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Biological materials, such as bones, teeth and mollusc shells, are well known for their excellent strength, modulus and toughness1-3. Such properties are attributed to the elaborate layered microstructure of inorganic reinforcing nanofillers, especially two-dimensional nanosheets or nanoplatelets, within a ductile organic matrix4-6. Inspired by these biological structures, several assembly strategies-including layer-by-layer4,7,8, casting9,10, vacuum filtration11-13 and use of magnetic fields14,15-have been used to develop layered nanocomposites. However, how to produce ultrastrong layered nanocomposites in a universal, viable and scalable manner remains an open issue. Here we present a strategy to produce nanocomposites with highly ordered layered structures using shear-flow-induced alignment of two-dimensional nanosheets at an immiscible hydrogel/oil interface. For example, nanocomposites based on nanosheets of graphene oxide and clay exhibit a tensile strength of up to 1,215 ± 80 megapascals and a Young's modulus of 198.8 ± 6.5 gigapascals, which are 9.0 and 2.8 times higher, respectively, than those of natural nacre (mother of pearl). When nanosheets of clay are used, the toughness of the resulting nanocomposite can reach 36.7 ± 3.0 megajoules per cubic metre, which is 20.4 times higher than that of natural nacre; meanwhile, the tensile strength is 1,195 ± 60 megapascals. Quantitative analysis indicates that the well aligned nanosheets form a critical interphase, and this results in the observed mechanical properties. We consider that our strategy, which could be readily extended to align a variety of two-dimensional nanofillers, could be applied to a wide range of structural composites and lead to the development of high-performance composites.
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Materiais Biomiméticos/química , Materiais Biomiméticos/síntese química , Nanocompostos/química , Resistência à Tração , Módulo de Elasticidade , Grafite/química , Hidrogéis/química , Nácar/químicaRESUMO
Although phage display selection using a library of M13 bacteriophage has become a powerful tool for finding peptides that bind to target materials on demand, a remaining concern of this method is the interference by the M13 main body, which is a huge filament >103 â times larger than the displayed peptide, and therefore would nonspecifically adhere to the target or sterically inhibit the binding of the displayed peptide. Meanwhile, filamentous phages are known to be orientable by an external magnetic field. If M13 filaments are magnetically oriented during the library selection, their angular arrangement relative to the target surface would be changed, being expected to control the interference by the M13 main body. This study reports that the magnetic orientation of M13 filaments vertical to the target surface significantly affects the selection. When the target surface was affinitive to the M13 main body, this orientation notably suppressed the nonspecific adhesion. Furthermore, when the target surface was less affinitive to the M13 main body and intrinsically free from the nonspecific adhesion, this orientation drastically changed the population of M13 clones obtained through library selection. The method of using no chemicals but only a physical stimulus is simple, clean, and expected to expand the scope of phage display selection.
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Técnicas de Visualização da Superfície Celular , Biblioteca de Peptídeos , Peptídeos/metabolismo , Bacteriófago M13/genética , Bacteriófago M13/metabolismo , Fenômenos MagnéticosRESUMO
Unlike absorption-based colors of dyes and pigments, reflection-based colors of photonic crystals, so called "structural colors", are responsive to external stimuli, but can remain unfaded for over ten million years, and therefore regarded as a next-generation coloring mechanism. However, it is a challenge to rationally design the spectra of structural colors, where one structure gives only one reflection peak defined by Bragg's law, unlike those of absorption-based colors. Here, we report a reconfigurable photonic crystal that exhibits single-peak and double-peak structural colors. This photonic crystal is composed of a colloidal nanosheet in water, which spontaneously adopts a layered structure with single periodicity (407â nm). After a temperature-gradient treatment, the photonic crystal segregates into two regions with shrunken (385â nm) and expanded (448â nm) periodicities, and thus exhibits double reflection peaks that are blue- and red-shifted from the original one, respectively. Notably, the transition between the single-peak and double-peak states is reversible.
