Spontaneous-Spin-Polarized 2D π-d Conjugated Frameworks Towards Enhanced Oxygen Evolution Kinetics.

Alternative strategies to design sustainable-element-based electrocatalysts enhancing oxygen evolution reaction (OER) kinetics are demanded to develop affordable yet high-performance water-electrolyzers for green hydrogen production. Here, it is demonstrated that the spontaneous-spin-polarized 2D π-d conjugated framework comprising abundant elements of nickel and iron with a ratio of Ni:Fe = 1:4 with benzenehexathiol linker (BHT) can improve OER kinetics by its unique electronic property. Among the bimetallic NiFex:y-BHTs with various ratios with Ni:Fe = x:y, the NiFe1:4-BHT exhibits the highest OER activity. The NiFe1:4-BHT shows a specific current density of 140 A g-1 at the overpotential of 350 mV. This performance is one of the best activities among state-of-the-art non-precious OER electrocatalysts and even comparable to that of the platinum-group-metals of RuO2 and IrO2. The density functional theory calculations uncover that introducing Ni into the homometallic Fe-BHT (e.g., Ni:Fe = 0:1) can emerge a spontaneous-spin-polarized state. Thus, this material can achieve improved OER kinetics with spin-polarization which previously required external magnetic fields. This work shows that a rational design of 2D π-d conjugated frameworks can be a powerful strategy to synthesize promising electrocatalysts with abundant elements for a wide spectrum of next-generation energy devices.

Lateral Heterometal Junction Rectifier Fabricated by Sequential Transmetallation of Coordination Nanosheet.

Heterostructures of two-dimensional materials realise novel and enhanced physical phenomena, making them attractive research targets. Compared to inorganic materials, coordination nanosheets have virtually infinite combinations, leading to tunability of physical properties and are promising candidates for heterostructure fabrication. Although stacking of coordination materials into vertical heterostructures is widely reported, reports of lateral coordination material heterostructures are few. Here we show the successful fabrication of a seamless lateral heterojunction showing diode behaviour, by sequential and spatially limited immersion of a new metalladithiolene coordination nanosheet, Zn3 BHT, into aqueous Cu(II) and Fe(II) solutions. Upon immersion, the Zn centres in insulating Zn3 BHT are replaced by Cu or Fe ions, resulting in conductivity. The transmetallation is spatially confined, occurring only within the immersed area. We anticipate that our results will be a starting point towards exploring transmetallation of various two-dimensional materials to produce lateral heterojunctions, by providing a new and facile synthetic route.

Controlling Microstructure-Transport Interplay in Poly(ether-block-amide) Multiblock Copolymer Gas Separation Membranes.

In this study, we investigated the effect of morphology on the gas-transport properties of a poly(ether-block-amide) (PEBA) multiblock copolymer. We annealed the copolymer samples and varied the annealing temperature to evaluate the influence of changes in the microstructure on the gas transport properties of PEBA. In addition, we used time-resolved attenuated total reflection Fourier transform infrared spectroscopy to evaluate the diffusion coefficient of CO2 in PEBA based on the Fickian model. The effect of the annealing temperature on the microphase-separated structure of the multiblock copolymer is discussed in detail. Furthermore, the gas diffusivity was significantly affected by the purity of the soft domains. The annealed sample demonstrated a 38% increase in CO2 permeability while maintaining a high CO2/N2 permselectivity of approximately 53. The findings of this study provide valuable insight into the design and optimization of PEBA membranes for gas separation applications.

Composition of Minor Ampullate Silk Makes Its Properties Different from Those of Major Ampullate Silk.

Spider's minor ampullate silk, or MI-silk, exhibits distinct mechanical properties and water resistance compared to its major ampullate counterpart (MA-silk). The principal protein constituent of MI-silk is known as minor ampullate spidroin, or MiSp, and while its sequence has been deciphered and is thought to underlie the differences in properties with MA-silk, the composition of MI-silk and the relationship between its composition and properties remain elusive. In this study, we set out to investigate the mechanical properties, water resistance, and proteome of MA-silk and MI-silk from Araneus ventricosus and Trichonephila clavata. We also synthesized artificial fibers from major ampullate spidroin, MaSp1 and 2, and MiSp to compare their properties. Our proteomic analysis reveals that the MI-silk of both araneids is composed of MiSp, MaSp1, and spidroin constituting elements (SpiCEs). The absence of MaSp2 in the MI-silk proteome and the comparison of the water resistance of artificial fibers suggest that the presence of MaSp2 is the reason for the disparity in water resistance between MI-silk and MA-silk.

