二维有机组装体的可控制备

二维有机组装体是一类具有特殊形貌和性质的有序结构, 有可能带来新功能和光电子领域的潜在应用, 但如何实现二维有机组装体的可控制备是尚待解决的问题. 针对这一问题, 我们通过对构筑基元的理性设计, 调控分子间的相互作用, 发展了三种可控制备二维有机组装体的新方法: (1)利用疏水有机阴离子作为Bola型两亲分子的抗衡离子, 能够削弱亲水头基间的静电排斥作用, 从而诱导两亲分子的组装结构从一维向二维转变; (2)基于非共价键形成超两亲分子, 通过设计和控制超两亲分子的拓扑结构, 简便有效地实现二维组装体的制备; (3)通过共价修饰或引入新的非共价键, 以限制三维结构在某一方向上的生长, 从而降低三维结构的维度, 也能实现二维组装体的可控制备. 未来, 上述研究有望进一步拓展, 并实现功能二维有机组装体的构筑.     

Gemini型两亲分子超分子组装研究进展

综述了国内外对Gemini型两亲分子在超分子组装方面的研究进展。总结了Gemini分子的体相组装、界面组装以及近几年应用领域的研究进展;着重介绍了基因传递、纳米材料模板、降解剂、药物缓释以及胶凝剂的制备等方面的应用进展;对相关研究领域的主要研究成果做了一些探讨和分析;为更加深入探索和研究Gemini型两亲分子的超分子组装提供参考信息。     

自组装共混制备PEG化基因载体

通过含PEG链段的两亲聚合物的自组装共混, 制备了基于疏水作用力的新型PEG化非病毒基因载体. 分别选用胆固醇-聚乙二醇和聚乙二醇-聚丙二醇-聚乙二醇作为共混改性剂, 研究两亲聚合物的种类对组装体在生理盐溶液中的稳定性及基因转染效率的影响. 结果表明, 疏水驱动力的大小是获得稳定的PEG化基因超分子组装体的关键. 通过对两亲聚合物中疏水链段的选择调控, 可制备稳定的PEG化基因超分子组装体, 提高基因传递体系在生理盐溶液中的稳定性及基因转染效率. 通过自组装共混, 为新型PEG化基因超分子组装体的制备提供了切实可行的新方法.     

基于芳香分子-糖类手性超分子组装体及功能

手性超分子组装体广泛存在于自然界中,因其在材料、化学和生物学等领域广阔的应用前景,引起了科学家们极大的兴趣。其中以糖类分子作为手性源,经分子自组装构筑手性超分子组装体的研究已成为超分子化学领域的研究热点之一。本文综述了基于糖类修饰的苝酰亚胺分子、偶氮苯分子、联苯类分子和卟啉类分子等芳香分子化合物经自组装构筑的手性超分子组装体,介绍了其在有机溶剂和水的混合溶剂、水中的凝胶性质,超分子手性特征和功能,糖分子类型与超分子组装体手性间的关系等,并对基于糖类的手性超分子组装体的前景进行了展望。     

科学家开发出超分子组装新方法

<正>英国和日本研究人员合作开发出一种超分子组装的新方法,有望带来比硅材料性能更优越的分子电子设备,研究人员认为,这种方法有着巨大应用潜力,有可能推动新材料生产的变革。相邻分子间存在微小的作用力,超分子组装就是利用了这种非共价键的微小力的累加效应,来形成有序的结构。新方法集中在研究分子间的作用力上,特别是那些"两亲"分子。"两亲"分子包含亲水和憎水两个部分。如家用洗涤剂     

基于超分子环糊精两亲分子的敏感型囊泡体系

敏感型囊泡可初步概括为由两亲分子通过非共价键构筑的、对外界的刺激具有特色响应性的一类新型囊泡体系。由"超分子环糊精两亲分子"自组装形成的囊泡体系是该类体系中重要的一类。本文重点介绍了环糊精参与的"超分子环糊精两亲分子"囊泡体系的研究进展。以与环糊精复合的化合物结构类型不同进行分类,介绍了该类囊泡体系的制备以及该体系在医药工程、新型"智能"材料以及生物模拟等方面的潜在应用;结合现阶段的研究状况,对该类囊泡体系的发展前景进行了展望。     

高中化学新教材中超分子、分子识别和自组装的解读和拓展

超分子是两种或两种以上分子通过非共价键作用形成的分子聚集体,是化学前沿研究的重要内容。2020年,超分子、分子识别和自组装等内容首次走进中学化学教材。解读了新教材中超分子、分子识别和自组装相关内容,并进行了拓展和延伸,为教师深度备课和学生深度学习提供资源,以达到培养学生学习兴趣和学科核心素养的目的。     

基于杯芳烃主体的分子自组装研究进展

分子自组装是超分子化学最重要的研究内容之一. 杯芳烃作为继冠醚、环糊精之后的第三代人工合成受体分子已在分子自组装研究方面取得了重要进展并显示了广泛的应用前景. 主要综述杯芳烃衍生物通过氢键、金属诱导配位、π-π作用、疏水作用等非共价键弱相互作用力在溶液状态、固态和界面的分子自组装方面的研究进展.     

