Ni(COD)₂. This ligand showed much higher asymmetric induction in the reaction of diethylzinc with benzaldehyde than the trifluoromethyl (1a) or pentafluoroethyl (1b) analogues.     

Racemization in stepwise solid-phase peptide synthesis at elevated temperatures

The present work is an attempt to assess racemization in stepwise solid-phase peptide synthesis at elevated temperatures (SPPS-ET), a high-speed approach in which peptide elongation occurs at 55-75 °C. This attempt was based on the notion that a high propensity for this side reaction would hamper employment of this alternative approach and would dampen interest in its further development. Simple peptide models were synthesized using customized protocols for classical SPPS or SPPS-ET. Systematic analyses of the resulting crude peptides by reversed-phase HPLC, ion-exchange HPLC, capillary electrophoresis and electrospray ionization mass spectrometry revealed low diastereomeric byproduct contents. These results indicate that, from the standpoint of racemization, classical SPPS and SPPS-ET protocols were equivalent. Therefore, further studies employing SPPS-ET protocols are justified.     

苯丙水溶胶的合成与性能研究(I) 聚合工艺和反应组分对聚合稳定性和胶体性能的影响

用一次投料法、半连续滴加法和单体预乳化法三种聚合工艺，合成了苯丙乳液聚合物，并加氨微细化，转化成水溶胶，考察了聚合工艺和反应组分（乳化剂，功能单体等）对苯丙乳液及其水溶胶反应稳定性和粒子大小及分布等胶体性能的影响。     

两个Pd(II)的异亚硝基乙酰丙酮亚胺配合物的合成和表征

合成了两个异亚硝基乙酰丙酮亚胺Pd(II)配合物，Pd(o-BrC_6H_4-IAI)_2 (1) 和Pd(C_6H_5CH_2-IAI)_2 (2)（IAI = isonitrosoacetylacetoneimino），用IR和 Raman光谱对两个配合物进行了表征，并测定了配合物1的晶体结构。配合物1晶体 属单斜晶系，空间群为P2_1/c，晶胞参数：a = 0.8013(2) nm，b = 1.8775(4) nm，c = 0.7905(2) nm，β = 98.22(3)°，V = 1.1770(5) nm~3，Z = 2，D_c = 1.892 g·cm~(-3)，F(000) = 656，R = 0.0663。在这两个配合物中，二齿 Schiff碱配体的异亚硝基（肟基）的N原子和亚胺的N原子与Pd(II)配位，形成反式 的PdN_4平面正方形配位构型。