氧化锰团簇粒子在有序多孔氧化锆孔道中的组装及其特殊性能研究

利用醇溶液浸渍法及后续的热处理工艺成功实现了氧化锰团簇粒子在有序多孔氧化锆孔道中的组装，借助XRD，TEM，UV-vis，EPR以及O~2-TPD等分析手段进行样品结构表征及性能分析。研究表明，氧化锰团簇粒子能比较均匀地分散于规则的孔道中；团簇粒子的生长随着热处理温度的提高受到孔道大小的限制；孔道中的氧化锰团簇粒子能显示出与较大尺寸氧化锰粒子完全不同的强顺磁信号，并且还具有优异的表面氧吸附特性。     

Trehalose-based cyclodextrin analogs: cyclotrehalans (CTs)

A new concept for the de novo synthesis of artificial glyconanocavities is presented. The use of alternating α,α′-trehalose building blocks and (thio)urea segments allows the efficient synthesis of a new family of cyclooligosaccharides, namely cyclotrehalans (CTs), featuring a convex-shaped cavity with an apolar environment. CTs are designed to exhibit molecular inclusion abilities similar to that of cyclodextrins (CDs). Contrary to CDs, CTs expose the monosaccharide β-face to the inner cavity, while the (thio)urea tethers provides some conformational adaptability. High-yielding syntheses of a series of CTs and a preliminary evaluation of their inclusion properties are reported.     

Metal Ion Guest Responsive Benzoxazine Dimers and Inclusion Phenomena of Cyclic Derivatives

This study was carried out with the aim to optimize the dissolution propertiesof diclofenac (DIC) – a non-steroidal anti-inflammatory drug sparingly solublein water – through association -with -cyclodextrin (CD). Theeffect of CD on the aqueous solubility of DIC was evaluated by thephase solubility method. The amount of DIC dissolved increased linearly withthe addition of CD according to an AL type plot and without precipitationof the complex. The apparent stability constant of the complex, calculated supposinga 1:1 stoichiometry, was 295 M^-1; this value was confirmed by circulardichroism analysis. DIC/CD interactions were also studied in water by¹H and ¹³C NMR spectroscopy. Equimolar DIC/CD solid systems were prepared by physical-mixing, kneading, co-evaporation andfreeze-drying, and their properties in the solid state studied by DifferentialScanning Calorimetry, X-ray powder diffractometry and Fourier-TransformInfrared analysis. For sake of comparison, the mixture of DIC and CDseparately lyophilized was investigated too. The results demonstrated that thefreeze-dried product had the highest degree of amorphization and they were inagreement with the existence of an inclusion complex in the solid state. Thedissolution profiles of the drug from each solid system were affected by its physico-chemical properties, the freeze-dried being the most rapidly dissolvingforms.     

A Comparative Study of Naproxen – Beta Cyclodextrin Complexes Prepared by Conventional Methods and Using Supercritical Carbon Dioxide

Naproxen is a poorly soluble anti-inflammatorydrug, the solubility of which canbe enhanced by complexation withbeta-cyclodextrin. Besides that, the inclusioncomplex reduces the incidence of gastrointestinal side effects of the drug. The aim of this work was to compare the physicochemical characteristics of the solid complexes prepared by traditional methods (kneading, freeze-drying and spray-drying) and using a supercritical fluid technology. The unusual solvent properties of carbon dioxide above their critical temperature and pressure were exploited in order to prepare inclusion compounds. Complexes prepared using supercritical fluid technology showed similar properties to those of freeze-drying andspray-drying complexes as proved by DSC, FT-IRand UV.     

Cu-P系稀土耐候钢中最佳稀土含量的研究

利用光学显微镜、图像分析仪和电子探针对低氧低硫的10PCuRE耐候钢板坯进行了观察和检测,采用干-湿周浸室内加速试验方法测得了试验钢的腐蚀率.用电化学方法测得了带锈样的阳极极化曲线.研究得出对于S:～0.004%,O:～0.002%的10PCuRE耐候钢,最佳稀土含量为0.0065%～0.012%,此稀土含量对非金属夹杂物的变质作用和耐蚀性能的提高最为有利.     