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The photocyclodimerization of 2-anthracenecarboxylic acid has been extensively studied as a model reaction of asymmetric photochemistry. So far, numerous chiral environments have been employed to control this photoreaction, while the scope of photoreactants has been limited only to 2-anthracenecarboxylic acid and its simple esters and amides. Here, we developed a systematic series of photoreactants (2 a-d) by introducing various substituents to 2-anthracenecarboxylic acid, which showed different reactivities and selectivities depending on the substituents. By using the photoreactants 2 a-d, we evaluated the performance of a chiral environment composed of an amphiphilic amino alcohol (1), where the photocyclodimerization of 2 a-d generally proceeded in excellent regio- and enantioselectivities (71-98 % regio ratio, 76-86 % ee). Furthermore, by reacting 2 a and 2 b together in the chiral environment of 1, we succeeded in the first stereocontrolled cross-photocyclodimerization between two prochiral anthracenes (58 % chemo ratio, 83 % regio ratio, 90 % ee).
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Amino Álcoois , Antracenos , Estereoisomerismo , Dimerização , Ciclização , Antracenos/químicaRESUMO
Chiral amphiphiles are useful for controlling the structures and properties of supramolecular assemblies, but their stereocontrolled synthesis is generally difficult, because their long alkyl chains tend to bring unfavorable effects on the solubility, reactivity, and crystallinity of molecules. Typical examples are amphiphilic 1,2-amino alcohols (S)-1 and (1S,2S)-2 developed by our group, which were known to serve as chiral reaction media for controlling the stereochemistry of asymmetric photoreactions. We previously developed synthetic schemes for these 1,2-amino alcohols, but their synthetic efficiencies were unsatisfactory (13 steps with 2% overall yield for (S)-1; eight steps with 8% yield for (1S,2S)-2). As the main reason of such low efficiencies, the stereocontrolling methods we previously employed (diastereomer-salt crystallization for (S)-1; stereoselective reactions for (1S,2S)-2) were not ideal. Here, we report highly improved synthetic schemes for (S)-1 and (1S,2S)-2 based on the enantioselective high performance liquid chromatography (HPLC) separation of intermediates in preparative scales. Compared with the previous schemes, the new schemes are advantageous in fewer number of steps, higher overall yield, and lower risk of racemization (seven steps with 15% overall yield for (S)-1; seven steps with 26% overall yield for (1S,2S)-2).
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Amino Álcoois , Amino Álcoois/química , Cromatografia Líquida de Alta Pressão/métodos , EstereoisomerismoRESUMO
Ultralong organic phosphorescence (UOP) has aroused enormous interest in recent years. UOP materials are mainly limited to crystals or rigid host-guest systems. Their poor processability and mechanical properties critically hamper practical applications. Here, we reported a series of ultralong phosphorescent foams with high mechanical strength. Phosphorescence lifetime of the foam can reach up to 485.8 ms at room temperature. Impressively, lightweight gelatin foam can bear a compressive pressure of 4.44 MPa. Moreover, phosphorescence emission of polymer foam can be tuned from blue to orange through varying the excitation wavelength. Experimental data and theoretical calculations revealed that ultralong phosphorescence was ascribed to the fixation of multiple hydrogen bonds to the clusters of carbonyl groups. These results will allow for expanding the scope of luminescent foams, providing an ideal platform for developing ultralong phosphorescent materials with high mechanical strength.
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Machine technology frequently puts magnetic or electrostatic repulsive forces to practical use, as in maglev trains, vehicle suspensions or non-contact bearings. In contrast, materials design overwhelmingly focuses on attractive interactions, such as in the many advanced polymer-based composites, where inorganic fillers interact with a polymer matrix to improve mechanical properties. However, articular cartilage strikingly illustrates how electrostatic repulsion can be harnessed to achieve unparalleled functional efficiency: it permits virtually frictionless mechanical motion within joints, even under high compression. Here we describe a composite hydrogel with anisotropic mechanical properties dominated by electrostatic repulsion between negatively charged unilamellar titanate nanosheets embedded within it. Crucial to the behaviour of this hydrogel is the serendipitous discovery of cofacial nanosheet alignment in aqueous colloidal dispersions subjected to a strong magnetic field, which maximizes electrostatic repulsion and thereby induces a quasi-crystalline structural ordering over macroscopic length scales and with uniformly large face-to-face nanosheet separation. We fix this transiently induced structural order by transforming the dispersion into a hydrogel using light-triggered in situ vinyl polymerization. The resultant hydrogel, containing charged inorganic structures that align cofacially in a magnetic flux, deforms easily under shear forces applied parallel to the embedded nanosheets yet resists compressive forces applied orthogonally. We anticipate that the concept of embedding anisotropic repulsive electrostatics within a composite material, inspired by articular cartilage, will open up new possibilities for developing soft materials with unusual functions.
