Thermoresponsive hydrogel of diblock methylcellulose: formation of ribbonlike supramolecular nanostructures by self-assembly

This article provides detailed insight into the thermoresponsive gelation mechanism of industrially produced methylcellulose (MC), highlighting the importance of diblock structure with a hydrophobic sequence of 2,3,6-tri-O-methyl-glucopyranosyl units for this physicochemical property. We show herein, for the first time, that well-defined diblock MC self-assembles thermoresponsively into ribbonlike nanostructures in water. A cryogenic transmission electron microscopy (cryo-TEM) technique was used to detect the ribbonlike nanostructures formed by the diblock copolymers consisting of hydrophilic glucosyl or cellobiosyl and hydrophobic 2,3,6-tri-O-methyl-cellulosyl blocks, methyl β-d-glucopyranosyl-(1→4)-2,3,6-tri-O-methyl-celluloside 1 (G-236MC, DP(n) = 10.7, DS = 2.65), and methyl β-d-glucopyranosyl-(1→4)-β-d-glucopyranosyl-(1→4)-2,3,6-tri-O-methyl-celluloside 2 (GG-236MC, DP(n) = 28.2, DS = 2.75). Rheological measurements revealed that the gel strength of a dispersion of GG-236MC (2, 2.0 wt %) in water at 70 °C was 3.0 times stronger than that of commercial MC SM-8000, although the molecular weight of GG-236MC (2) having M(w) = 8 × 10(3) g/mol was 50 times smaller than that of SM-8000 having M(w) = 4 × 10(5) g/mol. Cryo-TEM observation suggested that the hydrogel formation of the diblock copolymers could be attributed to the entanglement of ribbonlike nanostructures self-assembled by the diblock copolymers in water. The cryo-TEM micrograph of GG-236MC (2) at 5 °C showed rectangularly shaped nanostructures having a thickness from 11 to 24 nm, although G-236MC (1) at 20 °C showed no distinct self-assembled nanostructures. The ribbonlike nanostructures of GG-236MC (2) having a length ranging from 91 to 864 nm and a thickness from 8.5 to 27.1 nm were detected above 20 °C. Small-angle X-ray scattering measurements suggested that the ribbonlike nanostructures of GG-236MC (2) consisted of a bilayer structure with a width of ca. 40 nm. It was likely that GG-236MC (2) molecules were oriented perpendicularly to the long axis of the ribbonlike nanostructure. In addition, wide-angle X-ray scattering measurements revealed that GG-236MC (2) in its hydrogel formed the same crystalline regions as 2,3,6-tri-O-methylcellulose. The influence of the DP of diblock MC with a DS of around 2.7 on the gelation behavior will be discussed.     

Photonics of supramolecular nanostructures

The results of studying optical and photochemical properties of organic supramolecular nanostructures capable of self-organizing due to specific intermolecular interactions are generalized in the review. The linear and nonlnear optical properties of supramolecular nanostructures of the guest—host type based on cyclodextrins, intramolecular and intermolecular complexes of crown-containing styryl dyes with metal cations, and aggregates of carbocyanine dyes are described. Photolysis reactions in supramolecular nanostructures, including photoisomerization, photocycloaddition, and formation of excimeric and charge-transfer complexes are presented. A possibility of controlling photochemical transformations in these systems by the light and cations of metal salts is shown.     

Hierarchical self-assembly into chiral nanostructures

One basic principle regulating self-assembly is associated with the asymmetry of constituent building blocks or packing models. Using asymmetry to manipulate molecular-level devices and hierarchical functional materials is a promising topic in materials sciences and supramolecular chemistry. Here, exemplified by recent major achievements in chiral hierarchical self-assembly, we show how chirality may be utilized in the design, construction and evolution of highly ordered and complex chiral nanostructures. We focus on how unique functions can be developed by the exploitation of chiral nanostructures instead of single basic units. Our perspective on the future prospects of chiral nanostructures via the hierarchical self-assembly strategy is also discussed.

This review shows how chirality may be used for the design, construction and evolution of higher ordered and complex chiral nanostructures through hierarchical self-assembly.     

Combinatorial self-assembly of DNA nanostructures

Here we report a modular design of self-assembly of DNA nanostructures in a combinatorial approach; a square with approximately 25 nm cavity dimension, a chair with approximately 80 nm in height and a line with approximately 100 nm in length are formed through combinations of four cross-shaped DNA tiles which are kept constant and six variable linker tiles.     