Inclusion of Nonopiate Analgesic Drugs in Cyclodextrins. I. X-Ray Structure of a 1 : 1 β-Cyclodextrin-p-bromoacetanilide Complex

The preparation and X-ray crystal structure of a 1 : 1 complex between -cyclodextrin (-CD) and the analgesic p-bromoacetanilide are reported. Thermogravimetric and UV spectrophotometric analyses of single crystals grown from an aqueous solution containing host and guest in 1 : 1 molar ratio yielded the composition -CD p-bromoacetanilide $ 13.5H2O. Crystals of the complex are triclinic, space group P1, with a = 15.197(3), b = 15.613(2), c = 15.743(4) Å, = 87.16(2), = 98.29(2), = 103.39(1)° and Z = 2 crystallographically independent complex units per unit cell. The -CD molecules form head-to-head dimers which pack in the channel-mode. Each dimer contains two guest molecules whose acetylamino substituents are located at the dimer interface while the bromine atoms protrude from the -CD primary faces. The acetyl residues of both guest molecules were found to be disordered but the X-ray data permitted     

Preparation and crystal structure ofexo-2,exo-6-dihydroxy-2,6-dimethyl-9-oxabicyclo[3.3.1]nonane

In a further exploration of the structural factors causing alicyclic diols such asexo-2,exo-6-dihydroxy-2,6-dimethylbicyclo[3.3.1]nonane (1) to adopt the helical tubuland inclusion host structure, the title compound (8) has been synthesized and its crystal structure determined. This 9-oxa analogue of (1) has a totally different structure [C₁₀H₁₈O₃; orthorhombic;P2₁2₁2;a 18.989(4),b 19.064(3),c 14.256(3) Å;Z 20; with finalR 0.065] due to involvement of the ether oxygen atom in the hydrogen bonding network. The structure of the diol (8) approximatesP¯42₁ c symmetry, and 16 of the 20 molecules per cell create a hostlike structure of this symmetry, which consists of tightly bound hydrogen bonded pillars parallel toc. The remaining guestlike molecules occupy inequivalent pseudo ¯4 sites separated byc/2 to form weakly bound columns parallel toc. Hydrogen bonds also occur between the pillars and columns. An ordered structure with sensible intermolecular contacts can be formed inP2₁2₁2₁ with thec axis doubled. A difference betweena andb axial lengths correlates with a difference in occupancies of pseudo-¯4-related sites for the guest-like component of the structure.     

量化方法研究分子结BEMP和TEMP的电子输运特性

通过结合杂化密度泛函和前线轨道理论与弹性散射格林函数方法研究了BE- MP(benzene-1,4-di-ethynyl-4-mercaptophenyl)和TEMP(thiophene-2,5-di-ethynyl-4- mercaptophenyl)两分子结的输运性质。基于杂化密度泛函方法计算两扩展分子电子结构的基础上,计算了两分子的输运性质．计算结果显示:电流增加来源于电极和分子轨道的共振;电导曲线呈现出平台特征．在此基础上从扩展分子A(Au-BEMP-Au)中间的苯环的旋转而引起电流减小的角度解释了负微分电阻现象．     

Formation of Supramolecular Polymers Constructed by Cyclodextrins with Cinnamamide

-Cyclodextrin having cinnamamide at 6- or 3-positions (6-CiNH--CD, 3-CiNH--CD) and -cyclodextrin with cinnamamide on 6-position (6-CiNH--CD) have been prepared. Supramolecular structures were formed in the solid state or aqueous solutions and characterized by measurements of NMR and vapor pressure osmometry (VPO). The results indicate that 6-CiNH--CD formed insoluble supramolecular polymers in the solid state, while 6-CiNH--CD and 3-CiNH--CD formed supramolecular complexes in aqueous solutions. 6-CiNH--CD was found to form a dimer in an aqueous solution. 3-CiNH--CD formed intermolecular complexes to give supramolecular polymers. The differences of the position of guest part on cyclodextrins caused to give a variety of supramolecular structures in aqueous solutions.     

Studies on novel cyclodextrans: Inclusion of C60 and C70

Cycloisomalto-heptaose (CI-7) and cycloisomalto-octaose (CI-8) are two novel cyclodextrans. Treatment with C₆₀ or C₇₀ by kneading leads to the formation of four distinct water-soluble inclusion complexes: CI-7/C₆₀ (2: 1), CI-8/C₆₀ (2: 1), CI-7/C₇₀ (2: 1) and CI-8/C₇₀ (2: 1). Their formation and structures have been examined by UV vis spectroscopy, X-ray powder diffraction and fluorescence spectral studies. The reaction is a reversible process.