葫芦脲作为超分子纳米反应器/催化剂的研究

葫芦脲是近年来获得广泛关注和长足发展的一种新型超分子主体化合物,其刚性的结构、疏水性的空腔及电负性的端口赋予其极为特殊的识别性质--对有机阳离子客体的高选择性和高亲合性。过去的十几年里,学者们利用其独特的性质将其应用在包括从基本的分子识别与组装到复杂的三维材料的制备以及药物传输及缓释等各个领域中。此外,创造性地将葫芦脲分子用于控制化学反应进程则成为了葫芦脲化学又一备受瞩目的研究方向。本文介绍了葫芦脲及其衍生物作为超分子纳米反应器/催化剂的研究工作,重点介绍了近年来国际国内在此领域取得的部分研究成果,主要包括葫芦脲通过主客体作用对反应底物的反应活性的影响,希望能给对葫芦脲介入的化学反应感兴趣的研究人员提供参考。     

基于葫芦[7]脲主体的功能超分子体系的构筑及应用研究

<正>超分子化学是研究两个或两个以上分子通过非共价作用形成复杂有序体系的科学.主客体化学是超分子化学的重要研究内容之一,构筑具有环境响应性质的新型主客体功能化体系是主客体及超分子化学研究中的重要内容,具有广泛的应用前景。本论文合成了一系列外围修饰不同客体分子的功能树枝形聚合物体系,研究了葫芦[7]脲(CB[7])主体分子和树枝形聚合物外围客体分子的组装行为,探讨了主客体作用在药物可控释放和提高光捕获体系性能中的应用;构筑了一系列聚集诱导发光基团修饰的两亲分     

基于冠醚和柱芳烃主客体识别的超分子聚合物材料

超分子聚合物材料是高分子科学、超分子化学和材料科学3个学科相结合的产物.通过精妙的设计,我们不仅可以赋予它传统高分子材料所拥有的光学、电学以及力学等性能,同时还可以使其具有超分子材料的动态可逆性和刺激响应性.已用于构筑超分子聚合物材料的主客体识别体系有很多,从识别体系中的主体来说,包括基于冠醚、环糊精、杯芳烃、葫芦脲、柱芳烃等大环的主客体体系.其中,冠醚作为第一代大环主体,它的模板合成直接开辟了超分子化学这一领域,而柱芳烃是最近发展起来的一类新的大环主体,它具有刚性的骨架,并且制备简单,容易功能化,同样也受到超分子化学家们的广泛关注.本文着重综述了我们课题组基于冠醚和柱芳烃主客体识别所构筑的超分子聚合物材料.在这些材料的制备中,我们利用了主客体识别的刺激响应性、可逆性和选择性,来实现对这类材料的组装结构以及功能的精确调控.     

葫芦脲大环官能团功能化

新型大环化合物的设计与合成一直以来都是超分子化学的研究热点。冠醚、环糊精、杯芳烃和葫芦脲等经典大环分子,以及柱芳烃等新兴大环分子的发展丰富了超分子化学的研究内容。其中,官能团功能化的大环化合物被广泛应用于化学传感器、分子机器、仿生系统、超分子催化、刺激响应体系、功能材料以及药物传递等众多领域。葫芦脲大环具有一个刚性的疏水空腔,由于其独特而优秀的水相识别能力而备受关注。然而,相对于其他大环化合物,葫芦脲由于其官能团功能化难题而发展相当缓慢。近年来,葫芦脲大环官能团功能化的研究获得了巨大的突破,将葫芦脲大环的主客体识别性质从传统的超分子化学拓展到生物化学、材料化学以及药物化学等交叉研究领域。本文重点总结葫芦脲大环官能团功能化现阶段的研究进展,并对其合成方法进行简单明晰的总结与展望。     

