Reconstruction of Chitosan Network Orders Using the Meniscus Splitting Method for Designing pH-Responsive Materials.

Chitosan is a product of deacetylated chitin and a natural polymer that is attractive as a functional and biocompatible material in the pursuit of alternative materials to synthetic plastics for a sustainable society. Although hierarchical architectures, from precise molecular structures to nanofibers and twisted structures, have been clarified, the expansion of the anisotropic microstructures of chitosan into millimeter-scale materials is in the process of development. In this study, a chitosan network was reconstructed from an aqueous solution by using the meniscus splitting method to form a three-dimensionally ordered microstructure. A chitosan membrane deposited on the millimeter scale formed a useful anisotropically pH-responsive hydrogel. During the evaporation of the aqueous solution from a finite space, chitosan underwent ordered deposition by capillary force to form a membrane with oriented microstructures and microlayers. Unlike the cast films formed between solid-liquid and air-liquid interfaces, this membrane formed between two air-liquid interfaces. As a result, the membranes with ordered microstructures were capable of signifying directional swelling in aqueous environments and reversible/irreversible swelling-deswelling changes by controlling the pH range. We envision that the anisotropic pH response of the chitosan network can be utilized under physiological conditions as a next-generation material.

Cyanobacterial supra-polysaccharide: Self-similar hierarchy, diverse morphology, and application prospects of sacran fibers.

The biological functions of polysaccharides are influenced by their chemistry and chain conformation, which have resulted in various functional applications and new uses for polysaccharides in recent years. Sacran is an intriguing ampholytic polysaccharide with several key properties such as metal adsorption, anti-inflammatory nature, and transdermal drug-carrying capacity. It has an extremely high molecular weight over 107 g/mol, which is much higher than those of the previously reported microbial polysaccharides. In particular, it has a remarkable self-orienting characteristic over a large length scale, which could produce a bundle with twisted morphologies from the nanoscale to the microscale with diameters of ~1 µm and lengths of >800 µm. In this review, morphological variations, as well as novel self-organization and hierarchical self-assembly are comprehensively discussed. Sacran fibers deform into various forms, such as two- and three-dimensional flexible fibers and micro-nano fragments, during their evaporation. The self-assembly and disassembly of the sacran are explained in terms of the preparation process and factors that influence the morphology. This review will pave the way for the development of novel modules such as humidity-sensitive actuators, micro-patterned cell scaffolds, and uniaxially oriented membranes.

Super-Moisturizing Materials from Morphological Deformation of Suprapolysaccharides.

The evaporative interface on polysaccharides has evolved to form hierarchical structures with moisture sensitivity to enable organisms to live in drying environments. Here, the discovery of the morphological instability of polysaccharides, especially the reversible self-assembly/disassembly between micron-fibers and microparticles in response to changes in aquatic environments, is reported. This is similar but different to the dynamic instability observed in cytoskeletal proteins, in terms of an accompanying the polymeric deformation. The formation of the polymeric fibers containing crystalline structures can be flexibly controlled by controlling the polymer concentration and salt concentration in aqueous mixtures. Moreover, the microparticles having crosslinking points in the interior acquire the ability to retain a larger number of water molecules in drying environments and behave as super-moisturizing materials.

Vapor-Sensitive Materials from Polysaccharide Fibers with Self-Assembling Twisted Microstructures.

Polysaccharides play a variety of roles in nature, including molecular recognition and water retention. The microscale structures of polysaccharides are seldom utilized in vitro because of the difficulties in regulating self-assembled structures. Herein, it is demonstrated that a cyanobacterial polysaccharide, sacran, can hierarchically self-assemble as twisted fibers from nanoscale to microscale with diameters of ≈1 µm and lengths >800 µm that are remarkably larger than polysaccharides previously reported. Unlike other rigid fibrillar polysaccharides, the sacran fiber is capable of flexibly transforming into two-dimensional (2D) snaking and three-dimensional (3D) twisted structures at an evaporative air-water interface. Furthermore, a vapor-sensitive film with a millisecond-scale response time is developed from the crosslinked polymer due to the spring-like behavior of twisted structures. This study increases understanding of the functions of fibers in nature and establishes a novel approach to the design of environmentally adaptive materials for soft sensors and actuators.