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Hidrogel de Polietilenoglicol-Dimetacrilato/química , Nanoestruturas/química , Eletricidade Estática , Anisotropia , Biomimética , Cartilagem Articular/química , Nióbio/química , Titânio/químicaRESUMO
Based on the predesigned self-selective complexation, metallo-supramolecular P3HT-b-PEO diblock copolymers with varying block ratios were synthesized, and their oriented polymer films generated during solvent evaporation in a 9 T magnetic field were investigated. An anisotropic, ordered layer structure was achieved using [P3HT20 -Zn-PEO107 ] and carefully characterized by polarized optical microscopy (POM), AFM, polarized UV/Vis spectroscopy, and GI-SAXS/WAXS. The PEO-removed [P3HT20 -Zn-PEO107 ] film was obtained after decomplexation with TEA-EDTA under mild conditions, and the selective removal of PEO domains was evidenced by UV/Vis and ATR-FTIR spectroscopy. Anisotropic photoconductivity of the magnetically aligned film was evaluated by flash-photolysis time-resolved microwave conductivity (FP-TRMC) measurements. The results indicated that the presence of insulating crystalline PEO segments diminished the photoconductivity along the P3HT backbone direction.
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The longest bottlebrush polymers reported so far (up to 7â µm in length) were synthesized in two steps from a norbornene derivative bearing two 2-bromoisobutylate moieties (NB). The key to this achievement is the excellent reactivity of NB in ring opening metathesis polymerization, which proceeded in a well-controlled manner with quantitative conversion of NB for monomer-initiator ratios ranging up to 10,000. The resultant polymer derived from NB was readily converted to various bottlebrush polymers in a divergent synthetic route by grafting vinyl monomers from the 2-bromoisobutylate units in NB via atom transfer radical polymerization. The structure of the ultra-long bottlebrush polymer was directly observed using atomic force microscopy.
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Herein we report the synthesis and isolation of a shape-persistent Janus protein nanoparticle derived from the biomolecular machine chaperonin GroEL (AGroELB) and its application to DNA-mediated ternary supramolecular copolymerization. To synthesize AGroELB with two different DNA strands A and B at its opposite apical domains, we utilized the unique biological property of GroEL, i.e., Mg2+/ATP-mediated ring exchange between AGroELA and BGroELB with their hollow cylindrical double-decker architectures. This exchange event was reported more than 24 years ago but has never been utilized for molecular engineering of GroEL. We leveraged DNA nanotechnology to purely isolate Janus AGroELB and succeeded in its precision ternary supramolecular copolymerization with two DNA comonomers, A** and B*, that are partially complementary to A and B in AGroELB, respectively, and programmed to self-dimerize on the other side. Transmission electron microscopy allowed us to confirm the formation of the expected dual-periodic copolymer sequence -(B*/BGroELA/A**/A**/AGroELB/B*)- in the form of a laterally connected lamellar assembly rather than a single-chain copolymer.
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Ionic liquid crystals have emerged as a new class of functional soft materials in the last two decades, and they exhibit synergistic characteristics of ionic liquids and liquid crystals such as macroscopic orientability, miscibility with various species, phase stability, nanostructural tunability, and polar nanochannel formation. Owing to these characteristics, the structures, properties, and functions of ionic liquid crystals have been a hot topic in materials chemistry, finding various applications including host frameworks for guest binding, separation membranes, ion-/proton-conducting membranes, reaction media, and optoelectronic materials. Although several excellent review articles of ionic liquid crystals have been published recently, they mainly focused on the fundamental aspects, structures, and specific properties of ionic liquid crystals, while these applications of ionic liquid crystals have not yet been discussed at one time. The aim of this feature article is to provide an overview of the applications of ionic liquid crystals in a comprehensive manner.
