Macroscopic supramolecular assembly (MSA) is a new concept in supramolecular science with a focus on interfacial assembly of macroscopic building blocks, which has largely extended the applicable materials of supramolecular assembly and provided new solutions to fabricating tissue scaffolds, soft devices, etc. The precision of the assembled structures is of great interest; unlike molecular assemblies, MSA precision is highly dependent on the matching degree of assembled surfaces because of the large interactive area and group number, which result in remarkably increased kinetic possibilities and metastable assemblies. This Concept introduces the principle, history, and development of MSA, elaborates the low-precision challenge in MSA, summarizes the strategies for precise MSA based on the different thermodynamic stability of precise/imprecise structures and control over assembly kinetics, and finally demonstrates the applications of precise MSA structures in advanced manufacture such as tissue scaffolds. 相似文献
Macroscopic supramolecular assembly (MSA) is a recent development in supramolecular chemistry to associate visible building blocks through non‐covalent interactions in a multivalent manner. Although various substrates (e.g. hydrogels, rigid materials) have been used, a general design rule of building blocks in MSA systems and interpretation of the assembly mechanism are lacking and are required. Herein we design three model systems with varied elastic modulus and correlated the MSA probability with the elasticity. Based on the effects of substrate deformability on multivalency, we have proposed an elastic‐modulus‐dependent rule that building blocks below a critical modulus of 2.5 MPa can achieve MSA for the used host/guest system. Moreover, this MSA rule applies well to the design of materials for fast underwater adhesion: Soft substrates (0.5 MPa) can achieve underwater adhesion within 10 s with one order of magnitude higher strength than that of rigid substrates (2.5 MPa). 相似文献
Three‐dimensional unidirectionally aligned and responsive supramolecular hierarchical assemblies have much potential in adaptive materials for biomedical and soft actuator applications. However, to achieve systematical control of the motion of stimuli‐responsive materials by orthogonal external stimuli and to complete a series of complicated tasks remains a grand challenge. Herein, we demonstrate a novel designed hybrid supramolecular assembly of molecular motor amphiphiles that also serves as a template for iron nanoparticles growth, and as a consequence this soft hybrid material is orthogonally controlled by dual light/magnetic stimuli. Macroscopic motor amphiphile strings, decorated with iron nanoparticles, provide fast response photoactuations and magnet induced movements that allows a precisely controlled cargo transport process. 相似文献
Macroscopic supramolecular assembly bridges fundamental research on molecular recognition and the potential applications as bulk supramolecular materials. However, challenges remain to realize stable precise assembly, which is significant for further functions. To handle this issue, the Marangoni effect is applied to achieve spontaneous locomotion of macroscopic building blocks to reach interactive distance, thus contributing to formation of ordered structures. By increasing the density of the building blocks, the driving force for assembly transforms from a hydrophobic–hydrophobic interaction to hydrophilic–hydrophilic interaction, which is favorable for introducing hydrophilic coatings with supramolecular interactive groups on matched surfaces, consequently realizing the fabrication of stable precise macroscopic supramolecular assemblies. 相似文献
Glassy materials, with desirable mechanical rigidity, shaping ability, high transparency, are attracting great interest in diverse fields. However, optically bulk molecule-based glasses are still rare, mainly due to limited monomeric species and harsh preparation conditions. Herein, we report a facile bottom-up solution fabrication process to obtain metal-free supramolecular glasses (SMGs) at the macroscopic scale using L-Histidine and hexamethylenetetramine as building blocks. The chiral SMGs possess color-tunable ultralong room temperature phosphorescence (decay lifetime up to 141.2 ms) and circular polarized luminescence (g factor up to 8.7×10−3). The strong hydrogen bonds effectively drive the formation of SMGs, and provide a rigid microenvironment to boost triplet exciton generation. By virtue of excitation- and temperature-dependent ultralong phosphorescence of the SMGs, applications including multicolored displays, visual UV detection, and persistently luminescent thermometer are demonstrated. 相似文献