基于柱芳烃的有机功能材料

超分子化学起源于主客体化学,其发展亦很大程度上依赖于主客体化学。而大环受体分子作为主客体化学重要组成部分在有机功能材料的构筑方面已逐渐显示出其无穷的魅力。在过去的几十年里,科研工作者们深入研究了包括冠醚、环糊精、杯芳烃、葫芦脲、柱芳烃在内的多种有机超分子主体化合物。其中,柱芳烃作为一种新型的易官能化的主体分子,由于其独特的刚性柱状结构和优良的物理、化学性质日益受到广泛关注。它为有机功能材料的制备以及超分子化学的发展提供了更多可能。到目前为止,基于柱芳烃的有机功能材料已在分子识别、细菌病毒抑制、农药检测、重金属离子识别、光传感、纳米粒子的稳定、催化、生物传感及药物控释等多个领域得到运用。本文结合这些材料现阶段的研究进展,对其在上述领域的应用进行简单明晰地总结与展望。     

领结芳烃: 刺激响应性荧光双环分子

伴随着超分子化学的诞生与发展,大环分子一直是超分子体系的重要构筑基元[1].几十年来,以冠醚、环糊精、杯芳烃、葫芦脲、柱芳烃等为代表大环分子因其优异的客体识别性质而被广泛用于功能超分子体系的设计与构建[2].然而上述大环主体分子的基本分子骨架并不具备荧光基团,因此通常需要依赖客体分子的荧光性质或者通过多步反应对大环结构作进一步化学修饰才能实现荧光主客体体系的构筑[3].鉴于荧光性质在检测、传感、成像等领域的重要用途,发展具有丰富光物理性质的新型大环骨架是一个亟需突破的重要的研究方向.     

葫芦[n]脲超分子水凝胶的研究进展

超分子化学的发展一直是众多研究者所关注的一大热点,葫芦[n]脲作为第四代大环主体分子,拓宽了超分子化学领域的发展。水凝胶是一种具有可拉伸性、生物相容性、环境响应性等多种优异性能的软材料。人们充分利用葫芦[n]脲优异的分子识别能力和配位能力,研究出了一系列具有特殊功能的超分子水凝胶材料。本文在结合葫芦[n]脲特点的基础上,着重论述了葫芦[n]脲水凝胶在(刺激响应性、粘附性、自愈合性)功能性材料、(药物传递、伤口敷料、仿生)生物医学材料、超分子发光材料等领域的研究前沿和动态,并且对葫芦[n]脲水凝胶的主要设计思路进行了讨论。最后,针对当前存在的问题以及未来可能的发展方向对葫芦[n]脲水凝胶的研究前景作出了展望。     

主客体超分子囊泡及其药物载运性能研究

伴随着新型主体分子的不断出现,主客体超分子囊泡的研究受到越来越多的关注。环糊精、杯芳烃、葫芦脲和柱芳烃等主体分子均可以和特定结构的客体分子通过主客体识别作用构筑超分子双亲分子,得到的超分子双亲分子可以进一步自组装为主客体超分子囊泡。主客体超分子囊泡是一类具有敏感响应性的囊泡体系,具有制备简单、生物相容性好和易于控制组装等优点。该囊泡体系对外界刺激具有良好的响应性,从而可以实现药物分子的可控运输和释放,使其成为一种性能独特的药物载运系统。本文结合近年来主体分子的发展,首先介绍了环糊精、杯芳烃、葫芦脲和柱芳烃等主客体超分子囊泡的研究进展,然后对该类超分子囊泡的载药途径进行了总结。该囊泡体系不仅可以在囊泡膜层和空腔中载药,还可以在主体分子的空腔中载药。同时,对载药主客体超分子囊泡的不同刺激响应性进行了归纳概括。最后结合该体系现阶段的研究状况,对该类超分子囊泡的发展前景进行了展望。     

基于主客体作用构筑的聚集诱导发光型超分子组装体 在生物医用领域的研究进展

主客体相互作用是超分子自组装过程中最重要的作用方式之一,常被用于构建多功能超分子材料.基于主客体相互作用,利用具有聚集诱导发光性质的大环主体分子或客体分子作为自组装基元,构筑具有聚集诱导发光效应的超分子体系,并将其应用于药物递送、细胞成像、生物传感等生物领域,已成为超分子化学的研究热点.从超分子组装体的发光效应分别源于主体分子和客体分子两方面,介绍了近五年来以环糊精、杯芳烃、葫芦脲、柱芳烃及其它大环为主体化合物,基于主客体作用构筑的聚集诱导发光超分子组装体,并对其在生物医用领域的研究进展进行了简要综述.     