超分子自组装中的非共价键协同作用

本文综述了近年来氢键、π-π堆积作用、配位作用、供体-受体相互作用和疏溶剂作用等多种非共价键协同作用在超分子自组装研究中的新进展。     

Coordination-driven self-assembly of predesigned supramolecular triangles

The design and self-assembly of three supramolecular triangles is described. A novel 60 degrees corner unit directs the exclusive formation of triangular assemblies that are not in detectable equilibrium with other macrocycles. The resulting triangles have sides ranging from 2.7 to 3.5 nm in length and molecular masses as high as 5396 amu. The crystal structure of one of the assemblies shows an approximately 1.4 nm cavity; the crystal packing forms open, triangular channels. The characterization of the supramolecular triangles by multinuclear NMR, elemental analysis, and electrospray mass spectrometry is also reported.     

Confined supramolecular nanostructures of mesogen-bearing amphiphiles

Stable surface nanostructures with different morphology have been successfully constructed by modifying the chemical structure of synthetic amphiphiles; by introducing mesogenic groups into bolaform amphiphiles, stable spaghetti-like or stripe-like nanostructures can be obtained; it is believed that such a kind of surface structure could be used for templating synthesis and assembly.     

Physics and engineering of peptide supramolecular nanostructures

The emerging "bottom-up" nanotechnology reveals a new field of bioinspired nanomaterials composed of chemically synthesized biomolecules. They are formed from elementary constituents in supramolecular structures by the use of a developed nature self-assembly mechanism. The focus of this perspective paper is on intrinsic fundamental physical properties of bioinspired peptide nanostructures and their small building units linked by weak noncovalent bonds. The observed exceptional optical properties indicate a phenomenon of quantum confinement in these supramolecular structures, which originates from nanoscale size of their elementary building blocks. The dimensionality of the confinement gives insight into intrinsic packing of peptide supramolecular nanomaterials. QC regions, revealed in bioinspired nanostructures, were found by us in amyloid fibrils formed from insulin protein. We describe ferroelectric and related properties found at the nanoscale based on original crystalline asymmetry of the nanoscale building blocks, packing these structures. In this context, we reveal a classic solid state physics phenomenon such as reconstructive phase transition observed in bioorganic peptide nanotubes. This irreversible phase transformation leads to drastic reshaping of their quantum structure from quantum dots to quantum wells, which is followed by variation of their space group symmetry from asymmetric to symmetric. We show that the supramolecular origin of these bioinspired nanomaterials provides them a unique chance to be disassembled into elementary building block peptide nanodots of 1-2 nm size possessing unique electronic, optical and ferroelectric properties. These multifunctional nanounits could lead to a new future step in nanotechnology and nanoscale advanced devices in the fields of nanophotonics, nanobiomedicine, nanobiopiezotronics, etc.     

Controlled self-assembly of triphenylene-based molecular nanostructures

Molecular nanostructures of the disc-shaped molecule hexapentyloxytriphenylene have been fabricated on length scales ranging from 30 nm to 1.5 mum following self-assembly arising from pi-pi interactions in organic solvents. The size and density of the molecular nanostructures deposited onto glass and indium tin oxide-coated glass substrates were characterized by atomic force microscopy. Dynamic light scattering and spectroscopic evidence of predeposition aggregation in solution are presented, suggesting that the nanostructures are organized in solution and then deposited onto the substrate. Correlations between the relative solvent polarity and the size of molecular nanostructures as well as between the solute concentration in dilute solutions and their density on the substrate are discussed.     

Photoresponsive self-assembly and self-organization of hydrogen-bonded supramolecular tapes

Self-assembling building blocks that are readily functionalizable and capable of achieving programmed hierarchical organization have enabled us to create various functional nanomaterials. We have previously demonstrated that N,N'-disubstituted 4,6-diaminopyrimidin-2(1 H)-one (DAP), a guanine-cytosine hybridized molecule, is a versatile building block for the creation of tapelike supramolecular polymer species in solution. In the current study, DAP was functionalized with azobenzene side chains. 1H NMR, UV/Vis, and dynamic light scattering studies confirmed the presence of nanometer-scale tapelike supramolecular polymers in alkane solvents at micromolar regimes. At higher concentrations (millimolar regimes), the supramolecular polymers hierarchically organized into lamellar superstructures to form organogels, as shown by X-ray diffraction and polarized optical microscopy. Remarkably, the azobenzene side chains are photoisomerizable even in the supramolecular polymers, owing to their loosely packed state supported by the rigid hydrogen-bonded scaffold, enabling us to establish photocontrollable supramolecular polymerization and higher order organization of the tapelike supramolecular polymers into lamellar superstructures.     