The radial conjugated π-system of cycloparaphenylenes (CPPs) makes them intriguing fluorophores and unique supramolecular hosts. However, the bright photoluminescence (PL) of CPPs was limited to the blue light and the supramolecular assembly behavior of large CPPs was rarely investigated. Here we present the synthesis of tetra-benzothiadiazole-based [12]cycloparaphenylene (TB[12]CPP), which exhibits a lime to orange PL with an excellent quantum yield up to 82 % in solution. The PL quantum yield of TB[12]CPP can be further improved to 98 % in polymer matrix. Benefiting from its enlarged size, TB[12]CPP can accommodate a fullerene derivative or concave–convex complexes of fullerene and buckybowl through the combined π–π and C−H⋅⋅⋅π interactions. The latter demonstrates the first case of a ternary supramolecule of CPPs. 相似文献
Integrating irreplaceable features of both covalent chemistry and noncovalent interactions into a single entity to maximize the applicability is highly desired. Here, a discovery of this type of hybrid, developed by Stupp and co‐workers, is developed, where a synergistic combination of covalent and noncovalent compartments enables them to assemble by each other perfectively. The covalent compartments can grow into polymer chains assisted by a supramolecular compartment. The supramolecular compartments can be reversibly removed and re‐formed to reconstitute the hybrid structure. The obtained soft materials can serve as functional platforms for molecular delivery or self‐repairing materials.
We demonstrated recently that large nanomembranes became available from inorganic, organic/inorganic and totally organic precursors. Spin coating of mixtures of acrylate monomers and zirconium butoxide (or tetraethoxysilane), when combined with simultaneous radical polymerization and sol-gel reaction, gave 10–30 nm thick, free-standing nanomembranes composed of metal oxides and crosslinked acrylates as interpenetrating network. This approach was extended to thermosetting resins (epoxy, melamine and phthalic resins), to fabricate robust, free-standing nanomembranes. Mechanical properties of the nanomembranes as measured by the bulge test and by a compression method were comparable to those of the corresponding macroscopic resins. The hybrid nanomembrane was subsequently prepared by supramolecular assembly of the nanofilm with surfactants and lipids. These amphiphiles produced adsorbed monolayers on the nanomembrane and some of the assemblies were stably kept in water. 相似文献
The self-assembly of porphyrin arrays containing three, seven or eleven porphyrins results from the interaction of the bis-pyridyl porphyrin 1 with the zinc porphyrins 2, 3, or 4, respectively. 相似文献
Hierarchical carbohydrate architectures serve multiple roles in nature. Hardly any correlations between the carbohydrate chemical structures and the material properties are available due to the lack of standards and suitable analytic techniques. Therefore, designer carbohydrate materials remain highly unexplored, as compared to peptides and nucleic acids. A synthetic D -glucose disaccharide, DD , was chosen as a model to explore carbohydrate materials. Microcrystal electron diffraction (MicroED), optimized for oligosaccharides, revealed that DD assembled into highly crystalline left-handed helical fibers. The supramolecular architecture was correlated to the local crystal organization, allowing for the design of the enantiomeric right-handed fibers, based on the L -glucose disaccharide, LL , or flat lamellae, based on the racemic mixture. Tunable morphologies and mechanical properties suggest the potential of carbohydrate materials for nanotechnology applications. 相似文献
New synthetic methodologies towards hydrogen bonded supramolecular polymers are described. Focus is directed on synthetic work towards telechelics with hydrogen bonds either as side chain moieties or as endgroups. Physical ordering effects related to polymers and particles are discussed citing own and related work in ∼60 references. 相似文献
The templating effect of the tetrafluoroborate ion leads to assembly of four CoII ions and six bridging ligands around this anion to give a tetrahedral complex with a bridging ligand along each edge and the anion trapped in the central cavity (shown below). Surprisingly under identical conditions but with NiII a simpler dinuclear complex forms. 相似文献