A method of controllable supramolecular polymerization through kinetic trapping is developed. To this end, two bifunctional monomers with cucurbit[7]uril (CB[7]) and adamantane end groups were synthesized. The CB[7]‐containing monomer was presaturated with a pH‐responsive competitive guest for kinetic control. Then, the kinetics of supramolecular polymerization of the two monomers was easily controlled through the modulation of pH. As a result, supramolecular polymerization was kinetically trapped at certain stages, and supramolecular polymers with different molecular weights were obtained. It is anticipated that this research will enrich the methods of controllable supramolecular polymerization. 相似文献
Stereoselective and temporally controlled supramolecular polymerizations are ubiquitous in nature and are desirable attributes for the design of chiral, well-defined functional materials. Kinetically controlled, living supramolecular polymerization (LSP) has emerged recently for the synthesis of supramolecular polymers with controlled length and narrow dispersity. On the other hand, stringent design requirements for chiral-discriminating monomers precludes the stereoselective control of the supramolecular polymer structure. Herein, a synergetic stereo- and structural control of supramolecular polymerization by the realization of an unprecedented stereoselective seed-induced LSP is reported. Homochiral and seeded growth is demonstrated with bischromophoric naphthalene diimide (NDI) enantiomers with a chiral binaphthyl amine core, exhibiting strong self-recognition abilities and pathway complexity. 相似文献
A metal‐free, cationic, reversible addition–fragmentation chain‐transfer (RAFT) polymerization was proposed and realized. A series of thiocarbonylthio compounds were used in the presence of a small amount of triflic acid for isobutyl vinyl ether to give polymers with controlled molecular weight of up to 1×105 and narrow molecular‐weight distributions (Mw/Mn<1.1). This “living” or controlled cationic polymerization is applicable to various electron‐rich monomers including vinyl ethers, p‐methoxystyrene, and even p‐hydroxystyrene that possesses an unprotected phenol group. A transformation from cationic to radical RAFT polymerization enables the synthesis of block copolymers between cationically and radically polymerizable monomers, such as vinyl ether and vinyl acetate or methyl acrylate. 相似文献
Novel, chiral‐selective linear nanotubular heterojunctions were achieved by living supramolecular polymerization of perylenediimide (PDI) derivatives. We demonstrate that the chiral seed can effectively bias achiral PDI molecules to polymerize on its ends in the identical helical sense. More interestingly, the chiral seed can bias the opposite enantiomers to grow expitaxially from its ends even in excess amounts relative to the seed. Furthermore, we demonstrate that the biasing effect of the chiral seed on the opposite enantiomer is not dependent on the length of the chiral seed but is related to the intrinsic length of the elongated nanotube from the opposite enantiomer. The fabrication of chiral‐selective nanotubes was achieved by application of the unique biasing effect of the chiral seed in living supramolecular self‐assembly. 相似文献
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. 相似文献
The role of molecularly imprinted polymers (MIPs) is changing from academic to applied researches. Challenging problems about MIP will be more highlighted in applicable uses and solving these problems is vital. The controlled/“living” radical polymerization (CLRP) techniques are applicable to solve the challenging problems in MIPs. The “living” nature of CLRP helps to improve the heterogeneity of binding sites in MIPs as a main challenge where precise control over sizes, compositions, and surface functionalities is achieved. Among different techniques of CLRP, reversible addition-fragmentation chain transfer (RAFT) technique presents distinguished benefits such as compatibility and tolerance to a wide range of functional monomers and mild reaction conditions rather than other CLRP techniques. In this review, in order to obtain more insights into the potential benefits of RAFT polymerization in fabrication of nano and micro MIP networks, recent research in advanced MIP materials for different templates with improved morphology, efficiency, and binding capacities with respect to traditional free radical polymerization (FRP) will be discussed. MIPs prepared via RAFT method have advantages of MIPs as high performance molecular recognition devices and CLRP as controllable polymerization mechanism, simultaneously. 相似文献
We present the construction of long‐chain water‐soluble supramolecular polymers at low monomer concentrations. Naphthalene‐based host‐enhanced π–π interactions, which possess high binding constants, were used as the driving force of supramolecular polymerization. A monomer, DNDAB, with a rigid, bulky 1,4‐diazabicyclo[2.2.2]octane‐1,4‐diium linker was designed. The design of the monomer structure strongly influenced the efficiency of the supramolecular polymerization. The rigid, bulky linker in DNDAB effectively eliminates cyclization, promoting the formation of long‐chain supramolecular polymers at low monomer concentrations. In contrast, a reference monomer containing a flexible linker (DNPDN) only forms oligomers owing to cyclization. 相似文献
Functionalized, styrene based monomers were investigated for copolymerization with isobutylene (IB) via living carbocationic polymerization. The achieved incorporation of polar moieties into the polymer backbone yielded supramolecular networks, which were analyzed and characterized via rheological measurements. 相似文献
