前驱体水解对纳米铂形状控制合成的影响

以聚丙烯酸钠(NaPA: M_w ≈ 2100)为保护剂，对比研究了H_2还原K_2PtCl_4 和K_2PtCl_6水溶液制备纳米铂晶粒的形状选择性，揭示了前驱体的水解对纳米铂 晶粒的形状控制合成具有显著影响。文献中通常采用的合成立方形状纳米铂的 K_2PtCl_4前驱体在水溶液中不稳定，避光静置一周会析出黑色沉淀。这种不稳定 性导致了以K_2PtCl_4为Pt前驱体的合成结果难以重复。相比而言，避光静墨的 K_2PtCl_6水溶液很稳定，以它为前驱体合成的纳米铂通常为削角八面体。 K_2PtCl_6水溶液暴露于室内光线中会出现[PtCl_6]~(-2)的光致水解。当[PtCl_6] ~(2-)的紫外特征吸收峰(260nm)由于光致水解完全消失后，以聚丙烯酸钠为保护剂 ，通过H_2还原可以有选择性地(约80%)合成由{100}晶面包裹的立方体形状的纳米 铂。     

An Integrated Theory of Adsorption and Partition Mechanism and Eash Contribution to Solute Retention in Reversed Phase Liquid Chromatography

With the combination of the the stoichiometric displacement model for retention (SDM-R) in reversed phase liquid chromatography (RPLC) and the stoichiometric displacement model for adsorption (SDM-A) in physical chemistry,the total number of moles of the re-solvated methanol of stationary phase side.nr,and that of solute side in the mobile phase,q,corresponding the one mole of the desorbing solute,were separately determined and referred as the characterization parameters of the contributions of the adsorption mechanism and partition mechanism to the solute retention,respectively.A chromatographic system of insulin,using mobile phase consisting of the pseudo-homologue of alcohols(methanol,ethanol and 2-propanol)-water and trifluoroacetic acid was employed.The maximum number of the methanol layers on the stationary phase surface was found to be 10.6,only 3 of which being valid in usual RPLC,traditionally referred as a volume process in partition mechanism.However,it still follows the SDM-R.Both of q and nr of insulin were found not to be zero,indicating that the retention mechanism of insulin is a mixed mode of partition mechanism and adsorption mechanism.When methanol is used as the organic modifier,the ratio of q/nr was 1.13,indicating the contribution to insulin retention due to partition mechanism being a bit greater than that due to adsorption mechanism.A linear relationship between q,or nr and the carbon number of the pseudo-homologue in the mobile phase was also found.As a methodology for investigating the retention mechanism retention and behavior of biopolymers.a homologue of organic solvents as the organic modifier in mobile phase has also been explored.     

硝酸银及其产物银对六角相液晶流变性影响

用偏光显微镜测定了硝酸银及其产物银对NP－10／水六角相区的影响，用动态 （应力和频率扫描）和稳态（蠕变－恢复）方法研究了硝酸银的加入和银的生成对 该体系粘弹性的影响。无机前驱物硝酸银和银的生成能使六角相区略缩，动态流变 实验表明，无机物引入纯六角相液晶体系中会使其抗剪切的能力降低，对相区两侧 影响与振荡所采用的频率有关。生成的银原子会在胶束表面聚集，增加了胶束内部 不同EO链之间的交联，造成松弛时间变长，粘弹性指数降低，稳态实验所得到的结 果与动态实验一致，并将粘性和弹性定量化。用弹簧－粘壶模型和液晶的空间构型 及作用力解释了实验结果。     

制备具有光催化活性的金红石相纳米氧化钛粉体

以TiCl4为原料，通过控制盐浓度和水解温度可以在温和条件下制备出晶粒尺 寸为6nm的金红石相氧化钛粉体，比表面积为175m^2/g。测定了粉体的X衍射、红外 和拉曼光谱。TEM照片显示粉体呈放射状颗粒，其粒径尺寸在200－400nm。苯酚的 光催化降解实验表明它比具有相同比表面积的锐钛矿粉体有更高的光催化活性。其 较大的团聚颗粒尺寸有利于光催化反应后的分离。     

纳米结构TiO2／SiO2的逐层自组装

采用逐层自组装方法在二氧化硅球表面交替组装了十二烷基硫酸钠单分子膜和 二氧化钛纳米粒子膜，该复合多层膜经高温假烧后得到了核壳型纳米结构二氧化钛 ／二氧化硅复合颗粒．利用XRD，SEM，X射线能谱等对复合颗粒进行了表征．结果 表明：二氧化肽在复合颗粒表面排列紧密、均匀，粒径在50nm左右，为锐钛矿型结 构．复合颗粒中二氧化肽的含量随组装层数的增加而均匀增加．     

颜色可调Sr3Y（BO3）3∶Tm3+，Dy3+荧光粉的发光性能及能量传递

采用高温固相法制备了Sr_3Y(BO_3)_3:xTm~(3+),yDy~(3+)荧光粉,并通过XRD、SEM和荧光光谱仪对样品的物相、微观形貌、发光性能、能量传递机制和CIE色坐标进行了分析。结果表明:Sr_3Y(BO_3)_3:xTm~(3+)荧光粉在监测波长为359 nm时发射蓝光,Tm~(3+)的浓度淬灭点为x=0.08;在Sr_3Y(BO_3)_3:0.08Tm~(3+),yDy~(3+)荧光粉中,随着Dy~(3+)掺杂浓度的增加,Tm~(3+)的发光强度降低而Dy~(3+)发光强度却先增加后降低,Dy~(3+)的浓度淬灭点为y=0.1;通过改变Dy~(3+)掺杂浓度或改变激发光的波长,均可实现发射光的颜色可调;在Tm~(3+)-Dy~(3+)离子之间存在能量传递。当Dy~(3+)掺杂浓度(物质的量分数)为0.15时能量传递效率达75.14%,能量传递机制为电偶极-电偶极相互作用。     

微波辅助RGD环肽的固相合成

以2-氯代三苯甲基氯树脂为载体，采用Fmoc/t-Bu/Dmab正交保护策略，在微波辅助下合成了环肽c(fKRGD)，收率22.5%，纯度94.5%，其结构经MS(ESI), MS(MALDI-TOF)和HPLC确证。     

固相萃取新技术研究

固相萃取技术是一种用于样品分离、纯化、浓缩的重要的样品前处理手段。近年来,高分子材料合成技术、分子印迹技术等新技术与传统固相萃取技术相结合,衍生出众多技术改进和创新。主要对各种固相萃取新技术进行评述。