共查询到20条相似文献,搜索用时 718 毫秒
1.
Prof. Dr. Takashi Uemura 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(6):1482-1489
Controlled organization of polymer chains into ordered structures is highly important to tune or enhance the properties of the polymeric materials. A supramolecular approach using host–guest chemistry has allowed rational design of chain assemblies with many functional properties. Nanoporous materials with ordered channel structures are particularly useful for attaining precise assemblies of polymer chains through nanoconfinement. 相似文献
2.
Tomoki Ogoshi Takahiro Kakuta Tada‐aki Yamagishi 《Angewandte Chemie (International ed. in English)》2019,58(8):2197-2206
Macrocycles are an important player in supramolecular chemistry. In 2008, a new class of macrocycles, “pillar[n]arenes”, were first discovered. Research efforts in the area of pillar[n]arenes have elucidated key properties, such as their shape, reaction mechanism, host–guest properties, and their versatile functionality, which has contributed to the development of pillar[n]arene chemistry and their applications to various fields. This Minireview describes how pillar[n]arene‐based supramolecular assemblies can be applied to supramolecular gel formation, reactions, light‐harvesting systems, drug‐delivery systems, biochemical applications, separation and storage materials, and surface chemistry. 相似文献
3.
Takeharu Haino 《Chemical record (New York, N.Y.)》2015,15(5):837-853
Supramolecular polymeric assemblies represent an emerging, promising class of molecular assemblies with enormous versatility compared with their covalent polymeric counterparts. Although a large number of host–guest motifs have been produced over the history of supramolecular chemistry, only a limited number of recognition motifs have been utilized as supramolecular connections in polymeric assemblies. This account describes the molecular recognition of host molecules based on calix[5]arene and bisporphyrin that demonstrate unique guest encapsulations; subsequently, these host–guest motifs are applied to the synthesis of supramolecular polymers that display polymer‐like properties in solution and solid states. In addition, new bisresorcinarenes are developed to form supramolecular polymers that are connected via a rim‐to‐rim hydrogen‐bonded dimeric structure, which is composed of two resorcinarene moieties.
4.
Host–Guest Binding‐Site‐Tunable Self‐Assembly of Stimuli‐Responsive Supramolecular Polymers 下载免费PDF全文
Hao Yao Miao Qi Prof. Dr. Yuyang Liu Prof. Dr. Wei Tian 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(25):8508-8519
Despite the remarkable progress made in controllable self‐assembly of stimuli‐responsive supramolecular polymers (SSPs), a basic issue that has not been consideration to date is the essential binding site. The noncovalent binding sites, which connect the building blocks and endow supramolecular polymers with their ability to respond to stimuli, are expected to strongly affect the self‐assembly of SSPs. Herein, the design and synthesis of a dual‐stimuli thermo‐ and photoresponsive Y‐shaped supramolecular polymer (SSP2) with two adjacent β‐cyclodextrin/azobenzene (β‐CD/Azo) binding sites, and another SSP (SSP1) with similar building blocks, but only one β‐CD/Azo binding site as a control, are described. Upon gradually increasing the polymer solution temperature or irradiating with UV light, SSP2 self‐assemblies with a higher binding‐site distribution density; exhibits a flower‐like morphology, smaller size, and more stable dynamic aggregation process; and greater controllability for drug‐release behavior than those observed with SSP1 self‐assemblies. The host–guest binding‐site‐tunable self‐assembly was attributed to the positive cooperativity generated among adjacent binding sites on the surfaces of SSP2 self‐assemblies. This work is beneficial for precisely controlling the structural parameters and controlled release function of SSP self‐assemblies. 相似文献
5.
Masaki Nakahata Yoshinori Takashima Akira Harada 《Macromolecular rapid communications》2016,37(1):86-92
Flexible, tough, and self‐healable polymeric materials are promising to be a solution to the energy problem by substituting for conventional heavy materials. A fusion of supramolecular chemistry and polymer chemistry is a powerful method to create such intelligent materials. Here, a supramolecular polymeric material using multipoint molecular recognition between cyclodextrin (CD) and hydrophobic guest molecules at polymer side chain is reported. A transparent, flexible, and tough hydrogel (host–guest gel) is formed by a simple preparation procedure. The host–guest gel shows self‐healing property in both wet state and dry state due to reversible nature of host–guest interaction. The practical utility of the host–guest gel as a scratch curable coating is demonstrated.