超分子和高分子自组装的动力学模拟研究

超分子和高分子的自组装是发展新型高性能材料的有力手段.通过自组装构筑多级有序结构,从而显著提高材料的力学、光学或电学性能,是化学和材料科学研究的前沿.然而精确调控自组装需要深入理解范德华、氢键、静电、主客体复合和π-π等相互作用以及动力学机理所扮演的角色.计算机模拟,尤其是分子动力学模拟,为研究自组装结构和演化过程提供...     

Supramolecular Polymerization from Controllable Fabrication to Living Polymerization

Supramolecular polymers have attracted plenty of interest in the scientific community; however, developing controllable methods of supramolecular polymerization remains a serious challenge. This article reviews some recent developments of methods for supramolecular polymerization from controllable fabrication to living polymerization. Three facile methods with general applicability for controllable fabrication of supramolecular polymers have been established recently: the first method is a self‐sorting approach by manipulating ring–chain equilibrium based on noncovalent control over rigidity of monomers; the second is covalent polymerization from supramonomers formed by noncovalent interactions; and the third is supramolecular interfacial polymerization. More excitingly, living supramolecular polymerization has been achieved by two elegant strategies, including seeded supramolecular polymerization under pathway complexity control and chain‐growth supramolecular polymerization by metastable monomers. It is anticipated that this review may provide some guidance for precise fabrication of supramolecular polymers, leading to the construction of supramolecular polymeric materials with controllable architectures and functions.     

超分子化学发展简介

本文综述了超分子化学的定义 , 范围及内容. 着重介绍了分子识别, 分子自组装, 超分子催化, 超分子器件及超分子材料等概念. 对由此可能形成的新的前沿科学如分子电子学, 分子离子学, 分子光子学及超分子工艺学等作了扼要介绍 .     

Polymerization of supramonomers: A new way for fabricating supramolecular polymers and materials

Supramolecular polymers and materials are attracting more and more attention nowadays due to their dynamic properties such as reversibility, stimuli-responsiveness and self-healing. Conventionally, bifunctional or multi-functional monomers are first covalently synthesized, followed by the supramolecular complexation to form supramolecular polymers and materials. Recently, we have proposed the supramonomer concept to construct supramolecular polymers and materials in a different way. Supramonomers are bifunctional or multi-functional monomers fabricated by noncovalent synthesis, but can undergo traditional covalent polymerization. In this highlight article, we will summarize and discuss the fabrication of supramonomer and covalent polymerization methods of supramonomers; fabrication of multi-responsive supramolecular polymers from supramonomers; and fabrication of supramolecular materials from supramonomers. It is highly anticipated that the supramonomer concept will enrich the methodology towards supramolecular polymers and materials. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 604–609     

手性光学开关研究*

手性是自然界的普遍现象,有关超分子手性的研究由于超分子体系中分子间非共价相互作用的可调性逐渐引起了人们的研究兴趣。本文综述了手性光学开关研究的最新进展,介绍了如何设计分子体系,由手性分子制备手性光学开关;基于超分子思想,介绍了由非手性分子参与形成的手性光学开关,并最终制备出完全由非手性分子组装得到的手性光学开关。     

A Double Cation–π-Driven Strategy Enabling Two-Dimensional Supramolecular Polymers as Efficient Catalyst Carriers

The cation–π interaction is a strong non-covalent interaction that can be used to prepare high-strength, stable supramolecular materials. However, because the molecular plane of a cation-containing group and that of aromatic structure are usually perpendicular when forming a cation–π complex, it is difficult to exploit the cation–π interaction to prepare a 2D self-assembly in which the molecular plane of all the building blocks are parallel. Herein, a double cation–π-driven strategy is proposed to overcome this difficulty and have prepared 2D self-assemblies with long-range ordered molecular hollow hexagons. The double cation–π interaction makes the 2D self-assemblies stable. The 2D self-assemblies are to be an effective carrier that can eliminate metal-nanoparticle aggregation. Such 2D assembly/palladium nanoparticle hybrids are shown to exhibit recyclability and superior catalytic activity for a model reaction.     