Dynamic behaviours of epoxy resin thin films during the curing process.

Epoxy resin thin films are widely used in applications such as coating materials, insulator films, and adhesives; accordingly, investigations of their physical properties have garnered increasing importance. Although the physical properties of thermoset epoxy thin films are strongly affected by the curing conditions, such as the heating temperature and curing time, the dynamic properties during the curing process have not been studied thoroughly. In this study, we investigated the thermal fluctuations on the surface of epoxy resin thin films using grazing-incidence X-ray photon correlation spectroscopy, to elucidate the dynamic behaviours during the curing process. We thus succeeded in observing the freezing of capillary waves during the thermal curing process. These results are expected to facilitate a deeper understanding of the curing mechanisms of various thin films.

Direct determination of the π-helix structure and helix transition behavior of poly(ß-phenethyl l-aspartate) via synchrotron X-ray diffraction.

The helix-sense inversions of poly(ß-phenethyl l-aspartate) (2P) and diblock copolymers (2P-3P), with 2P and poly(ß-phenylpropyl l-aspartate) (3P) blocks, were studied in their solid states using synchrotron wide-angle X-ray diffraction and small-angle X-ray scattering. The characteristic parameters of the π-helix structure of 2P were directly determined in situ after the helix transition at a high temperature. In the 2P-3P block copolymers, the main chains of the 3P blocks initially convert from right- to left-handed α-helices, and then the 2P blocks convert irreversibly from right-handed α-helices to left-handed π-helices. The chemical structures of the side chains of poly(l-aspartic acid ester)s significantly affect their helix transition behaviors.

Direct determination of helix structures involved in the screw-sense reversal of poly(ß-phenylpropyl l-aspartate) by synchrotron X-ray diffraction.

The helix-sense reversal of poly(ß-phenylpropyl l-aspartate) (3PLA) in the solid state was studied by synchrotron wide-angle X-ray diffraction and small-angle X-ray scattering. The direct determination of the characteristic helical pitch before and after the transition revealed that the transition takes place reversibly between the two α-helices having opposite screw-sense during the heating and cooling cycle. While the hexagonal packing remains unaltered, the helix-sense inversion causes discontinuous changes in the molecular arrangement and, by extension, the crystalline dimension. In this study, another transition was detected at a higher temperature from the left-handed α-helix to the π-helix, the molecular chirality being unaffected.

Glassy Porphyrin/C60 Composites: Morphological Engineering of C60 Fullerene with Liquefied Porphyrins.

Morphological control of C60 fullerene using liquefied porphyrins (1 and 2) as the host matrices was explored. Slow evaporation of the solvent of the equimolar mixture of porphyrin and C60 in toluene afforded the porphyrin/C60 composite with a 3:1 molar ratio. The stoichiometric binding behaviors suggest that specific porphyrin-C60 interactions operate the formation of the porphyrin/C60 composites, as corroborated by spectroscopic and thermal properties, and glazing-incidence wide-angle X-ray diffraction. Under the bulk conditions, the conventional thermodynamic advantage of multiple binding cooperativity for molecular recognition is unlikely to explain the stoichiometric binding behaviors. Instead, we propose a size-matching effect on the porphyrin-C60 interaction in the bulk porphyrin matrices, i.e., "supramolecular solvation". The glassy nature of the porphyrin matrices was transmitted to C60 through the specific interaction, and the porphyrin/C60 composites adopted glassy states at room temperature.

Zwitterionic Polypeptides: Chemoenzymatic Synthesis and Loosening Function for Cellulose Crystals.

