新型铱(Ⅲ)配合物有机磷光材料的合成及性能研究

以苯甲酰氯及其衍生物、邻氨基苯硫酚等为原料, 通过与无水三氯化铱及乙酰丙酮配合, 合成了一系列新型的取代2-苯基苯并噻唑合铱(Ⅲ)的乙酰丙酮类配合物有机磷光材料, 并对产物进行了核磁、红外、质谱和元素分析等结构表征及溶解性能、热稳定性和紫外吸收光谱、荧光光谱等发光性能的研究. 结果表明, 此类配合物在二甲亚砜和三氯甲烷等有机溶剂中具有良好的溶解性; 配合物分解温度高, 可达338～360 ℃, 具有较高的热稳定性, 其高温升华现象十分有利于真空热蒸镀薄膜的制备; 此类配合物在紫外-可见吸收光谱上的250～350 nm处出现了强的配体自旋, 允许单重态π-π*跃迁吸收峰, 在400～530 nm处出现了配合物分子内金属铱到配体的单重态和三重态电荷跃迁吸收峰(1MLCT和3MLCT); 同时, 该类铱(Ⅲ)配合物在发射光谱560～600 nm处出现了强的黄光发射, 并且在室温下表现出较高的荧光量子效率.     

关于噪声社会反应测定方法的国际共同研究——中国语噪声调查问题和评价尺度的建构

在有关噪声问题的社会调查中,由于不同的研究者采用了不同的调查问题和反应尺度,使得这些研究结果难以进行比较和借鉴。为了解决这个问题,ICBEN Team 6提出了制订标准的噪声社会反应测定方法的提案。本文就是在国际噪声联合专家研究结果的基础上,尝试建立中国语标准噪声调查问题和5级噪声反应言语尺度。     

Finite size effect on the Raman frequency of phonons in nano-semiconductors

A comprehensive study on Raman spectroscopy with different excitation wavelengths, sample sizes, and sample shapes for optic phonons (OPs) and acoustic phonons (APs) in polar and non-polar nano-semiconductors has been performed. The study affirms that the finite size effect does not appear in the OPs of polar nano-semiconductors, while it exists in all other types of phonons. The absence of the FSE is confirmed to originate from the long-range Fr¨ohlich interaction and the breaking of translation symmetry. The result indicates that the Raman spectra of OPs cannot be used as a method to characterize the scale and crystalline property of polar nano-semiconductors.     

锥体上滚实验的力学分析

分析了锥体上滚运动的动力学方程,并通过受力分析方法求解出锥体上滚的条件,结果与通过能量最低原理得出的结论一致.     

Microwave Solvothermal Synthesis,Crystal Structures and in Vitro Antitumor Activities of Di-n-butyltin Piperonylate with a Sn_4O_4 Ladder Framework

A two-dimensional supramolecular compound di-n-butyltin piperonylate, {(μ_3-O)(μ_2-OMe)(n-Bu_2Sn)_2[O_2CAr(C_2H_4O)]}_2 constructed by hydrogen bonds with a Sn_4O_4 ladder-like framework, was obtained by the microwave-assisted solvothermal reaction of di-n-butyltin oxide precursor with the piperonylic acid in methanol environments. The composite was characterized by elemental analysis and IR(~1H, ~(13)C and ~(119)Sn) NMR spectra. The compound crystallizes in monoclinic system, space group P21/n with a = 13.3690(12), b = 14.1442(14), c = 16.4022(16) ?, β = 107.191(6)°, V = 2963.0(5) ?~3, Z = 2, Dc = 1.520 g/cm~3, F(000) = 1368, μ = 1.719 mm~(-1), Mo Kα radiation(λ = 0.71073 ?), the final R = 0.0495 and w R = 0.1260 for 6780 observed reflections with I 2σ(I). Its X-ray crystallography diffraction analyses show a Sn_4O_4 ladder-like skeleton, in which two endocyclic tin and one exo tin atoms are bonded to the μ_3-O atom. In addition, one endocyclic tin and one exo tin atoms are respectively bonded to the μ_2-O atom from methanol. The ladder-like molecule has a three-ring fused skeleton, which is almost coplanar. The endocyclic and exocyclic tin atoms were all five-coordinated with distorted trigonal bipyramidal geometry. The antitumor activity showed that the compound had higher activities than cisplatin in HT-29, HepG2, MCF-7, KB and A549 cell line in vitro.     

中立型分数阶微分滑模系统的稳定性

文章主要讨论中立型分数阶微分滑模控制系统的稳定性问题.首先介绍分数阶积分、微分及广义Gronwall不等式的一些定义,然后构造切换面,给出控制律,最后通过李雅普诺夫定理来证明切换面存在,并得出系统的稳定性成立.     

三环己基锡吡啶酸甲酯的合成、结构、热稳定性及其量子化学计算研究

利用吡啶-3-甲酸与Cy3SnOH反应合成了[(C5H4N)COOSnCy3]n,经元素分析、1H NMR、IR和X-射线衍射表征分子结构。在该配合物的结构中,中心Sn原子呈现五配位畸变三角双锥构型,并通过分子间的N→Sn配位形成一维链状线型聚合物,分子链间的C-H…O氢键作用将配合物分子组装成三维超分子网络结构。利用量子化学G03W软件,在LANL2DZ基组对配合物的稳定性、前沿分子轨道组成及能量进行研究。热重分析表明该化合物在273℃开始发生分解。     

基于Diels-Alder点击反应构建壳聚糖-O-聚乙二醇接枝共聚物

通过Diels-Alder(D-A)反应,合成了具有规整化学结构的接枝共聚物,壳聚糖-O-聚乙二醇(CS-O-PEG).D-A反应所需双烯体(呋喃环)通过糠基硫醇与端甲基丙烯酸酯聚乙二醇之间的巯基-丙烯酸酯(thio-acrylate)反应合成得到;马来酰亚胺基丙酸通过活泼酯法偶联到十二烷基硫酸钠-壳聚糖复合物(SCC)羟基上,从而获得亲双烯体.采用红外光谱(FTIR)和核磁共振(1H-NMR)表征了中间产物与最终产物的结构,并用原位核磁监测D-A反应及其逆反应过程.结果表明,聚乙二醇双烯体可在水介质中温和条件下定量接枝到壳聚糖羟基上,反应具有点击特征;同时,聚乙二醇与壳聚糖之间的连接键在高温下(90℃)可通过D-A逆反应而发生断裂.