氟尿嘧啶与磁性层状复合氢氧化物的离子交换反应动力学

以共沉淀法合成的磁性层状复合氢氧化物(Magnetic layered double hydroxide, MLDH)为前驱体, 通过对原位反应系统液相数据的拟合与固相样品的表征, 研究了0~50 ℃条件下MLDH与氟尿嘧啶(5-FU)的离子交换动力学特征. 结果表明, MLDH及离子交换产物MLDH-FU为以六方晶系为主并混杂微量氧化铁的复合磁性晶相; MLDH-FU离子交换速率随温度的升高而显著加快, FU, OH^-和Cl^- 3种客体的浓度变化分别服从二级、 零级及一级反应速率模型, 反应活化能依次为12.69, 27.88和3.580 kJ/mol. 固相表征参数的变化与液相动力学过程、 主-客体结构调整及MLDH-FU粒子陈化过程相符; 离子交换限定在LDH层间, 不涉及层板内部秩序, 不改变前驱体的结构与形貌特征, 具有侧向非断层反应习性, 是交换剂在MLDH外周经吸附亲和、 侧向进攻、 层间置换及柱撑模型转换再到新的插层客体主导调整及晶粒发育陈化的有序过程.     

“右旋糖酐-磁性层状复合氢氧化物-氟尿嘧啶”给药系统的超分子组装表征与急毒性水平

用"前体共沉淀-离子交换插层-原位复合-溶剂转换"技术合成"右旋糖酐-磁性层状复合氢氧化物-氟尿嘧啶"(DET-MLDH-FU,DMF)运载系统,通过XRD,IR,TEM,TG表征及体外释放实验研究了DMF的物相特征与缓释性能,通过对小鼠灌胃和腹腔注射给药考察了DMF与载体MLDH的急毒性水平.结果表明,DMF等超分子的XRD与R-六方LDH衍射特征相符,是Fe3.6Fe0.9(O,OH,Cl)9型LDH及微量Fe3O4的复合晶相,DMF具有DET,MLDH与FU分级组装形成的核壳式构造.体外pH 7.35 PBS溶出介质中,DMF的药物释放遵守零级模型C-1.162×10-5=4.566×10-7t,速率常数4.566×10-7 mol-1?L?m-1.DMF,MLDH-FU及MLDH可经正常代谢排出体外,口服毒性小;腹腔注射DMF的LD50为2542.8 mg?kg-1,MLDH的LD50为1951.0 mg?kg-1,均属低毒性物质.DET的复合组装对Fe(II,III)LDH构架有抗氧化保护作用,对不同MLDH-FU粒子进行选择、分离与包封,提高MLDH-FU的缓释效果、强化MLDH的控释性能,降低给药系统DMF的急毒性水平.     

近红外响应硫化铜纳米粒子/液晶弹性体复合材料研究

报道了一种新型近红外响应光热转换试剂/液晶弹性体复合材料.目前绝大多数近红外吸收的无机金属纳米粒子,由于自身或其稳定剂(如长链硫醇或季铵盐)的化学性质,会致使经典的Finkelmann两步硅氢化加成反应中所使用的催化剂中毒失活,从而极大地限制了无机金属纳米粒子/液晶弹性体复合材料的拓展与应用.为了解决这一科学问题,我们采用了两步硫醇-烯点击化学快速制备单畴取向液晶弹性体薄膜的技术,将对近红外光有强吸收的油溶性硫化铜纳米粒子,成功地掺杂入聚硅氧烷液晶弹性体体系中,制备了近红外响应的硫化铜纳米粒子/液晶弹性体复合薄膜.通过使用紫外可见光谱、透射电子显微镜、扫描电子显微镜、偏光显微镜、示差扫描量热法、变温广角X射线散射对该复合材料进行了深入的研究,结果表明:该薄膜材料在980 nm近红外光源的照射下,可以实现高效的光热转换,从而实现快速、可逆的二维伸缩运动.     

Morphological studies of a (self-assembling oil gelator/liquid crystal) composite system

The aggregation structure of a novel (self-assembling oil gelator/liquid crystal) composite was investigated using light scattering studies and morphological observations. The oil gelator forms a self-assembled-networks aggregate in an organic solvent with a low molecular weight liquid crystal (LC). It became apparent from Hv light scattering patterns and polarizing optical microscopy that two types of LC molecular alignments exist in the composite: a random orientation and a spherulite type one in a nematic gel state. Also, optical and atomic force microscopic observations revealed that fibrils which formed bundles in the fibre-like and spherulite-like aggregates, were formed in the composite. The alignment of the liquid crystal molecules was related to the aggregation structure of the self-assembling oil gelator in a liquid crystal gel state.     