6.
Designed Enclosure Enables Guest Binding Within the 4200 Å3 Cavity of a Self‐Assembled Cube 下载免费PDF全文
William J. Ramsay Filip T. Szczypiński Dr. Haim Weissman Dr. Tanya K. Ronson Dr. Maarten M. J. Smulders Prof. Boris Rybtchinski Prof. Jonathan R. Nitschke 《Angewandte Chemie (International ed. in English)》2015,54(19):5636-5640
Metal–organic self‐assembly has proven to be of great use in constructing structures of increasing size and intricacy, but the largest assemblies lack the functions associated with the ability to bind guests. Here we demonstrate the self‐assembly of two simple organic molecules with CdII and PtII into a giant heterometallic supramolecular cube which is capable of binding a variety of mono‐ and dianionic guests within an enclosed cavity greater than 4200 Å3. Its structure was established by X‐ray crystallography and cryogenic transmission electron microscopy. This cube is the largest discrete abiological assembly that has been observed to bind guests in solution; cavity enclosure and coulombic effects appear to be crucial drivers of host–guest chemistry at this scale. The degree of cavity occupancy, however, appears less important: the largest guest studied, bound the most weakly, occupying only 11 % of the host cavity. 相似文献
7.
Ying‐Ming Zhang Jiang‐Hua Liu Qilin Yu Xin Wen Yu Liu 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(31):10663-10667
Tunable protein assemblies not only hold a dominant position in vital biological events but are also a significant theme in supramolecular chemistry. Herein, we demonstrated that the intertubular aggregation of microtubules (MTs) could be efficiently regulated by a synergistic polypeptide–tubulin interaction and host–guest complexation. The benzylimidazolium‐modified antimitotic peptide (BP) could recognize the MTs and concurrently form stable inclusion complexes with avirulent cucurbit[7]uril (CB[7]) and cucurbit[8]uril (CB[8]) in different binding stoichiometries. The self‐assembling morphology of MTs was converted from fibrous to nanoparticulate aggregates via extensive BP?CB[8] cross‐linkage, leading to significant cell apoptosis and tumor ablation in vivo. The targeted (BP?CB[8])@MT ternary assembly provides a facile supramolecular method to enhance the protein–protein interactions, which may be developed as a therapy for degenerative diseases, such as cancer. 相似文献
8.
Self‐Healing,Expansion–Contraction,and Shape‐Memory Properties of a Preorganized Supramolecular Hydrogel through Host–Guest Interactions 下载免费PDF全文
Kohei Miyamae Dr. Masaki Nakahata Dr. Yoshinori Takashima Prof. Dr. Akira Harada 《Angewandte Chemie (International ed. in English)》2015,54(31):8984-8987
Supramolecular materials cross‐linked between polymer chains by noncovalent bonds have the potential to provide dynamic functions that are not produced by covalently cross‐linked polymeric materials. We focused on the formation of supramolecular polymeric materials through host–guest interactions: a powerful method for the creation of nonconventional materials. We employed two different kinds of host–guest inclusion complexes of β‐cyclodextrin (βCD) with adamantane (Ad) and ferrocene (Fc) to bind polymers together to form a supramolecular hydrogel (βCD‐Ad‐Fc gel). The βCD‐Ad‐Fc gel showed self‐healing ability when damaged and responded to redox stimuli by expansion or contraction. Moreover, the βCD‐Ad‐Fc gel showed a redox‐responsive shape‐morphing effect. We thus succeeded in deriving three functions from the introduction of two kinds of functional units into a supramolecular material. 相似文献
9.
Kohei Miyamae Masaki Nakahata Yoshinori Takashima Akira Harada 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2015,127(31):9112-9115
Supramolecular materials cross‐linked between polymer chains by noncovalent bonds have the potential to provide dynamic functions that are not produced by covalently cross‐linked polymeric materials. We focused on the formation of supramolecular polymeric materials through host–guest interactions: a powerful method for the creation of nonconventional materials. We employed two different kinds of host–guest inclusion complexes of β‐cyclodextrin (βCD) with adamantane (Ad) and ferrocene (Fc) to bind polymers together to form a supramolecular hydrogel (βCD‐Ad‐Fc gel). The βCD‐Ad‐Fc gel showed self‐healing ability when damaged and responded to redox stimuli by expansion or contraction. Moreover, the βCD‐Ad‐Fc gel showed a redox‐responsive shape‐morphing effect. We thus succeeded in deriving three functions from the introduction of two kinds of functional units into a supramolecular material. 相似文献
10.
