柱芳烃单分子管人工通道构筑及其对手性氨基酸的选择性跨膜输送  

Construction of Pillarene Single Molecular Tubes as Artificial Transmembrane Channels for Selective Transport of Chiral Amino Acids

作　　者：黎占亭[1] 张丹维[1] 侯军利[1] 赵亮[2] Li Zhanting;Zhang Danwei;Hou Junli;Zhao Liang(Fudan University;Tsinghua University)

机构地区：[1]复旦大学 [2]清华大学

出　　处：《科技资讯》2016年第22期176-177,共2页Science & Technology Information

摘　　要：该课题通过设计结构精确的分子单体,通过氢键、配位作用及疏溶剂作用和pi-pi堆积作用等为驱动力,构筑多层次的自组装体系,进而探索组装体的功能。2013年度,我们根据计划书要求开展工作,在以下几个方面取得重要进展:(1)设计了一类三角型平面分子,在其周围引入单N-苯基联二吡啶VB+,通过葫芦脲[8]对两个VB单元的强络合作用,在水相中实现了有序蜂窝型超分子有机框架(SOF)结构的自组装。(2)设计了两类刚性四面体分子,分别引入4个紫精和四硫富瓦烯片段,在把紫精还原或把四硫富瓦烯氧化为正离子自由基后,这两类正离子自由基在水相强烈堆积,从而诱导其形成三维网络超分子组装结构。(3)利用氢键控制芳香酰胺线性分子的构象,从而研究其结构-性质关系,并进而利用构象控制开展分子识别与自组装研究。1利用单分子力谱首次研究了驱动形成芳香酰胺螺旋孔状结构的氢键的强度及不同位置氢键强度的差异;2利用手性离子对识别,从并入氢键折叠片段的UPy四氢键组装单体构筑了一类交替堆积的手性超分子聚合物;3设计合成了两个大环分子,引入酰胺和1,2,3-三氮唑片段,通过对二酰胺和三碘客体分子的氢键和卤键结合,研究了分子间氢键和卤键的相对强度;4设计了新的双卟啉和三卟啉主体分子,通过分子内氢键诱导其形成刚性梳型构象,进而用于研究配位作用和堆积作用协同诱导的多组分超分子结构组装。(4)在配位自组装研究方面取得重要进展:1研究了含有氮杂环卡宾-金属键的金属有机大环分子的合成,发现氮杂环卡宾与11族金属(Cu,Ag,Au)可以形成较强的配位键,由此获得了中间桥连基团是不同长度、含有不同吡啶数目的系列金属有机大环分子;2对含有多配位位点的氮杂杯吡啶大环分子进行配位组装及金属簇可控合成的机理进行了深入研究。发现含有多个�We achieved progresses in the following aspects: (1) We designed and synthesized a new kind of triangular planar molecules which were attached with three N-phenyl 4,4’-bipyridyl (BP) units. By utilizing the strong encapsulation of cucurbit[8]uril (CB[8]) for two BP, for the first time, we assembled a series of 2D honeylcomb-styled supramolecular organic framework (SOF). (2) We designed and prepared two tetrahedral monomers which contained four viologen or tetrathiafulvalene (TTF) units. We found that when the viologen was reduced or TTF was oxidized to its cation radical, due to the tetrahedral feature of the molecules, the cation radicals could strongly dimerize in solution for the molecules to form 3D supramolecular networks. (3) We also succeeded in using hydrogen bonding to control the required conformation of aromatic amide sequences.By investigating their structure-property relationship, we constructed several series of supramolecular systems. ①We utilized single molecular force spectroscopy to evaluate the strength of intramolecular hydrogen bonding; ②By making use of ion pair recognition, we constructed a new kind of alternately arranged chiral supramolecular copolylmers from two aromatic amidelinked UPy ditopic monomers.③We designed and prepared two macrocycles which contained amide and 1,2,3-triazole segments. By investigating their binding toward diamide and triiodide guests, we evaluated the relative strength of intermolecular hydrogen bonding. (4) We also made progresses in the area of coordination self-assembly.①We succeeded in preparing new coordination macrocycles which contained azaheterocyclic carbine units and found that the azaheterocyclic carbenes could coordinate to Cu(II), Ag (I) or Au (III) to form coordination macrocycles that contained different pyridine rings;②We also investigated the mechanism of the formation of the above coordination macrocycles and found that the N atoms of pyridines incorporated in the macrocycles might bind to multiple metal ions to form separated enti

关 键 词：自组装 多层次 氢键 配位作用 人工通道 

分 类 号：O629.12[理学—有机化学]