Rotational Motion of a Solute Molecule in a Highly Viscous Liquid Studied byC NMR: 1,3-Dibromoadamantane in Polymeric Chlorotrifluoroethene

The viscosity-dependent retarding effect of a polymeric solvent on the rotation of small solute molecules is investigated by¹³C NMR relaxation measurements. It is found that the relaxation data of 1,3-dibromoadamantane in highly viscous polymeric chlorotrifluoroethene can be explained neither by isotropic nor by realistic anisotropic tumbling in a single environment. The experimental data are rationalized in terms of fast exchange between at least two environments with correlation times differing by up to two orders of magnitude. The study shows that a uniform retardation of molecular tumbling by a polymeric solvent, desirable for shifting the NMR observation window in studies of intramolecular mobility, is not always feasible.     

Synthesis and characterization of novel perfluorinated polyimides with 3D‐controlled structures for photonic applications

We have designed and synthesized novel perfluorinated polyimides with 3D controlled structure. At first, we successfully developed the new synthetic routes to diamines with pendant bulky perfluorinated aromatic units in a multi‐step synthetic procedure. Novel perfluorinated polyimides were prepared in a two‐step reaction in N‐methyl‐2‐pyrrolidinone (NMP) solution: The first step was for the synthesis of polyamic acids (PAAs) and the second reaction was for the imidization of PAA. The polymer yield was over 89% and the inherent viscosity of PAAs was in the range of 0.24–0.36 dL/g. The thin films were prepared by spin‐coating the PAA solution in NMP onto various substrates such as a Si wafer or a KBr pellet, dried at 80 °C and further cured at 230 °C. The resultant polyimides are thermally stable over 400 °C. The refractive index and birefringence of the resultant polyimides are 1.5858–1.6452 and 0.01–0.005, respectively. The refractive index of polyimide decreases with increasing the fluorine content. The copolymerization and the ether linkages into the backbone reduce the birefringence of polyimides. Surprisingly, the pendant ether linkage is not a crucial factor in reducing the polyimide birefringence. Their birefringence is comparatively very low, compared with that of previous polyimides. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1326–1342, 2006     

立体定向合成粘虫性信息素

粘虫是一种多食性害虫,分布极广。它的危害对象包括麦类、水稻、玉米等十多种粮食和经济作物。1979年Takahashi等首先确定粘虫雄蛾(Mythimna Separata male)的性信息素,这是由8:1比例混合的(Z)-11-十六碳烯-1-醇乙酸酯3和(Z)-11-十六碳烯-1-醇4组     

New Chiral Kemp's Acid Diamides for Chiral Amine Recognition by 1 H NMR

Two Kemp's acid diamides were synthesized and applied to chiral amine recognition using ¹H NMR analysis. One derivative based on 1-(1-naphthyl)ethylamine had good chiral recognition of six amines and was useful to determine the optical purity for three amines, i.e., methylbenzylamine, 1-(1-naphthyl)ethylamine and 1- henylpropylamine,however, the cyclohexylethylamine derivative showed little discrimination for the amines studied. Together with the results for alkylamines, it was shown that aromatic structure was important for aromatic shielding anisotropy and –– interactions between host and guest. The structure of the 1-(1-naphthyl)ethylamine derivative in solution was also considered based on ¹H NMR data and computer simulation.     

微波辐射下蒙脱土K10固载氯化铁氧化二芳基乙醇酮

微波辐射下以蒙脱土K-10固载氯化铁为氧化剂, 氧化二芳基乙醇酮生成二芳基乙二酮化合物, 反应时间短, 产率高, 操作简便, 污染小, 是一种有效的由二芳基乙醇酮氧化制备二芳基乙二酮的方法.     

聚丙烯酰胺/醋酸铬与聚丙烯酰胺/酚醛胶态分散凝胶的纳米颗粒自组织分形结构

采用原子力显微镜 ,分别对无机交联体系聚丙烯酰胺 Cr3+ 和有机交联体系聚丙烯酰胺 酚醛胶态分散凝胶的微观结构进行了显微图像分析 .发现无论是在有机还是无机交联体系中 ,也无论聚丙烯酰胺和交联剂浓度如何变化 ,在微米尺度上最终形成的都是具有自相似性的树枝状分形图像 ,在更小尺度上则发现单个小树杈分形体都是由纳米级的颗粒紧密堆积而成 .在所研究的胶态分散凝胶体系中 ,树枝状分形结构的形成及其具体的形态取决于聚丙烯酰胺的浓度 ,而交联剂的有无及其多少只对树枝状凝胶分形的几何形态产生一定影响 .实验结果还表明纳米级 (≤ 10 0nm)的胶体颗粒构成的分形结构的凝胶其弹性模量G′比微米级的高出一个数量级 .且粒子尺度越小 ,则凝胶的力学稳定性越强     

Synthesis of 1,3-diarylbenzo[c]selenophenes

For the first time, syntheses of 1,3-diarylbenzo[c]selenophenes are reported involving a selenium transfer reaction of keto-alcohol/benzo[c]furan using Woollins reagent.     

高纯度植酸的制备

高纯度植酸的制备孙定光胡佩廖显威（四川师范大学化学系成都６１００６６）关键词植酸制备高纯试剂中图分类号Ｏ６２９．９植酸（ＰｈｙｔｉｃＡｃｉｄ）又名肌醇六磷酸酯，分子式：Ｃ６Ｈ１８Ｏ２４Ｐ６，结构为植酸是中等强度的有机酸，因其结构特殊，具极强的螯合作用...     

铜催化下格氏试剂与α,ω-二溴代烷的偶合反应

七十年代发展了铜催化下格氏试剂与卤代物、磺酸酯、酰卤的选择性交叉偶合反应,以后对这类反应并未深入研究。我们以几种铜     

聚氯乙烯接枝丙烯酸稀土的研究

将无机稀土有机化后与聚氯乙烯(PVC)进行接枝共聚。探讨了氧化稀土与丙烯酸反应、PVC接枝丙烯酸稀土的原理和方法，并通过红外光谱、扫描电镜对接枝共聚物进行定性表征，用微量热天平对接枝共聚物的热性能进行测定。实验结果表明，经丙烯酸稀土接枝共聚后的PVC，其耐热分解性能和韧性有了明显的提高。