Propagation of Enzyme‐Induced Surface Events inside Polymer Nanoassemblies for a Fast and Tunable Response 下载免费PDF全文
Dr. Jiaming Zhuang Dr. Hatice Seçinti Bo Zhao Prof. Dr. S. Thayumanavan 《Angewandte Chemie (International ed. in English)》2018,57(24):7111-7115
We report a new molecular design strategy that allows for the propagation of surface enzymatic events inside a supramolecular assembly for accelerated molecular release. The approach addresses a key shortcoming encountered with many of the currently available enzyme‐induced disassembly strategies, which rely on the unimer–aggregate equilibria of amphiphilic assemblies. The enzymatic response of the host to predictably tune the kinetics of guest‐molecule release can be programmed by controlling substrate accessibility through electrostatic complexation with a complementary polymer. Accelerated guest release in response to the enzyme is shown to be accomplished by a cooperative mechanism of enzyme‐triggered supramolecular host disassembly and host reorganization. 相似文献
11.
A Rapidly Self‐Healing Supramolecular Polymer Hydrogel with Photostimulated Room‐Temperature Phosphorescence Responsiveness 下载免费PDF全文
Hui Chen Prof. Xiang Ma Dr. Shuaifan Wu Prof. He Tian 《Angewandte Chemie (International ed. in English)》2014,53(51):14149-14152
Development of self‐healing and photostimulated luminescent supramolecular polymeric materials is important for artificial soft materials. A supramolecular polymeric hydrogel is reported based on the host–guest recognition between a β‐cyclodextrin (β‐CD) host polymer (poly‐β‐CD) and an α‐bromonaphthalene (α‐BrNp) polymer (poly‐BrNp) without any additional gelator, which can self‐heal within only about one minute under ambient atmosphere without any additive. This supramolecular polymer system can be excited to engender room‐temperature phosphorescence (RTP) signals based on the fact that the inclusion of β‐CD macrocycle with α‐BrNp moiety is able to induce RTP emission (CD‐RTP). The RTP signal can be adjusted reversibly by competitive complexation of β‐CD with azobenzene moiety under specific irradiation by introducing another azobenzene guest polymer (poly‐Azo). 相似文献
12.
Smart Organic Two‐Dimensional Materials Based on a Rational Combination of Non‐covalent Interactions 下载免费PDF全文
Dr. Wei Bai Ziwen Jiang Dr. Alexander E. Ribbe Prof. S. Thayumanavan 《Angewandte Chemie (International ed. in English)》2016,55(36):10707-10711
Rational design of organic 2D (O2D) materials has made some progress, but it is still in its infancy. A class of self‐assembling small molecules is presented that form nano/microscale supramolecular 2D materials in aqueous media. A judicial combination of four different intermolecular interactions forms the basis for the robust formation of these ultrathin assemblies. These assemblies can be programmed to disassemble in response to a specific protein and release its non‐covalently bound guest molecules. 相似文献
13.
Pim G. A. Janssen Joost L. J. van Dongen E. W. Meijer Prof. Dr. Albertus P. H. J. Schenning Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(2):352-360
Supramolecular complexes consisting of a single‐stranded oligothymine ( dTn ) as the host template and an array of guest molecules equipped with a complementary diaminotriazine hydrogen‐bonding unit have been studied with electrospray‐ionization mass spectrometry (ESI‐MS). In this hybrid construct, a supramolecular stack of guest molecules is hydrogen bonded to dTn . By changing the hydrogen‐bonding motif of the DNA host template or the guest molecules, selective hydrogen bonding was proven. We were able to detect single‐stranded‐DNA (ssDNA)–guest complexes for strands with lengths of up to 20 bases, in which the highest complex mass detected was 15 kDa; these complexes constitute 20‐component self‐assembled objects. Gas‐phase breakdown experiments on single‐ and multiple‐guest–DNA assemblies gave qualitative information on the fragmentation pathways and the relative complex stabilities. We found that the guest molecules are removed from the template one by one in a highly controlled way. The stabilities of the complexes depend mainly on the molecular weight of the guest molecules, a fact suggesting that the complexes collapse in the gas phase. By mixing two different guests with the ssDNA template, a multicomponent dynamic library can be created. Our results demonstrate that ESI‐MS is a powerful tool to analyze supramolecular ssDNA complexes in great detail. 相似文献
14.