Morphological studies of a (self-assembling oil gelator/liquid crystal) composite system

The aggregation structure of a novel (self-assembling oil gelator/liquid crystal) composite was investigated using light scattering studies and morphological observations. The oil gelator forms a self-assembled-networks aggregate in an organic solvent with a low molecular weight liquid crystal (LC). It became apparent from Hv light scattering patterns and polarizing optical microscopy that two types of LC molecular alignments exist in the composite: a random orientation and a spherulite type one in a nematic gel state. Also, optical and atomic force microscopic observations revealed that fibrils which formed bundles in the fibre-like and spherulite-like aggregates, were formed in the composite. The alignment of the liquid crystal molecules was related to the aggregation structure of the self-assembling oil gelator in a liquid crystal gel state.     

Thermo-recording in (side chain type smectic A liquid crystal polymer/nematic liquid crystal/chiral dopant/dichroic dye) composite with a low power laser

Thermo-recording in a [side chain type smectic A liquid crystal polymer (SmA-LCP)/nematic liquid crystal (N-LC)/chiral dopant/dichroic dye] composite has been realized by using 2mW of power from a He-Ne laser. The laser irradiation-induced phase transitions of smectic A (SmA) → chiral nematic (N*) → SmA formed the dominant thermo-recording mechanism in the composite. Thermo-recording in the (SmA-LCP/N-LC/chiral dopant/dichroic dye) composite exhibited a higher contrast when compared with the non-polymeric (SmA-LC)/N-LC/chiral dopant/dichroic dye composite.     

复合镀层中ZrO2微粒对基质Ni晶体结构的影响

采用复合电沉积方法制备了Ｎｉ－ＺｒＯ２复合镀层，探讨了ＺｒＯ２微粒引起的基质金属Ｎｉ的晶体择优取向及点阵常数的变化，及其对析氢电催化活性的影响。结果表明，ＺｒＯ２微粒的存在改变了Ｎｉ的电沉积层结构，使基质金属Ｎｉ产生新的沿（２２０）晶面的择优取向。这一新的择优取向不利于析氢反应。择优取向的改变说明复合电沉积过程中，Ｎｉ与ＺｒＯ２微粒是以一定的界面匹配进入复合镀层的，基质金属Ｎｉ点阵参数的改变也证明     

核壳结构碳化钨/碳化钨铁复合材料的制备与电催化活性

以铁黄为载体,偏钨酸铵为钨源,将直接包覆与原位还原碳化技术相结合制备了碳化钨/碳化钨铁复合材料.经X射线衍射(XRD)分析和透射电子显微镜(TEM)观察,复合材料的主要物相为碳化钨铁(Fe3W3C)、碳化钨(WC)和碳化二钨(W2C),且构成了以Fe3W3C为核、WC和W2C为壳的核壳结构.采用三电极体系循环伏安法测试了复合材料在酸性、中性和碱性体系中对甲醇的电催化氧化活性.结果表明,与颗粒状碳化钨和介孔空心球状碳化钨相比,复合材料的电催化活性有了明显的提高;进一步研究发现,复合材料的电催化活性不仅受到体系性质的影响,还与其物相组成和微结构相关.上述结果说明,通过控制复合材料的物相组成及微结构,以及反应体系的性质可实现对其电催化活性的调控;同时表明,核壳结构是提高碳化钨催化材料活性的有效途径之一.     

Characterization and gas permeation of polycarbonateliquid crystal composite membrane

Polymer/liquid crystal composite membranes were cast from a 1,2-dichloroethane solution of polycarbonate (PC) and N-(4-ethoxybenzylidene-4'-n- butylaniline) (EBBA). The mixing state of the polymer/liquid crystal composite membrane was investigated on the basis of differential scanning calorimetry, x-ray, density, sorption isotherm and sorption—desorption studies and also by electron microscopic observations. EBBA molecules in the composite membrane exist in an almost molecularly dispersed state up to an EBBA fraction of 30 wt%, and in the case of EBBA fractions above 30 wt% form a crystal domain as the mutual continuous phase among the network of polycarbonate fibrils. The composite membrane containing EBBA of 60 wt% can be handled as a homogeneous medium when considering gas permeation.The diffusive permeability coefficient to water reveals a distinct jump in the vicinity of the crystal—liquid crystal phase transition temperature of EBBA. The permeability coefficients, P, to hydrocarbon gases increases 100-200 times over several degrees in the phase transition temperature range. P for hydrocarbon gases decreases with increasing number of carbon atoms below the phase transition temperature, but increases with increasing number of carbon atoms above it. These results suggest that the permeation process is predominantly controlled by diffusion mechanism below the transition temperature of EBBA, while the solubility factor significantly affects gas permeation above it.     