基于天然小分子化合物的超分子自组装

天然产物来源广泛、手性结构独特、具有多修饰位点、良好的生物相容性和可控的降解性, 与其他非天然产物的自组装体系相比, 具有更多的优势. 简单修饰的天然产物在溶剂中容易形成氢键、π-π堆积、范德华作用等非共价键作用, 促使分子有序排列形成聚集体, 成为超分子自组装体系的重要构筑基元. 同时, 其独特的手性结构在分子有序排列过程中, 通常会实现手性由分子层次到超分子层次的传递和放大, 因此, 可用于构建螺旋带、纳米管等多种手性组装体. 天然产物良好的生物相容性和生物活性, 也使得基于此类化合物的组装体可应用于组织工程、药物传递、细胞成像等生命科学领域, 显示其广阔的应用前景. 本文介绍了基于氨基酸、糖、核苷碱基、甾体、三萜等天然产物缀合物在超分子自组装特性方面的研究概况及其发展趋势.     

基于冠醚衍生物的超分子聚合物

自组装现象是生命科学最本质的内容之一,生物体系可以精确地利用非共价键相互作用形成高度有序的功能组装体.受到大自然的启发,近年来利用分子自组装构筑包括超分子聚合物在内的有序聚集体是超分子科学的研究热点.此类组装体不仅在拓扑学上具有重要的意义,而且可以用来制备动态的超分子功能材料.冠醚作为第一代超分子主体化合物,由于其结构...     

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。     

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。     

Self‐assembly of supramolecular polymers into tunable helical structures

There is growing interest in the design of synthetic molecules that are able to self‐assemble into a polymeric chain with compact helical conformations, which is analogous to the folded state of natural proteins. Herein, we highlight supramolecular approach to the formation of helical architectures and their conformational changes driven by external stimuli. Helical organization in synthetic self‐assembling systems can be achieved by the various types of noncovalent interactions, which include hydrogen bonding, solvophobic effects, and metal‐ligand interactions. Since the external environment can have a large influence on the strength and configuration of noncovalent interactions between the individual components, stimulus‐induced alterations in the intramolecular noncovalent interactions can result in dynamic conformational change of the supramolecular helical structure thus, driving significant changes in the properties of the materials. Therefore, these supramolecular helices hold great promise as stimuli‐responsive materials. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1925–1935, 2008     

Hydrophobic Self‐Assembly Affords Robust Noncovalent Polymer Isomers

In covalent polymerization, a single monomer can result in different polymer structures due to positional, geometric, or stereoisomerism. We demonstrate that strong hydrophobic interactions result in stable noncovalent polymer isomers that are based on the same covalent unit (amphiphilic perylene diimide). These isomers have different structures and electronic/photonic properties, and are stable in water, even upon prolonged heating at 100 °C. Such combination of covalent‐like stability together with structural/functional variation is unique for noncovalent polymers, substantially advancing their potential as functional materials.     

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     

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.     

Self‐Assembling Hydrogels Crosslinked Solely by Receptor–Ligand Interactions: Tunability,Rationalization of Physical Properties,and 3D Cell Culture

We report a novel, noncovalent hydrogel system crosslinked solely by receptor–ligand interactions between biotin and avidin. The simple hydrogel synthesis and functionalization together with the widespread use of biotinylated ligands in biosciences make this versatile system suitable for many applications. The gels possess a range of tunable physical properties, including stiffness, lifetime, and swelling. The erosion rates, unexpectedly fast compared to the kinetic parameters for biotin–avidin, are explored in terms of stretching tensions on the polymers, a concept well‐known on the single‐molecule level, but largely unexplored in supramolecular systems. As proof of utility, the gels were functionalized with different peptide sequences to control human mesenchymal stromal cell morphology in 3D culture.     

Advances in switchable supramolecular nanoassemblies

Supramolecular nanoassemblies are gaining increasing importance as promising new materials with considerable potential for novel and promising applications. Within supramolecular nanoassemblies the connectivity of the monomeric units is based on reversible noncovalent interactions, like van der Waals interactions, hydrogen bonding, or ionic interactions. As the strength of these interactions depends on the molecular surrounding, the formation of nanoassemblies in principle can be controlled externally by changing the environment and/or the molecular shape of the underlying monomer. This way it is not only possible to switch the self-assembly on or off, but also to change between different aggregation states. In this minireview we present some recent selected approaches to supramolecular stimuli-responsive nanoassemblies.     

A Periodic System of Supramolecular Elements

Chemistry “beyond the molecule” is based on weak, noncovalent, and reversible interactions. As a consequence of these bonds being weak, structural organization by folding and self‐assembly can only be fully exploited with larger molecules that can provide multiple binding sites. Such “supramolecules” can now be synthesized and their folding into desired conformations predicted. A new level of chemistry can now be realized through the creation of non‐natural entities composed of molecular building blocks with defined secondary structures. Herein we define these building blocks as “supramolecular elements”. We anticipate that further research on such large molecules will reveal construction principles dictated by recurring motifs that govern structure formation through folding and self‐assembly. These principles are comparable to the organization of atoms in the Periodic Table of Chemical Elements and may lead to the establishment of a Periodic System of Supramolecular Elements.     

超分子双膦配体的构筑及应用研究进展

超分子双膦配体是一类新兴起的基于非共价键作用构筑的双膦配体,近年来引起人们的重视.与传统的共价键连接的双膦配体相比,利用非共价相互作用的可逆性和选择性,超分子双膦配体具有合成简便,组合灵活,易于合成超分子配体库,并利用组合化学的方法对催化体系进行优化和筛选等优点.详细综述了近几年发展的基于氢键、配位键、主客体作用和静电作用等弱相互作用的超分子双膦配体,重点讨论了它们的构建方法以及在不对称催化反应中的应用,并对其发展前景进行了展望.