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Multisubstituted ortho-anisidines were efficiently synthesized via cationic N-heterocyclic carbene-Cu-catalyzed domino rearrangement of N-methoxyanilines that possess an electron-donating functional group, such as an alkyl or an aryl group, at the ortho position. The reaction proceeded first through a [1,3]-rearrangement of the methoxy group to the ortho position bound to the electron-donating substituent, followed by a semipinacol type [1,2]-rearrangement of the electron-donating group from the ortho to the meta position. Mechanistic studies suggest that both rearrangement reactions are promoted by a cationic Cu catalyst.
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Optical properties of aqueous colloidal dispersions of 2D electrolytes, if their aspect ratios are extra-large, can be determined by their orientation preferences. Recently, we reported that a colloidal dispersion of diamagnetic titanate(IV) nanosheets (TiIVNSs), when placed in a magnetic field, is highly anisotropic because TiIVNS anomalously orients its 2D plane orthogonal to the magnetic flux lines due to its large anisotropic magnetic susceptibility. Herein, we report a serendipitous finding that TiIVNSs can be in situ photochemically reduced into a paramagnetic species (TiIV/IIINSs), so that their preference of magnetic orientation changes from orthogonal to parallel. This transition distinctly alters the structural anisotropy and therefore optical appearance of the colloidal dispersion in a magnetic field. We also found that TiIV/IIINSs is autoxidized back to TiIVNSs under non-deaerated conditions. By using an elaborate setup, the dispersion of TiIVNSs serves as an optical switch remotely operable by magnet and light.
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Mixtures of a phospholipid (1,2-dipalmitoyl-sn-glycero-3-phosphatidylcholine, DPPC) and a sodium-cholate-derived surfactant (SC-C5 ) at room temperature formed phospholipid bilayer fragments that were edge-stabilized by SC-C5 : so-called "bicelles". Because the bilayer melting point of DPPC (41 °C) is above room temperature and because SC-C5 has an exceptionally low critical micelle concentration (<0.5â mm), the bicelles are kinetically frozen at room temperature. Consequently, they exist even when the mixture is diluted to a concentration of 0.04â wt %. In addition, the lateral size of the bicelles can be fine-tuned by altering the molar ratio of DPPC to SC-C5 . On heating to ≈37 °C, the bicelles transformed into micelles composed of DPPC and SC-C5 . By taking advantage of the dilution tolerance, size tunability, and thermoresponsiveness, we demonstrated in vitro drug delivery based on use of the bicelles as carriers, which suggests their potential utility in transdermal drug delivery.
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Preparações de Ação Retardada/química , Bicamadas Lipídicas/química , Fosfatidilcolinas/química , Tensoativos/química , Antibióticos Antineoplásicos/administração & dosagem , Antibióticos Antineoplásicos/farmacocinética , Linhagem Celular , Doxorrubicina/administração & dosagem , Doxorrubicina/farmacocinética , Sistemas de Liberação de Medicamentos , Liberação Controlada de Fármacos , Humanos , Cinética , Micelas , TemperaturaRESUMO
Owing to their water-rich structures, which are similar to those of biological tissues, hydrogels have long been regarded as promising scaffolds for artificial tissues and organs. However, in terms of the structural anisotropy, most synthetic hydrogels are substantially different from biological systems. Synthetic hydrogels are usually composed of randomly oriented three-dimensional polymer networks whereas biological systems adopt anisotropic structures with hierarchically integrated building units. Such anisotropic structures often play essential roles in biological systems to exhibit particular functions. In this context, anisotropic hydrogels provide an entry point for exploring biomimetic applications of hydrogels. Reflecting these aspects, an increasing number of studies on anisotropic hydrogels have been reported recently. This Minireview highlights the use and perspectives of these anisotropic hydrogels, particularly focusing on their preparation, structures, and applications.