Switching between supramolecular dimer and nonthreaded supramolecular self-assembly of stilbene amide-alpha-cyclodextrin by photoirradiation

3-trans-Stilbene amide-alpha-cyclodextrin (3-trans-Sti-alpha-CD) formed a double-threaded dimer in aqueous solutions. In contrast, the photoisomerization of the stilbene moiety in 3-Sti-alpha-CD from trans to cis leads to the structural changes from the double-threaded dimer to nonthreaded supramolecular assemblies in aqueous solutions. The structures of these supramolecular complexes have been found to be controllable by photoirradiation.     

Tunable symmetry and periodicity in binary supramolecular nanostructures

We present a route to change the "compositional" order of highly crystalline binary layers comprising diindenoperylene and copper-phthalocyanines from two- to one-dimensional periodicity. This is achieved by exchanging fluorine with hydrogen atoms in the phthalocyanines, thereby reducing the C-F···H-C interactions and allowing the interplay of long-range electrostatic interactions in mesoscopic phases. Linear patterns are thus obtained, whose periodicity can be additionally tuned by an appropriate stoichiometry of the components.     

Advanced supramolecular polymers constructed by orthogonal self-assembly

Large aggregates, constructed by linking together monomer building blocks via non-covalent interactions with polymer properties, are regarded as supramolecular polymers. Many kinds of non-covalent interactions, such as metal-ligand coordination, hydrogen bonding, π-π stacking, ionic interaction, and host-guest interaction etc., can be involved in the binding interactions of monomer building blocks, as well as in the modification of the side chain for the construction of variable supramolecular polymers. In this tutorial review, we summarized the reported supramolecular polymers fully- or partially-created from the combination of multiple non-covalent binding interactions, mainly of two kinds, in the orthogonal way.     

DNA directed self-assembly of anisotropic plasmonic nanostructures

Programmable positioning of one-dimensional (1D) gold nanorods (AuNRs) was achieved by DNA directed self-assembly. AuNR dimer structures with various predetermined inter-rod angles and relative distances were constructed with high efficiency. These discrete anisotropic metallic nanostructures exhibit unique plasmonic properties, as measured experimentally and simulated by the discrete dipole approximation method.     

Physical mechanisms and biological significance of supramolecular protein self-assembly

In living cells, chemical reactions of metabolism, information processing, growth and development are organized in a complex network of interactions. At least in part, the organization of this network is accomplished as a result of physical assembly by supramolecular scaffolds. Indeed, most proteins function in cells within the context of multimeric or supramolecular assemblies. With the increasing availability of atomic structures and molecular thermodynamics, it is possible to recast the problem of non-covalent molecular self-assembly from a unified perspective of structural thermodynamics and kinetics. Here, we present a generalized theory of self-assembly based on Wegner's kinetic model and use it to delineate three physical mechanisms of self-assembly: as limited by association of assembly units (nucleation), by association of monomers (isodesmic), and by conformational reorganization of monomers that is coupled to assembly (conformational). Thus, we discuss actin, tubulin, clathrin, and the capsid of icosahedral cowpea chlorotic mottle virus with respect to assembly of architectural scaffolds that perform largely mechanical functions, and pyruvate dehydrogenase, and RING domain proteins PML, arenaviral Z, and BRCA1:BARD1 with regard to assembly of supramolecular enzymes with metabolic and chemically directive functions. In addition to the biological functions made possible by supramolecular self-assembly, such as mesoscale mechanics of architectural scaffolds and metabolic coupling of supramolecular enzymes, we show that the physical mechanisms of self-assembly and their structural bases are biologically significant as well, having regulatory roles in both formation and function of the assembled structures in health and disease.     

卟啉超分子的组装合成及其应用新进展

卟啉超分子已被广泛地用于光学、催化、仿生等方面的研究,部分研究成果已获得实际应用．本文综述了卟啉超分子在组装合成及应用方面的新进展,包括基于不同结构卟啉砌块的新型二维与三维超分子的构筑以及卟啉超分子在光学、催化和分子识别等方面的应用．