Polymeric Design for Electron Transfer in Photoinduced Hydrogen Generation through a Coil-Globule Transition.

To realize a renewable energy society, a polymeric system for photoinduced hydrogen generation utilizing a copolymer containing an electron acceptor was designed. In this system, the redox changes of viologen introduced into poly(N-isopropylacrylamide) cause cyclic conformational changes owing to the shifting of the phase transition temperature (PTT). The polymeric coil-globule transitions with hydrophilic/hydrophobic changes accelerate the electron transfer for hydrogen generation. In particular, hydrogen generation using visible-light energy with high efficiency is achieved around the PTT. In contrast to conventional solution systems, our polymeric system enables efficient hydrogen generation in a close molecular arrangement without the aggregation of catalytic nanoparticles. The utilization of conformational changes will provide a new strategy for synthesizing artificial photosynthetic hydrogels that split water to generate both hydrogen and oxygen.

Micelle-Mediated Self-Assembly of Microfibers Bridging Millimeter-Scale Gap To Form Three-Dimensional-Ordered Polysaccharide Membranes.

Micelle-mediated three-dimensional-ordered polysaccharide membranes are constructed by introducing cationic/anionic surfactant into a liquid crystalline polysaccharide solution. Upon drying mixtures of the polysaccharide solution with the surfactant such as cetyltrimethylammonium bromide or sodium dodecyl sulfate (SDS), the polymeric microfibers deposit as a nucleus to form a membrane, bridging millimeter-scale gap with high probability. In particular, in a solution with SDS micellar structures, the microscale fibers with diameter ∼1 µm disassemble into nanoscale fibers with diameter ∼50 nm. This transformation allows the polymeric network to become finer in nanoscale, and the vertical membrane is formed much more easily than that from a pure polysaccharide solution. Furthermore, it is clarified that the vertical membrane has been successfully formed with three-dimensionally ordered microstructures with a linearly oriented and layered structure. This method will shed light on the preparation of hybrid materials with biocompatibility and responsivity to stimuli such as magnetics, electrics, and optics via hybridization with nanomaterials dispersed by surfactants.

Drying-Induced Self-Similar Assembly of Megamolecular Polysaccharides through Nano and Submicron Layering.

We propose a self-similar assembly to generate planar orientation of megamolecular polysaccharides on the nanometer scale and submicron scale. Evaporating the aqueous liquid crystalline (LC) solution on a planar air-LC interface induces polymer layering by self-assembly and rational action of macroscopic capillary forces between the layers. To clarify the mechanisms of nanometer- and submicron-scale layering, the polymer films are investigated by electron microscopy.

Design of Polymer Networks Involving a Photoinduced Electronic Transmission Circuit toward Artificial Photosynthesis.

Many strategies have been explored to achieve artificial photosynthesis utilizing mediums such as liposomes and supramolecules. Because the photochemical reaction is composed of multiple functional molecules, the surrounding microenvironment is expected to be rationally integrated as observed during photosynthesis in chloroplasts. In this study, photoinduced electronic transmission surrounding the microenvironment of Ru(bpy)3(2+) in a polymer network was investigated using poly(N-isopropylacrylamide-co-Ru(bpy)3), poly(acrylamide-co-Ru(bpy)3), and Ru(bpy)3-conjugated microtubules. Photoinduced energy conversion was evaluated by investigating the effects of (i) Ru(bpy)3(2+) immobilization, (ii) polymer type, (iii) thermal energy, and (iv) cross-linking. The microenvironment surrounding copolymerized Ru(bpy)3(2+) in poly(N-isopropylacrylamide) suppressed quenching and had a higher radiative process energy than others. This finding is related to the nonradiative process, i.e., photoinduced H2 generation with significantly higher overall quantum efficiency (13%) than for the bulk solution. We envision that useful molecules will be generated by photoinduced electronic transmission in polymer networks, resulting in the development of a wide range of biomimetic functions with applications for a sustainable society.

Milliscale Self-Integration of Megamolecule Biopolymers on a Drying Gas-Aqueous Liquid Crystalline Interface.

