Chiral Interlocked Corrole Dimers Directly Linked at Inner Carbon Atoms of Confused Pyrrole Rings

A facile synthetic strategy towards conformationally stable chiral chromophores based on dimeric porphyrinoids has been established. A peculiar class of face-to-face intramolecularly interlocked corrole dimers were formed by the oxidative C−C coupling linked at the inner carbon sites upon simple treatment of copper(II) ions. Their intrinsic electronic structures were modulated by the peripheral corrole ring annulations, which lead to distinct optical properties and redox profiles. The stereogenic carbon centers implemented in the confused corrole skeleton provided a rationale for designing novel chiral materials.     

Synthesis and applications of chiral bis-THF in asymmetric synthesis

The synthesis of enantiopure bis-THF is described, starting from d-mannitol. Bis-THF is used as chiral ligand for organolithium reagents in four different reactions. The enantioselectivity provided by this ligand is moderate, and the asymmetric induction is in line with the expected model.     

WZW–Poisson manifolds

We observe that a term of the WZW-type can be added to the Lagrangian of the Poisson σ-model in such a way that the algebra of the first class constraints remains closed. This leads to a natural generalization of the concept of Poisson geometry. The resulting “WZW–Poisson” manifold M is characterized by a bivector Π and by a closed three-form H such that 1/2[Π,Π]_Schouten=H,ΠΠΠ.     

Epimerization, diastereoselectivity and hemilability in dicationic chiral ruthenium complexes with bidentate (PS) bisphosphine monosulfide ligands

The binding of heterobidentate P^∧S ligands introduces metal-centered chirality to the planar chiral parent complex Ru(η⁶:η¹-NMe₂C₆H₄C₆H₄PCy₂)Cl₂. Observed diastereomeric ratios for the kinetic product vary dramatically depending upon ring size of the chelate formed with the P^∧S ligand. The complexes epimerize very slowly to thermodynamic product ratios that are substantially different from the kinetic product ratios.     

聚(酪氨酸酯对苯二甲酰胺)碳酸酯药物控制释放材料的研究

报道了一类生物可降解聚（酪氨酸酯对苯二甲酰胺）碳酸酯的合成和结构表征，研究了聚合物的性质和体外降解性能，并以５ 氟脲嘧啶和牛血清白蛋为模型，对它们作为药物控制释放材料的性能进行了初步评价．     

聚醋酸乙烯酯的光引发可控合成——介绍一个高分子化学综合实验

本实验开展了醋酸乙烯酯的可逆加成-断裂链转移自由基聚合(RAFT),分别运用偶氮二异丁腈(AIBN)引发和可见光引发两种方式进行了聚合反应,运用核磁共振和凝胶色谱等多种手段对所得聚合物结构进行了表征与分析。通过比较AIBN引发与光引发所获得聚合物端基结构的异同,加深了学生对RAFT聚合方法原理的理解。同时,运用该方法实现了聚合物两端端基结构的高度功能化,深入体会聚合物合成设计概念。本综合实验教学不仅通过对比法加深了学生对实验原理和专业知识的理解,提升了学生创新研究能力,而且训练了学生的实验操作技能、大型仪器使用能力和结果分析能力,提升了综合素质。     

固体CD光谱研究及其应用于手性席夫碱M(II)配合物

结合课题组近期的相关研究,对固体CD光谱在手性配合物研究中的应用,特别是手性样品固体CD光谱的测试方法进行了概述,通过对四对手性席夫碱M(II)(M=Ni、Cu)配合物的固体和溶液CD光谱进行比较研究,发现配合物的手性构型在固液相中保持一致,但其固液CD光谱之间存在不同程度的差异,可能是由于相应配合物在固体和溶液相中的四面体扭曲或构象的微妙不同所致.     

温度及pH敏感的树枝状高分子衍生物合成及药物控制释放研究

对合成的系列聚酰胺-胺型(PAMAM)树枝状高分子进行端基的羟基化和氯乙酰化两步修饰,使PAMAM最外层接上烷基氯.以修饰产物为引发剂,通过原子转移自由基引发甲基丙烯酸N,N-二甲氨基乙酯(DMAEMA)聚合得到树枝状PAMAM高分子衍生物,并对其结构用FTIR、1H-NMR和粒径分析进行了表征.紫外可见分光光度仪测定证实此高分子具有温度及pH敏感性.通过对小分子药物控制释放研究表明,此树枝状高分子衍生物通过环境pH值可有效地控制小分子药物的释放.     

Electrochiroptical systems based on biphenyl-2,2′-diyl-type dicationic dyes: strong chiroptical signals through the transmission of point chirality to axial chirality

Huge CD amplitude (A = +538) was attained by diastereomeric preference (50% de) for the title dication with two bis[4-(R)-sec-butoxyphenyl]methylium units in benzene at 23 °C. Intramolecular π-π stacking is the origin for effective transmission of point chirality to axial chirality to attain the chiroptical enhancement of 400-times. Thanks to the strong CD signaling, chiroptical changes upon electrolysis could be readily detected, thus realizing a new class of electrochiroptical response systems. Chiroptical properties could also be modified by solvent polarity.     

Chiral Derivatives of Achiral Molecules: Standard Classes and the Problem of a Right-Left Classification

Chemistry judging by its applications, physics according to its methods, and heavily reliant upon the tools of mathematics—that is what makes theoretical chemistry. And yet that is where its strength lies—in the variety of these sciences. It is quite natural that, in answer to specific problems, results and methods can sometimes be developed whose scope extends far beyond the original application. Rather it is a mark of quality if consequences can be found in chemistry and physics and the pathway leads via new mathematical procedures and concepts. Regrettably, any publication aiming to present such aspects will usually encounter little resonance since the linguistic confusion in science, its disciplines, and subdisciplines, lies like a veil over our understanding. The author nevertheless wishes to attempt to present, in a series of articles, results of research into chemical themes in a manner designed to appeal to the interest of chemists, without neglecting interdisciplinary aspects. All that is required to understand the argumentation is a lively interest. The first two articles are concerned with the chirality of molecules, and in particular with questions relating to the chirality phenomenon of molecules in the framework of molecular classes. In view of the algebraic nature of the mathematical methods adopted, it is not surprising that precise statements result. It appears of primary interest to establish the degree to which such statements can be considered valid for molecular models or molecules themselves.