Cationic polymerizations have long been industrialized; however, stimulus‐regulated cationic polymerization remains to be developed. An electrochemically controlled living cationic polymerization is presented for the first time. In the presence of external potential and organic‐based electrocatalyst, a series of monomers can be polymerized under a cationic chain‐transfer mechanism. The resulting polymers exhibit well‐defined molecular mass, narrow dispersity, and good chain‐end fidelity. By controlling the external potential to switch the electrocatalyst between its oxidized and reduced states, ON/OFF polymerization can be achieved. This method is a versatile way to a large range of monomers, including vinyl ether‐type and p‐substituted styrene‐type monomers. Given the sustainability feature and broad interest of electrochemical synthetic techniques, we envisaged that this method would lead a new direction of external regulated living ionic polymerization. 相似文献
Functionalized or multivalent organotellurium chain‐transfer agents (CTAs) for living radical polymerization were synthesized by post‐modification, which involved the condensation between a carboxylic‐acid‐functionalized CTA and various amines in excellent yields without affecting the reactive tellurium moiety. The CTAs exhibited high synthetic versatility for radical polymerization and gave structurally well‐controlled polymers, such as multiarmed polymers, from various monomers. Because all new CTAs are easily available on a large scale by simple purification, the current method significantly facilitates macromolecular engineering based on organotellurium‐mediated radical polymerization (TERP). 相似文献
A new method in which supramolecular polymerization is promoted and controlled through self‐sorting is reported. The bifunctional monomer containing p‐phenylene and naphthalene moieties was prepared. Supramolecular polymerization is promoted by selective recognition between the p‐phenylene group and cucurbit[7]uril (CB[7]), and 2:1 complexation of the naphthalene groups with cucurbit[8]uril (CB[8]). The process can be controlled by tuning the CB[7] content. This development will enrich the field of supramolecular polymers with important advances towards the realization of molecular‐weight and structural control. 相似文献
The idea to synthesize and self-assemble nano-graphenes with structural precision into supramolecular polymers is just one of Klaus Müllen's many pioneering contributions to the chemical sciences. To honor his impact in the field of polymer science, we here describe a study that combines experimental and computational methods in studying the stability of kinetically trapped states of supramolecular polymers. We show that the introduction of stereocenters in the sidechains allow helical supramolecular polymers based on chiral triphenylene-2,6,10-tricarboxamide monomers to escape a kinetic trap more efficiently than polymers based on their achiral analogs. Partial depolymerization of the kinetically trapped state by increasing the temperature followed by polymerization by lowering the temperature shows that monomers either polymerize on existing stacks or self-nucleate to form the thermodynamically more stable state. Chiral monomers prefer the latter more than achiral monomers. 相似文献
The incorporation of metallic units into polymer chains has emerged as a promising route towards functional metal‐containing (nano)materials. The resulting polymers possess rich functions derived from their metallic elements, such as redox, optical, catalytic and magnetic properties. In addition, the directional and dynamic nature of metal coordination interactions provides further variables for the exploration of novel materials with designed nanostructures. These types of polymers can be synthesized through direct metal‐ligand coordination or chain polymerization of metal containing monomers. Depending on the polymerization techniques and starting components, the resulting polymers, akin to their organic counterparts, can be produced in the form of insoluble networks, processible chain structures, gels or colloids. Research into this rising multidisciplinary subject has benefited from recent progress in several related areas such as supramolecular chemistry, colloidal chemistry etc., with the combination of the relative merits of each ensuring further developments in each individual discipline. For example, as a result of studies into organometallic block copolymers self‐assembly behavior, living supramolecular polymerization has been unprecedentedly realized for the architectural design of micelles (see image on the right). Nevertheless, the field is still in a developmental stage and offers ample opportunities for fundamental research, as well as material exploration. In this Feature Article, we intend to overview the field with a brief survey of recent literature.
Molecularly imprinted polymers (MIPs) are artificial receptors which can be tailored to bind target molecules specifically. A new method, using photoinitiated atom‐transfer radical polymerization (ATRP) for their synthesis as monoliths, thin films and nanoparticles is described. The synthesis takes place at room temperature and is compatible with acidic monomers, two major limitations for the use of ATRP with MIPs. The method has been validated with MIPs specific for the drugs testosterone and S‐propranolol. This study considerably widens the range of functional monomers and thus molecular templates which can be used when MIPs are synthesized by ATRP, as well as the range of physical forms of these antibody mimics, in particular films and lithographic patterns, and their post‐functionalization from living chain‐ends. 相似文献