Supramolecular Fullerene Polymers and Networks Directed by Molecular Recognition between Calix[5]arene and C60

A biscalix[5]arene–C₆₀ supramolecular structure was utilized for the development of supramolecular fullerene polymers. Di‐ and tritopic hosts were developed to generate the linear and network supramolecular polymers through the complexation of a dumbbell‐shaped fullerene. The molecular association between the hosts and the fullerene were carefully studied by using ¹H NMR, UV/Vis absorption, and fluorescence spectroscopy. The formation of the supramolecular fullerene polymers and networks was confirmed by diffusion‐ordered ¹H NMR spectroscopy (DOSY) and solution viscometry. Upon concentrating the mixtures of di‐ or tritopic hosts and dumbbell‐shaped fullerene in the range of 1.0–10 mmol L^?1, the diffusion coefficients of the complexes decreased, and the solution viscosities increased, suggesting that large polymeric assemblies were formed in solution. Scanning electron microscopy (SEM) was used to image the supramolecular fullerene polymers and networks. Atomic force microscopy (AFM) provided insight into the morphology of the supramolecular polymers. A mixture of the homoditopic host and the fullerene resulted in fibers with a height of (1.4±0.1) nm and a width of (5.0±0.8) nm. Interdigitation of the alkyl side chains provided secondary interchain interactions that facilitated supramolecular organization. The homotritopic host generated the supramolecular networks with the dumbbell‐shaped fullerene. Honeycomb sheet‐like structures with many voids were found. The growth of the supramolecular polymers is evidently governed by the shape, dimension, and directionality of the monomers.     

基于氢键作用结合的超分子聚合物

非共价键结合的超分子聚合物由于其特殊的结构及性能引起了广泛的关注。本文在介绍超分子化学、氢键及超分子聚合物的基础上,主要综述了以氢键为结合力的多重氢键作用、羧基（D）与吡啶基（A）作用以及氢键与其它非共价键协同作用形成的超分子聚合物体系,并对超分子聚合物的研究现状及前景进行了评述。     

Supramolecular Diblock Copolymers Featuring Well‐defined Telechelic Building Blocks

We report supramolecular AB diblock copolymers comprised of well‐defined telechelic building blocks. Helical motifs, formed via reversible addition‐fragmentation chain‐transfer (RAFT) or anionic polymerization, are assembled with coil‐forming and sheet‐featuring blocks obtained via atom‐transfer radical polymerization (ATRP) or ring‐opening metathesis polymerization (ROMP). Interpolymer hydrogen bonding or metal‐coordination achieves dynamic diblock architectures featuring hybrid topologies of coils, helices, and/or π‐stacked sheets that, on a basic level, mimic protein structural motifs in fully synthetic systems. The intrinsic properties of each block (e.g., circular dichroism and fluorescence) remain unaffected in the wake of self‐assembly. This strategy to develop complex synthetic polymer scaffolds from functional building blocks is significant in a field striving to produce architectures reminiscent of biosynthesis, yet fully synthetic in nature. This is the first plug‐and‐play approach to fabricate hybrid π‐sheet/helix, π‐sheet/coil, and helix/coil architectures via directional self‐assembly.     

基于氢键作用结合的超分子聚合物

非共价键结合的超分子聚合物由于其特殊的结构及性能引起了广泛的关注。本文在介绍超分子化学、氢键及超分子聚合物的基础上,主要综述了以氢键为结合力的多重氢键作用、羧基(D)与吡啶基(A)作用以及氢键与其它非共价键协同作用形成的超分子聚合物体系,并对超分子聚合物的研究现状及前景进行了评述。