Complex study of reorientational dynamics of the liquid crystal in PDLC films

Morphological, electro-optical and switching properties of polyester resin/nematic liquid crystal composite films have been studied for varying composition (10-40 wt% of LC), temperature (20-50 C), film thickness (10-75 mum) and UV curing time of the matrix (0.25-12 min). The PDLC films were formed by LC separation in a UV polymerization process of the thin layer of oligoester resin (liquid crystal mixture) between ITO coated glass plates. The electro-optical and response behaviour based on the electric field controlled light scattering of the composite films was observed. The results were interpreted in terms of effective anchoring strength at the interface of the polymer and liquid crystal depending either on the area fraction of the interface in the composite film (dependent on the size and shape of the liquid crystal droplets) or the stiffness and resistivity of the polyester resin changing in the course of the crosslinking polymerization.     

Preparation and properties of ZnO nanorod array/liquid crystal composite system

ABSTRACT

In this study, By hydrothermal reaction, we prepared ZnO nanorod array of high aspect ratio with different growth time. The prepared ZnO nanorod array was on one side of the liquid crystal cell, the another side of the liquid crystal cell is ITO-glass, then the ZnO nanorod array/liquid crystal composite was injected into the liquid crystal cell. Experimental results showed that the bandwidth of the reflection spectrum of the ZnO nanorod array/liquid crystal composite system was wider than the system without ZnO nanorod array. In addition, effects of polymerisation temperatures and the length of ZnO nanorod array on the broad-band reflection of N*-LC composite films were systematically investigated.     

晶种和溶剂对复合分子筛形成的影响

采用包埋法合成ZSM-5/SAPO-5核壳结构复合分子筛,研究了凝胶组成对该材料性能的影响,并利用X射线衍射和扫描电镜等手段对其进行了表征。结果表明,合成的分子筛是以ZSM-5为核,SAPO-5为壳的双结构复合分子筛。通过向凝胶中加入晶种或者调节溶剂性质可以明显改变复合材料的结晶度和颗粒形貌。引入晶种合成材料的颗粒形貌以椭圆型为主,分子筛的结晶度增加;以醇和水混合物为溶剂合成分子筛的颗粒仍以球形为主,分子筛的结晶速率降低,结晶度的最高值降低。     

顺丁橡胶／酯－醚液晶复合膜的富氧性能研究

首次制成顺丁橡胶（ＰＢ）与具有二重液晶相转变（近晶相，向列相）的液晶化合物双４－（４’－乙氧基苯甲酰氧基）苯甲酸一缩乙二醇酯（ＤＥＢＥＢ）的复合膜并研究了其富氧性能。ＰＢ／ＤＥＢＥＢ复合膜在液晶含量１０％时，室温下具有比基质聚合物ＰＢ膜大几倍的氧透过系数（ｐｏ２）。透过系数与温度的关系曲线呈现“Ｎ”型特征。这些现象与液晶的二重相变行为和膜的形态结构有关。     

Biomimetic strengthening polylactide scaffold materials for bone tissue engineering

In this paper, a new polylactide (PLA)-based scaffold composite by biomimetic synthesis was designed. The novel composite mainly consists of nano-hydroxyapatite (n-HA), which is the main inorganic content in natural bone tissue for the PLA. The crystal degree of the n-HA in the composite is low and the crystal size is very small, which is similar to that of natural bone. The compressive strength of the composite is higher than that of the PLA scaffold. Using the osteoblast culture technique, we detected cell behaviors on the biomaterial in vitro by SEM, and the cell affinity of the composite was found to be higher than that of the PLA scaffold. The biomimetic three-dimensional porous composite can serve as a kind of excellent scaffold material for bone tissue engineering because of its microstructure and properties. Translated from Journal of Hunan University (Natural Sciences), 2006, 33(2) (in Chinese)     