Dr. Huacheng Zhang Prof. Dr. Yanli Zhao 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(50):16862-16879
In this review, we highlight recent advancements on pillararene‐based assemblies. The driving forces for the formation of the pillararene‐based assemblies are discussed first. The host–guest interactions are deemed as not only general strategy for constructing assemblies but also essential components for preventing the assemblies from the dissociation. Solvent effect is also important in the assembling process, since it could influence the host–guest interactions and provide solvophobic effect on pillararenes for the assembly. Then, several pillararene‐based assembly architectures are introduced, including pillararene‐based interlocked structures, such as (poly)pseudorotaxanes, (poly)rotaxanes, and daisy chains, classified by their topological structures and synthetic strategy. The morphologies of the supramolecular assemblies are divided into several types, for example, nanospheres, nanotubes and supramolecular polymers. Furthermore, the functions and potential applications are summarized accompanied with related assembly structures. The review not only provides fundamental findings, but also foresights future research directions in the research area of pillararene‐based assemblies. 相似文献
15.
Luyang Zhao Yamei Liu Ruirui Xing Xuehai Yan 《Angewandte Chemie (International ed. in English)》2020,59(10):3793-3801
Supramolecular assemblies have been very successful in regulating the photothermal conversion efficiency of organic photothermal materials in a simple and flexible way, compared with conventional molecular synthesis. In these assemblies, it is the inherent physiochemical mechanism that determines the photothermal conversion, rather than the assembly strategy. This Minireview summarizes supramolecular photothermal effects, which refer to the unique features of supramolecular chemistry for regulating the photothermal conversion efficiency. Emphasis is placed on the mechanisms of how self‐assembly affects the photothermal performance. The supramolecular photothermal effects on various types of light‐harvesting species are discussed in detail. The timely interpretation of supramolecular photothermal effects is promising for the future design of the photothermal materials with high efficiency, precision, and multiple functionalities for a wide array of applications. 相似文献
16.
Léna Sambe Victor R. de La Rosa Khaled Belal Dr. François Stoffelbach Dr. Joel Lyskawa Dr. François Delattre Marc Bria Prof. Graeme Cooke Prof. Richard Hoogenboom Prof. Patrice Woisel 《Angewandte Chemie (International ed. in English)》2014,53(20):5044-5048
A new class of polymeric thermometers with a memory function is reported that is based on the supramolecular host–guest interactions of poly(N‐isopropylacrylamide) (PNIPAM) with side‐chain naphthalene guest moieties and the tetracationic macrocycle cyclobis(paraquat‐p‐phenylene) (CBPQT4+) as the host. This supramolecular thermometer exhibits a memory function for the thermal history of the solution, which arises from the large hysteresis of the thermoresponsive LCST phase transition (LCST=lower critical solution temperature). This hysteresis is based on the formation of a metastable soluble state that consists of the PNIPAM–CBPQT4+ host–guest complex. When heated above the transition temperature, the polymer collapses, and the host–guest interactions are disrupted, making the polymer more hydrophobic and less soluble in water. Aside from providing fundamental insights into the kinetic control of supramolecular assemblies, the developed thermometer with a memory function might find use in applications spanning the physical and biological sciences. 相似文献
17.
Squeezing,Then Stacking: From Breathing Pores to Three‐Dimensional Ionic Self‐Assembly under Electrochemical Control 下载免费PDF全文
Kang Cui Dr. Kunal S. Mali Dr. Oleksandr Ivasenko Dongqing Wu Dr. Xinliang Feng Dr. Michael Walter Prof. Klaus Müllen Prof. Steven De Feyter Dr. Stijn F. L. Mertens 《Angewandte Chemie (International ed. in English)》2014,53(47):12951-12954
We demonstrate the spontaneous and reversible transition between the two‐ and three‐dimensional self‐assembly of a supramolecular system at the solid–liquid interface under electrochemical conditions, using in situ scanning tunneling microscopy. By tuning the interfacial potential, we can selectively organize our target molecules in an open porous pattern, fill these pores to form an auto‐host–guest structure, or stack the building blocks in a stratified bilayer. Using a simple electrostatic model, we rationalize which charge density is required to enable bilayer formation, and conversely, which molecular size/charge ratio is necessary in the design of new building blocks. Our results may lead to a new class of electrochemically controlled dynamic host–guest systems, artificial receptors, and smart materials. 相似文献
18.