A polypeptide with a GlyHisGly repeating sequence containing zwitterionic structures that effectively interact with cellulose was synthesized for dissociation of cellulose crystals. Polypeptide with the GlyHisGly sequence was synthesized by chemoenzymatic polymerization and postfunctionalization of the His residues was performed to afford imidazolium butyrate on the side chains. The resulting zwitterionic polypeptide effectively dissociated bundles of tunicate cellulose nanocrystals, even when the conditions were mild and the concentration of the polypeptide was as low as 1-2 mg mL-1. Polypeptide treatment also affected the morphology of the cell walls in cultured plant cells, and the cellulose microfibril networks and amorphous polysaccharide layer were dissociated according to atomic force microscopy (AFM). The zwitterionic polypeptide treatment did not change the crystal structure of the cellulose nanocrystals. Analysis of the mechanical properties of the cellulose nanocrystals by force curve measurements using AFM revealed that the elastic modulus of the cellulose nanocrystals increased after treatment with the zwitterionic polypeptide, indicating that the amorphous part of the cellulose nanocrystals was removed by interactions with the polypeptide. At a concentration of the polypeptide that enabled the dissociation of the cellulose network, the zwitterionic polypeptide showed negligible cytotoxicity to the plant cells. The mild and noncytotoxic technique for loosening cellulose microfibrils/nanocrystals that was developed in this study has tremendous significance for the modification of cellulose in terms of polymer chemistry, material science, and plant biotechnology.

Silk/Natural Rubber (NR) and 3,4-Dihydroxyphenylalanine (DOPA)-Modified Silk/NR Composites: Synthesis, Secondary Structure, and Mechanical Properties.

Silk composites with natural rubber (NR) were prepared by mixing degummed silk and NR latex solutions. A significant enhancement of the mechanical properties was confirmed for silk/NR composites compared to a NR-only product, indicating that silk can be applied as an effective reinforcement for rubber materials. Attenuated total reflection Fourier transform infrared (ATR-FTIR) and wide-angle X-ray diffraction (WAXD) analysis revealed that a ß-sheet structure was formed in the NR matrix by increasing the silk content above 20 wt%. Then, 3,4-dihydroxyphenylalanine (DOPA)-modified silk was also blended with NR to give a DOPA-silk/NR composite, which showed superior mechanical properties to those of the unmodified silk-based composite. Not only the chemical structure but also the dominant secondary structure of silk in the composite was changed after DOPA modification. It was concluded that both the efficient adhesion property of DOPA residue and the secondary structure change improved the compatibility of silk and NR, resulting in the enhanced mechanical properties of the formed composite. The knowledge obtained herein should contribute to the development of the fabrication of novel silk-based elastic materials.

Combination of Amorphous Silk Fiber Spinning and Postspinning Crystallization for Tough Regenerated Silk Fibers.

An artificial spinning system using regenerated silk fibroin solutions is adopted to produce high-performance silk fibers. In previous studies, alcohol-based agents, such as methanol or ethanol, were used to coagulate silk dope solutions, producing silk fiber with poor mechanical properties compared with those of native silk fibers. The alcohol-based coagulation agents induce rapid ß-sheet crystallization of the silk molecules, which inhibits subsequent alignment of the ß-sheet crystals. Here, we induce gradual ß-sheet formation to afford adequate ß-sheet alignment similar to that of native silk fiber. To this aim, we developed an amorphous silk fiber spinning process that prevents fast ß-sheet formation in silk molecules by using tetrahydrofuran (THF) as a coagulation solvent. In addition, we apply postdrawing to the predominantly amorphous silk fibers to induce ß-sheet formation and orientation. The resultant silk fibers showed a 2.5-fold higher extensibility, resulting in 1.5-fold tougher silk fibers compared with native Bombyx mori silk fiber. The amorphous silk fiber spinning process developed here will pave the way to the production of silk fibers with desired mechanical properties.

Crystalline Graphdiyne Nanosheets Produced at a Gas/Liquid or Liquid/Liquid Interface.

Synthetic two-dimensional polymers, or bottom-up nanosheets, are ultrathin polymeric frameworks with in-plane periodicity. They can be synthesized in a direct, bottom-up fashion using atomic, ionic, or molecular components. However, few are based on carbon-carbon bond formation, which means that there is a potential new field of investigation into these fundamentally important chemical bonds. Here, we describe the bottom-up synthesis of all-carbon, π-conjugated graphdiyne nanosheets. A liquid/liquid interfacial protocol involves layering a dichloromethane solution of hexaethynylbenzene on an aqueous layer containing a copper catalyst at room temperature. A multilayer graphdiyne (thickness, 24 nm; domain size, >25 µm) emerges through a successive alkyne-alkyne homocoupling reaction at the interface. A gas/liquid interfacial synthesis is more successful. Sprinkling a very small amount of hexaethynylbenzene in a mixture of dichloromethane and toluene onto the surface of the aqueous phase at room temperature generated single-crystalline graphdiyne nanosheets, which feature regular hexagonal domains, a lower degree of oxygenation, and uniform thickness (3.0 nm) and lateral size (1.5 µm).