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In our previous work, we have shown that "electrostatic forces", when generated anisotropically in aqueous media by 2D electrolytes upon cofacial orientation, enable the formation of a hydrogel with an anisotropic parameter, as defined by the ratio of elastic moduli E⥠/E⥠, of 3.0. Herein, we successfully developed the design strategy for a hydrogel with an anisotropic parameter of no less than 85. This value is not only 28 times greater than that of our previous anisotropic hydrogel but also 6 times larger than the current champion record in synthetic hydrogels (E⥠/E⥠â¼15). Firstly, we simply lowered ionic contaminants in the hydrogel and were able to enhance the anisotropic parameter from 3.0 to 18. Then, we chose a supporting polymer network allowing the hydrogel to carry a higher interior permittivity. Consequently, the anisotropic parameter was further enhanced from 18 to 85. Owing to the enhanced mechanical anisotropy, our new hydrogel displayed a superb ability of seismic isolation.
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Peristaltic crawling, which is the moving mechanism of earthworm-like limbless creatures in narrow spaces, is a challenging target to mimic by using soft materials. Here we report an unprecedented hydrogel actuator that enables not only a peristaltic crawling motion but also reversing its direction. Our cylindrically processed hydrogel contains gold nanoparticles for photothermal conversion, a thermoresponsive polymer network for switching the electrical permittivity of the gel interior, and cofacially oriented 2D electrolytes (titanate nanosheets; TiNSs) to synchronously change their anisotropic electrostatic repulsion. When a hydrogel, which was designed to include cofacially oriented TiNSs along the cylindrical gel axis, is pointwisely photoirradiated with a visible-light laser, it spatiotemporally expands immediately (<0.5â s) and largely (80 % of its original length) in an isovolumetric manner. When the irradiation spot is moved along the cylindrical gel axis, the hydrogel undergoes peristaltic crawling due to quick and sequential elongation/contraction events and moves oppositely toward the laser scanning direction. Thus, when the scanning direction is switched, the crawling direction is reversed. When gold nanorods are used in place of gold nanoparticles, the hydrogel becomes responsive to a near-infrared light, which can deeply penetrate into bio tissues.
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A series of octamer (8-mer) and hexadecamer (16-mer) oligopeptides of 4-aminopiperidine-4-carboxylic acid (Api) with l-leucine as a chiral auxiliary at their N or Câ termini were synthesized. By using circular dichroism spectroscopy, the conformational profiles of the peptides were systematically studied, which revealed that the α-helix-formation ability of the peptides is determined by the combination of parameters, which includes peptide length, state of the piperidine groups in the Api units, and position of the chiral auxiliary. When the piperidines were in the free-base state, the peptides showed a low propensity to form helical structures. However, the protonation and acylation of the piperidines enhanced the formation of helical structures, such that the order for helix-formation ability was protonated>acylated>free base. In terms of peptide length, the 16-mers generally showed higher helix-formation ability than the corresponding 8-mers, and one of the 16-mers showed helicity at the highest level reported thus far for oligopeptides of a similar length. It was also found that the sensitivity of the helical structure towards the state of the piperidine groups changed drastically depending on the chiral auxiliary position; the N-terminal chiral peptides were more sensitive than the C-terminal chiral analogues.
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Oligopeptídeos/química , Aminoácidos/química , Dicroísmo Circular , Concentração de Íons de Hidrogênio , Oligopeptídeos/síntese química , Oligopeptídeos/metabolismo , Piperidinas/química , Estrutura Secundária de Proteína , EstereoisomerismoRESUMO
Electrostatic repulsion, long used for attenuating surface friction, is not typically employed for the design of bulk structural materials. We recently developed a hydrogel with a layered structure consisting of cofacially oriented electrolyte nanosheets. Because this unusual geometry imparts a large anisotropic electrostatic repulsion to the hydrogel interior, the hydrogel resisted compression orthogonal to the sheets but readily deformed along parallel shear. Building on this concept, here we show a hydrogel actuator that operates by modulating its anisotropic electrostatics in response to changes of electrostatic permittivity associated with a lower critical solution temperature transition. In the absence of substantial water uptake and release, the distance between the nanosheets rapidly expands and contracts on heating and cooling, respectively, so that the hydrogel lengthens and shortens significantly, even in air. An L-shaped hydrogel with an oblique nanosheet configuration can thus act as a unidirectionally proceeding actuator that operates without the need for external physical biases.