超分子聚合物复合材料及其自愈合行为

超分子聚合物复合材料定义为纤维、填料等增强体均匀分散在超分子聚合物基体中的复合材料。根据超分子聚合物与增强体之间化学键连接的不同可分为三种类型:(1)无化学键;(2)共价键;(3)非共价键。超分子聚合物复合材料与分子聚合物复合材料共同组成了完整的聚合物复合材料体系。本文综述可自愈合的氢键、π-π堆叠和金属配位型超分子聚合物复合材料的研究进展。     

超分子树枝聚合物的起源与发展

超分子树枝聚合物起源于聚合物链结构的2个重要进化(树枝链和超分子),是通过建筑模块在芯、支化单元或表面的分子自组装(非共价键连接)生成的树枝聚合物,具有独特的结构特征和新颖的物理、化学等功能。超分子树枝聚合物的进一步自组织可形成液晶态或柱状体等有序结构。超分子树枝聚合物可分为氢键型、金属配位型、π-π堆叠型、离子型、拓扑型(含轮烷和索烃结构)、混合型(含2种或2种以上不同非共价键)等类型。本文综述各种类型超分子树枝聚合物的合成、结构、聚集态和应用。     

界面超分子聚合

超分子聚合物诞生于高分子化学与超分子化学的交叉融合,一般是指单体间通过非共价键作用连接形成的聚合物,并在溶液或体相中表现出类似聚合物的性质。目前超分子聚合物一般通过均相溶液聚合制备得到,但溶液中的超分子聚合是一个自发的组装过程,具有浓度依赖性,组装过程不易可控。为解决此问题,研究人员可以将超分子聚合从均相溶液转移到界面,在界面上可控地制备超分子聚合物。通过界面聚合制备超分子聚合物具有一些独特的优势,如可以制备得到分子量更高的超分子聚合物,易于制备一些缺陷少、面积大、有序的二维超分子聚合物等。本文基于在液-液、气-液和固-液三种界面上制备超分子聚合物的一些代表性工作,介绍了界面超分子聚合方法和应用,并展望其未来发展。     

基于环糊精主客体包合作用构筑的聚合物

在由超分子作用构筑聚合物的研究中,环糊精因能与多种客体分子形成超分子包合物而被广泛应用。本文根据超分子构筑单元的不同,综述了两类基于环糊精主客体包合作用的聚合物:(1)通过具有环糊精及客体基团的大分子间的包合构筑的非共价键嵌段聚合物,包括不同拓扑结构聚合物的制备及其功能化;(2)通过客体基团修饰环糊精的相互包合构筑的超分子聚合物,主要涉及高聚合度超分子聚合物的制备及其研究进展。     

基于平面有机硼烷的超分子聚合物

超分子聚合物,即单体通过非共价键作用连接而成的链状聚集体,具有独特的物化性质和功能.经过30年的发展,超分子聚合物领域已取得了一系列重大创新成果.目前,超分子聚合物领域亟需探索的问题主要在超分子聚合驱动力、超分子构筑基元、可控超分子聚合、超分子聚合物功能等方面.近期,荷兰埃因霍温理工大学的Meijer课题组和日本名古屋...     

三聚氰胺和对苯二氧乙酸共晶中的三维氢键网络(英文)

合成了一个新的超分子聚合物{(MAH+)2(p-BDOA2-)·4H2O}n(MA=三聚氰胺;p-BDOAH2=对苯二氧乙酸),通过X-射线对其结构进行了表征。在该聚合物中,三聚氰胺被质子化,相邻的三聚氰胺分子通过氢键形成一维阳离子链(MAH+)n,相邻的阳离子链由p-BDOA2-阴离子连接构成波浪状的二维层,层状结构通过水分子的氢键和π-π堆积形成三维结构。     

三聚氰胺和对苯二氧乙酸共晶中的三维氢键网络

合成了一个新的超分子聚合物{(MAH+)2(p-BDOA2-)·4H2O}n(MA=三聚氰胺;p-BDOAH2=对苯二氧乙酸),通过X-射线对其结构进行了表征。在该聚合物中,三聚氰胺被质子化,相邻的三聚氰胺分子通过氢键形成一维阳离子链(MAH+)n,相邻的阳离子链由p-BDOA2-阴离子连接构成波浪状的二维层,层状结构通过水分子的氢键和π-π堆积形成三维结构。     