Crystal Orientation Mapping Applied to the Y-TZP/WC Composite

 Crystal orientation measurements made by electron backscattered diffraction (EBSD) in the scanning electron microscope (SEM) and microscopic observations provided the basis for a quantitative investigation of microstructure in an yttria stabilised, tetragonal zirconia-based (Y-TZP) composite. Automatic crystal orientation mapping (ACOM) in a SEM can be preferable to transmission electron microscopy (TEM) for microstructural characterisation, since no sample thinning is required, extensive crystal data is already available, and the analysis area is greatly increased. A composite with a 20 vol.% tungsten carbide (WC) content was chosen since it revealed crystal relationships between the matrix and carbide phase already established by TEM analysis. However, this composite was difficult to investigate in the EBSD/ SEM since it is non-conductive, the Y-TZP grain size is of the order of the system resolution, and the sample surface, though carefully prepared, reveals a distinctive microtopography. In this paper, some useful solutions to these problems are discussed and the resulting data, which confirm crystal correlations previously established by TEM analysis, are presented.     

核壳结构的Beta-Y复合分子筛的合成与表征

采用两种不同的水热晶化法合成Beta-Y复合分子筛,并采用XRD、SEM-EDS、FT-IR、N₂ 吸附-脱附技术对其进行表征。结果表明,以Beta分子筛为唯一硅源合成的sample A具有Y和Beta分子筛两种晶型结构,为机械混合形式;而以Beta分子筛母液为前躯体合成的sample B为核壳结构的复合分子筛,具有Y和Beta分子筛两种晶型结构,其核相为Beta分子筛,壳层为Y型分子筛,其晶体中具有介孔结构,并且介孔孔径比较集中。     

Fabrication of tunable colloid crystals from amine-terminated polyamidoamine dendrimers

A pH-responsive colloidal crystal was assembled using core-shell composite spheres, poly(styrene-methyl methacrylate-acrylic acid) (P(St-MMA-AA)) spheres covered by generation 4 amine-terminated polyamidoamine dendrimers. The light reflection of the colloidal crystal film can be tuned at different pH due to different protonation level of the dendrimers. The method shows a facile way to fabricate diffraction-based chemical and biological sensors by exploiting the effect of photonic crystal cooperated with tunable nanoparticles.     

3D-ordered macroporous materials comprising DNA

Macroporous materials comprising DNA were fabricated with the colloidal crystal template. First, DNA and diazoresin (DR) molecules are fully filled into the voids of a colloidal crystal template. After thermal treatment and removal of the colloids, DNA porous materials with highly ordered structure were obtained. In the process of thermal treatment the cross-linking reaction takes place between DR and DNA, which plays an important role for sustaining the porous framework. The DNA porous materials will turn into a fluorescent DNA/dye composite after staining with Hoechst 33258 (Hoe), a characteristic fluorescent dye for DNA. This kind of composite DNA porous material may have potential applications in optical devices.     

Interfacial Interaction of Polymer/Liquid Crystal Molecules and Electrooptical Properties of their Composite Systems

Polymer/liquid crystal composite films were prepared from a solution of polymer and nematic liquid crystal (LC) by a solvent casting method. The phase-separated structure of the composite film was controlled by the solvent evaporation rate. The light-scattering profile of a poly(diisopropyl fumarate)/LC: 40/60 w/w solution during solvent evaporation exhibited a periodic structure, indicating that the phase-separated structure was formed by spinodal decomposition. The aggregation structure of the composite film was investigated with a scanning electron microscope (SEM). SEM observation of the composite film suggested the presence of periodicity and dual connectivity of polymer and LC phases. The faster the solvent was evaporated, the smaller the LC channel (domain) size in the composite film. The composite film, composed of poly(methyl methacrylate) (PMMA) and a nematic LC (E44) with a positive dielectric anisotropy, exhibited remarkable and reversible light-scattering-light-transmission switching, under the modulation of an ac electric field. The light-scattering state was dependent on such optical heterogeneities as spatial distribution of the nematic directors and/or mismatching in the refractive indices of the components. The electrooptical behavior of the composite film was strongly dependent on the LC channel (domain) size in the composite film. The transmittance increased and the rise and decay response times (τ_R and τ_D), decreased and increased, respectively, with an increase in the size of the LC channel (domain).

The electrooptical switching properties for the polymer/LC composite film should be influenced by miscibility between the polymer and the LC phases. The miscibility between both phases was evaluated from a distribution of relaxation time for interfacial polarization. The anchoring effect was also investigated by measuring the nonlinearity of the dielectric constant for the composite system.     

Reduced graphene oxide/2D colloidal array composite membrane fabricated layer-by-layer

A layer-by-layer composite membrane based on reduced graphene oxide (RGO) and two-dimensional (2D) colloidal crystal array (CCA) was fabricated, which showed promising potential for the applications as sensors and optoelectronic devices.