Marina Frank Dr. Mark D. Johnstone Prof. Dr. Guido H. Clever 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(40):14104-14125
This Review covers design strategies, synthetic challenges, host–guest chemistry, and functional properties of interlocked supramolecular cages. Some dynamic covalent organic structures are discussed, as are selected examples of interpenetration in metal–organic frameworks, but the main focus is on discrete coordination architectures, that is, metal‐mediated dimers. Factors leading to interpenetration, such as geometry, flexibility and chemical makeup of the ligands, coordination environment, solvent effects, and selection of suitable counter anions and guest molecules, are discussed. In particular, banana‐shaped bis‐pyridyl ligands together with square‐planar metal cations have proven to be suitable building blocks for the construction of interpenetrated double‐cages obeying the formula [M4L8]. The peculiar topology of these double‐cages results in a linear arrangement of three mechanically coupled pockets. This allows for the implementation of interesting guest encapsulation effects such as allosteric binding and template‐controlled selectivity. In stimuli‐responsive systems, anionic triggers can toggle the binding of neutral guests or even induce complete structural conversions. The increasing structural and functional complexity in this class of self‐assembled hosts promises the construction of intelligent receptors, novel catalytic systems, and functional materials. 相似文献
19.
Photo‐Controlled Reversible Microtubule Assembly Mediated by Paclitaxel‐Modified Cyclodextrin 下载免费PDF全文
Dr. Ying‐Ming Zhang Ni‐Yuan Zhang Kui Xiao Dr. Qilin Yu Prof. Dr. Yu Liu 《Angewandte Chemie (International ed. in English)》2018,57(28):8649-8653
The design and construction of multi‐stimuli‐responsive supramolecular nanoassemblies that can mimic and regulate the fundamental biological processes have become a focus of interest in supramolecular chemistry. In this work, a perfect combination has been achieved between naturally occurring microtubules and artificially macrocyclic receptors. The self‐assembling morphology of microtubules can be photo‐tuned by the host–guest interaction of paclitaxel‐modified β‐cyclodextrin (PTX‐CD) and photochromic arylazopyrazole (PTX‐AAP). Moreover, the supramolecularly aggregated microtubules in a cellular environment can induce a pronounced cell morphological change and cell death. This supramolecular approach based on the secondary PTX‐AAP?PTX‐CD complexation provides us a facile method to reversibly control the intertubular aggregation behaviors of microtubules, which may bring new perspectives in the treatment of diseases related to improper protein aggregation. 相似文献
20.
Cucurbituril‐mediated immobilization of fluorescent proteins on supramolecular biomaterials 下载免费PDF全文
Olga J. G. M. Goor Ralph P. G. Bosmans Luc Brunsveld Patricia Y. W. Dankers 《Journal of polymer science. Part A, Polymer chemistry》2017,55(21):3607-3616
The reversible introduction of functionality at material surfaces is of interest for the development of functional biomaterials. In particular, the use of supramolecular immobilization strategies facilitates mild reaction and processing conditions, as compared to other covalent analogues. Here, the engineering of multicomponent supramolecular materials, beyond the use of a single supramolecular entity is proposed. Cucurbit[8]uril (Q8) mediated host–guest chemistry is combined with hydrogen bonding supramolecular 2‐ureido‐4‐pyrimidinone (UPy)‐based materials. The modular incorporation of a UPy‐additive that presents one guest to incorporate into the Q8 host allows for selective supramolecular functionalization at the water–polymer material interface. Supramolecular ternary complex formation at the material surface was studied by X‐ray photoelectron spectroscopy, which as a result of large overlap in atomic composition of the different components showed minor changes is surface composition upon complex formation. Surface MALDI‐ToF MS measurements revealed useful insights in the formation of complexes. Protein immobilization was monitored using both fluorescence spectroscopy and quartz crystal microbalance with dissipation monitoring, which successfully demonstrated ternary complex formation. Although proteins could selectively be immobilized onto the surfaces, control of the system's stability remains a challenge as a result of the dynamicity of the host–guest assembly. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3607–3616 相似文献