Liquid/Liquid Interfacial Synthesis of a Click Nanosheet.

A liquid/liquid interfacial synthesis is employed, for the first time, to synthesize a covalent two-dimensional polymer nanosheet. Copper-catalyzed azide-alkyne cycloaddition (CuAAC) between a three-way terminal alkyne and azide at a water/dichloromethane interface generates a 1,2,3-triazole-linked nanosheet. The resultant nanosheet, with a flat and smooth texture, has a maximum domain size of 20 µm and minimum thickness of 5.3 nm. The starting monomers in the organic phase and the copper catalyst in the aqueous phase can only meet at the liquid/liquid interface as a two-dimensional reaction space; this allows them to form the two-dimensional polymer. The robust triazole linkage generated by irreversible covalent-bond formation allows the nanosheet to resist hydrolysis under both acidic and alkaline conditions, and to endure pyrolysis up to more than 300 °C. The coordination ability of the triazolyl group enables the nanosheet to act as a reservoir for metal ions, with an affinity order of Pd2+ >Au3+ >Cu2+ .

Tensile Reinforcement of Silk Films by the Addition of Telechelic-Type Polyalanine.

An appropriate modification technique for silk materials is needed to effectively improve their physical properties for specific applications. A telechelic-type polyalanine (T-polyA) was synthesized by papain-catalyzed polymerization as a novel reinforcing agent for silk materials. A silk fibroin obtained from Bombyx mori was homogeneously doped with T-polyA, and casting a solution of silk fibroin and T-polyA in 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP) resulted in a robust and transparent film. Tensile deformation studies of the silk composite film containing T-polyA with prestretching revealed that the tensile strength and toughness were enhanced relative to those of a silk-only film. To determine the capability of T-polyA to reinforce the tensile property of silk films, the secondary structure in the silk composite film was characterized by wide-angle X-ray diffraction (WAXD) analysis. Antiparallel ß-sheet structures of T-polyA and GAGAGS motifs of silk fibroin formed independently in the prestretched composite film. In addition, measuring the tensile deformation and performing WAXD analysis simultaneously demonstrated that the ß-sheet structures of both T-polyA and the silk fibroin were aligned along the stretching direction and that T-polyA had no significant effect on the final morphology of the silk crystal domains. The silk film was toughened by the addition of T-polyA because of the generation of the T-polyA ß-sheet in the amorphous region of the composite film. This work provides novel insight into the design and development of tough silk materials with controlled and aligned ß-sheet structures.

Silk Resin with Hydrated Dual Chemical-Physical Cross-Links Achieves High Strength and Toughness.

Native silk fibers are known to demonstrate excellent mechanical properties such as high strength and ductility. However, regenerated silk material has not yet been used as a tough structural material in our everyday life. To recreate the mechanical properties with regenerated silk material, the network structure and hydration state of silk materials are studied and optimized in this study. This is the first to demonstrate the effect of chemical and physical cross-links in hydrated and dehydrated silk materials, namely, silk hydrogels and resins. Mild hydration conditions (relative humidity 20-60%) realizes tough and strong silk materials with chemical and physical cross-links. In the case of relatively high concentrations of silk molecules, contributions to the high strength and toughness of silk-based materials are considered to come not only from ß-sheet cross-links and chemical dityrosine links but also from entanglements and assembly via the hydrophobic interactions of silk molecules. In addition, dehydration treatment does not disturb the biodegradability of the silk resins in natural environments. Based on the overall results, the silk resins with controlled network structures and hydration state have successfully achieved the highest toughness possible for a bulk silk material while maintaining favorable biodegradability.

Liquid Crystalline Granules Align in a Hierarchical Structure To Produce Spider Dragline Microfibrils.

The spider silk spinning process converts spidroins from an aqueous form to a tough fiber. This spinning process has been investigated by numerous researchers, and micelles or liquid crystals of spidroins have been reported to form silk fibers, which are bundles of silk microfibrils. However, the formation process of silk microfibrils has not been clarified previously. Here, we report that silk microfibrils are generated through the formation, homogenization, and linkage of liquid crystalline granules without micelle-like structures. Heterogeneous granules on the submicron to micron scale were observed in the storage sac, whereas homogeneous granules with diameters of approximately 100 nm were aligned along the tapering duct. In the spun fibers, the homogeneous granules were connected along the fiber axis. This is the first clear description of the formation of granule-based microfibrils in the spinning process, which is the key conversion process leading to the unique hierarchical structure of spider dragline.