多重氢键超分子聚合物

超分子聚合物是通过单体单元间的可逆非共价作用(包括氢键、π-π相互作用和金属配位作用等)形成的,由于非共价键的方向性和强度,这类聚合物显示了许多有趣的功能,例如刺激响应性和纳米结构自组装.本文总结了近三年来多重氢键超分子聚合物在改善聚合物性能、形成复杂分子构造、自组装纳米结构等方面的作用,并对超分子聚合物的应用进行了展...     

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。     

基于金属配位和主客体相互作用分级自组装构筑超分子凝胶

将金属配位和主客体相互作用引入到同1个超分子体系中,设计合成了2个超分子单体1和2.通过这2个超分子单体分级自组装形成的交联网状超分子聚合物构建了一种多重刺激响应性和良好自修复性能的超分子凝胶.同时,进一步将具有聚集诱导发光性能的四苯乙烯引入到这种超分子体系中,以赋予超分子体系新颖的发光性能.单体分子1是由中间为双苯并24-冠-8的冠醚连接2个四苯基乙烯荧光生色团,两端为2个三联吡啶分子构成的1个主体分子.单体分子1两端的三联吡啶基团可以与过渡金属Zn(OTf)2进行金属配位形成线型超分子聚合物3;而中间的冠醚基团与双二级铵盐客体分子2通过主客体相互作用进一步形成交联超分子聚合物4.当该交联超分子聚合物的浓度达到30 mmol/L时,可形成荧光超分子聚合物凝胶.通过核磁共振(1H-NMR和DOSY)与黏度等测试方法,证明了线形和交联超分子聚合物的形成,并进一步通过流变的测试证明了超分子聚合物凝胶的形成及其良好的自修复性能.除此之外,由于引入的主客体相互作用以及金属配位固有的刺激响应性,该荧光超分子聚合物凝胶表现出对温度、p H值、K+离子和竞争配体的刺激响应性能.     

氢键型超分子聚合物的合成、结构与应用

氢键型超分子聚合物是重复单元经氢键相互作用连接在一起的阵列,可生成液晶态,多样化的几何形状和高有序的凝聚态结构。氢键的温度敏感性和可逆性导致氢键型超分子聚合物具有和传统共价键结合的聚合物不同的性能。氢键型超分子聚合物是一类动态的智能型功能高分子材料,可在光化学、光电转换、非线性光学、弹性体、水凝胶和生物医用工程等领域广泛应用。本文从氢键型超分子聚合物化学(合成与机理)、物理(结构与性能)和工程(加工与应用)三个方面介绍氢键型超分子聚合物的进展。     

Supramolecular perspectives in colloid science

Supramolecular chemistry puts emphasis on molecular assemblies held together by non-covalent bonds. As such, it is very close in spirit to colloid science which also focuses on objects which are small, but beyond the molecular scale, and for which other forces than covalent bonds are crucial. We discuss in this review the preparation and properties of new colloidal systems which borrow on the one hand from classical topics in colloid science, such as micellization, and on the other hand from concepts in supramolecular chemistry, such as reversible supramolecular polymers.     

Investigation of the Amide Linkages on Cooperative Supramolecular Polymerization of Organoplatinum(II) Complexes

Cooperative supramolecular polymerization of π-conjugated compounds into one-dimensional nanostructures has received tremendous attentions in recent years. It is commonly achieved by incorporating amide linkages into the monomeric structures, which provide hydrogen bonds for intermolecular non-covalent complexation. Herein, the effect of amide linkages is elaborately studied, by comparing supramolecular polymerization behaviors of two structurally similar monomers with the same platinum(II) acetylide cores. As compared to the N-phenyl benzamide linkages, N-[(1S)-1-phenylethyl] benzamide linkages give rise to effective chirality transfer behaviors due to the closer distances between the chiral units and the platinum(II) acetylide core. They also provide stronger intermolecular hydrogen bonding strength, which consequently brings higher thermo-stability and enhanced gelation capability for the resulting supramolecular polymers. Supramolecular polymerization is further strengthened by varying the monomers from monotopic to ditopic structures. Hence, with the judicious modulation of structural parameters, the current study opens up new avenues for the rational design of supramolecular polymeric systems.     