Chiral-Linkage-Induced Hierarchical Ordering of Colloidal Achiral Nanotubes in their Thixotropic Gel.

Macroscopic continuous hierarchical ordering of achiral nanotube "imogolite" was achieved by thixotropic gelation of imogolite with chiral hydroxy acid and their flow-orienting/subsequent standing for uniaxial alignments of imogolite. The chirality change of the hydroxy acids resulted in an inversion of the helical ordering. The study presented here first exhibits the millimeter-scale supramolecular chirality induced by angstrom-scale molecular handedness in the architecture of nanotubes.

Influence of Water Content on the ß-Sheet Formation, Thermal Stability, Water Removal, and Mechanical Properties of Silk Materials.

Silk, which has excellent mechanical toughness and is lightweight, is used as a structural material in nature, for example, in silkworm cocoons and spider draglines. However, the industrial use of silk as a structural material has garnered little attention. For silk to be used as a structural material, its thermal processability and associated properties must be well understood. Although water molecules influence the glass transition of silk, the effects of water content on the other thermal properties of silks are not well understood. In this study, we prepared Bombyx mori cocoon raw fibers, degummed fibers, and films with different water contents and then investigated the effects of water content on crystallization, degradation, and water removal during thermal processing. Thermal gravimetric analyses of the silk materials showed that water content did not affect the thermal degradation temperature but did influence the water removal behavior. By increasing the water content of silk, the water molecules were removed at lower temperatures, indicating that the amount of free water in silk materials increased; additionally, the glass transition temperature decreased with increasing water plasticization. Differential scanning calorimetry and wide-angle X-ray scattering of the silk films also suggested that the water molecules in the amorphous regions of the silk films acted as a plasticizer and induced ß-sheet crystallization. The plasticizing effect of water was not detected in silk fibers, owing to their lower amorphous content and mobility. The structural and mechanical characterizations of the silk films demonstrated the silk film prepared at RH 97% realized both crystallinity and ductility simultaneously. Thus, the thermal stability, mechanical, and other properties of silk materials are regulated by their water content and crystallinity.

Enzyme-Mimic Peptide Assembly To Achieve Amidolytic Activity.

Amyloid fibers are classified as a new generation of tunable bionanomaterials that exhibit new functions related to their distinctive characteristics, such as their universality, tunability, and stiffness. Here, we introduce the catalytic residues of serine protease into a peptide catalyst (PC) via an enzyme-mimic approach. The rational design of a repeating pattern of polar and nonpolar amino acids favors the conversion of the peptides into amyloid-like fibrils via self-assembly. Distinct fibrous morphologies have been observed at different pH values and temperatures, which indicates that different fibril packing schemes can be designed; hence, fibrillar peptides can be used to generate efficient artificial catalysts for amidolytic activities at mild pH values. The results of atomic force microscopy, Raman spectroscopy, and wide-angle X-ray scattering analyses are used to discuss and compare the fibril structure of a fibrillar PC with its amidolytic activity. The pH of the fibrillation reaction crucially affects the pKa of the side chains of the catalytic triads and is important for stable fibril formation. Temperature is another important parameter that controls the self-assembly of peptides into highly stacked and laminated morphologies. The morphology and stability of fibrils are crucial and represent important factors for demonstrating the capability of the peptides to exert amidolytic activity. The observed amidolytic activity of PC4, one of the PCs, was validated using an inhibition assay, which revealed that PC4 can perform enzyme-like amidolytic catalysis. These results provide insights into the potential use of designed peptides in the generation of efficient artificial enzymes.

Observation of an Orientation Change in Highly Oriented Layer-by-Layer Films of a Ruthenium Complex upon Oxidation Reaction.

Layer-by-layer films composed of redox-active ruthenium dimer and Zr(IV) ions were fabricated on an indium tin oxide electrode. The fabricating behavior was monitored by cyclic voltammetry and UV-vis absorption spectral measurements. The orientation of the film was also monitored by grazing-incidence small-angle and wide-angle X-ray scattering (GISAXS) measurements, and it has been clarified that this film has a crystalline structure. The peaks obtained by GISAXS were changed upon oxidation reaction, which indicates that a change in the orientation of the ruthenium dimer occurred in the film.