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.     

Characterization of supramolecular polymers

Supramolecular polymers are made of monomers that are held together by noncovalent interactions. This is the reason for the wide range of novel properties, such as reversibility and responses to stimuli, exhibited by supramolecular polymers. A range of supramolecular polymerization methods have been developed leading to a number of novel supramolecular materials. However, standard techniques for the characterization of supramolecular polymers have yet to be established. The dynamic nature of supramolecular polymers makes them difficult to be fully characterized using conventional polymer techniques. This tutorial review summarizes various methods for characterizing supramolecular polymers, including theoretical estimation, size exclusion chromatography, viscometry, light scattering, vapor pressure osmometry, mass spectrometry, NMR spectroscopy, scanning probe microscopy, electron microscopy, and atomic force microscopy-based single molecule force spectroscopy. Each of these methods has its own particular advantages and disadvantages. Most of the methods are used to characterize the supramolecular polymer chain itself. However, some of the methods can be used to study the self-assembled state formed by supramolecular polymers. The characterization of a supramolecular polymer cannot be realized with a single method; a convincing conclusion relies on the combination of several different techniques.     

Water-soluble supramolecular polymers constructed by macrocycle-based host-guest interactions

Water soluble supramolecular polymers are especially important due to their superior biocompatibility and environmental adaptation, which determined they have wide applications in various areas, such as drug delivery, self-healing, shape memory. On the other hand, macrocyclic compounds are the most used building blocks in the preparation of supramolecular polymers. Macrocycle-based supramolecular polymers, which introduce the host-guest interaction in the system, endow these polymers with interesting and smart physicalchemical properties. In this review, we summarized recent studies about supramolecular polymers in aqueous solution based on macrocyclic compounds.     

Supramolecular polymers: from scientific curiosity to technological reality

Supramolecular polymers^[1] are introduced as a new approach to come to materials in which the repeating units are not connected by covalent bonds but by specific secondary interactions. Self-complementary quadruple hydrogen bonded structures with high association constants are presented as easy to synthesize fragments in supramolecular polymers. Some of the many possibilities of equilibrium polymers are discussed, while it is shown that these supramolecular polymers can obtain materials properties normally only obtained with macromolecules.     

Aggregate Engineering in Supramolecular Polymers via Extensive Non-covalent Networks

Aggregate engineering of non-covalent networks endows supramolecular polymers with thermo-mechanical versatility, stimuliresponsive phase transitions and intrinsic damage-healing capabilities. However, most non-covalent networks are vulnerable at elevated temperatures, which suppresses the robustness of supramolecular polymers. Herein, ureidocytosine(UCy) motifs, which are capable of forming extensive non-covalent networks and thus robust molecular aggregates via multivalent hydrogen bonds and aromatic stackings, are proposed to enable precise programming of the thermo-mechanical versatility. Molecular simulations reveal that the enthalpic contributions from the UCy aggregates play dominant roles to compensate the entropic loss from the redistributions of polymeric spacers and stabilize the non-covalent networks over wide temperature windows. Such aggregate-level strategy offers prospects for applications which require thermo-mechanical versatility of supramolecular polymers, such as 3 D printing, microfabrication and damage-healing coating.     

Hooking Together Sigmoidal Monomers into Supramolecular Polymers

Supramolecular polymers show great potential in the development of new materials because of their inherent recyclability and their self‐healing and stimuli‐responsive properties. Supramolecular conductive polymers are generally obtained by the assembly of individual aromatic molecules into columnar arrays that provide an optimal channel for electronic transport. A new approach is reported to prepare supramolecular polymers by hooking together sigmoidal monomers into 1D arrays of π‐stacked anthracene and acridine units, which gives rise to micrometer‐sized fibrils that show pseudoconductivities in line with other conducting materials. This approach paves the way for the design of new supramolecular polymers constituted by acene derivatives with enhanced excitonic and electronic transporting properties.