A drying environment is always a proposition faced by dynamic living organisms using water, which are driven by biopolymer-based micro- and macrostructures. Here, we introduce a drying process for aqueous liquid crystalline (LC) solutions composed of biopolymer with extremely high molecular weight components such as polysaccharides, cytoskeletal proteins, and DNA. On controlling the mobility of the LC microdomain, the solutions showed milliscale self-integration starting from the unstable gas-LC interface during drying. In particular, we first identified giant rod-like microdomains (∼1 µm diameter and more than 20 µm length) of the mega-molecular polysaccharide, sacran, which is remarkably larger than other polysaccharides. These microdomains led to the formation of a single milliscale macrodomain on the interface. In addition, the dried polymer films on a solid substrate also revealed that such integration depends on the size of the microdomain. We envision that this simple drying method will be useful not only for understanding the biopolymer hierarchization at the macroscale level but also for preparation of surfaces with direction controllability, as seen in living organisms, for use in various fields such as diffusion, mechanics, and photonics.

Small-Angle X-ray Scattering Study on Internal Microscopic Structures of Poly(N-isopropylacrylamide-co-tris(2,2'-bipyridyl))ruthenium(II) Complex Microgels.

Internal microscopic structures of poly(N-isopropylacrylamide-co-tris(2,2'-bipyridyl))ruthenium(II) complex microgels were investigated using small-angle X-ray scattering (SAXS) in the extended q-range of 0.07 ≤ q/nm(-1) ≤ 20. The microgels were prepared by aqueous free-radical precipitation polymerization, resulting in formation of monodispersed, submicrometer-sized microgels, which was confirmed by transmission electron microscopy and dynamic light scattering. To reveal the changes in the microscopic structures of the microgels during swelling/deswelling or dispersing/flocculating oscillation, the redox state of Ru(bpy)3 complexes was fixed in the microgels using Ce(IV) or Ce(III) ions under high ionic strength (1.5 M) during the SAXS measurements. The scattering intensity of the microgels manifested five different structural features. In particular, the correlation length (ξ), which was obtained from the fitting analysis using the Ornstein-Zernike equation, of the microgels both in the reduced and oxidized Ru(bpy)3 states exhibited divergent-like behavior. In addition, a low-q peak centered at q ≈ 5 nm(-1) did not appear clearly in both the reduced [Ru(bpy)3](2+) and oxidized [Ru(bpy)3](3+) states, indicating that the formation of a polymer-rich domain was suppressed; thus, Ru(bpy)3 complexes can be active even though the microgels are deswollen or flocculated during the oscillation reaction.

Precise design of copolymer-conjugated nanocatalysts for active electron transfer.

A copolymer-conjugated nanocatalytic system has been designed for active electron transfer. To enhance photoinduced H2 generation, we precisely synthesize ternary random copolymers capable of transferring electrons through phase transitions, extending and shrinking in response to viologen's redox changes within 2 nm distance from the surface of the catalytic nanoparticle.

Effect of nanointegration on photoinduced hydrogen-generating nanogel systems.

The nanointegration mechanism for photoinduced hydrogen nanogenerators using nanogels is described. By spatially integrating poly(N-isopropylacrylamide-co-Ru(bpy)(3)) nanogels as a photosensitizer and Pt nanoparticles as a catalyst, a mechanism using electrostatic interactions and the shrinking behavior of the thermosensitive polymer network is revealed. In addition, to evaluate the sensitivity to exterior energy, light, and heat, the integrated nanospace is controlled by using thermosensitive nanogels, which drastically shrink above the volume phase transition temperature. Such nanospatial control of multiple kinds of functional molecules in a photochemical reaction is important for the realization of artificial photosynthetic systems.

Convective meniscus splitting of polysaccharide microparticles on various surfaces.

In contrast to convective self-assembly methods for colloidal crystals etc., "convective meniscus splitting method" was developed to fabricate three-dimensionally ordered polymeric structures. By controlling the geometry of evaporative interface of polymer solution, a deposited membrane with uniaxial orientation and layered structures can be prepared. Here it is demonstrated that xanthan gum polysaccharide microparticles with diameter ~ 1 µm can bridge a millimeter-scale gap to form such a membrane because the capillary force among the particles is more dominant than the gravitational force on the evaporative interface. This method is applicable for various substrates with a wide range of wettability (water contact angle, 11°-111°), such as glass, metals, and plastics. The specific deposition can be also confirmed between frosted glasses, functional-molecules-modified glasses, and gold-sputtered substrates. By using such a universal method, the membrane formed on a polydimethylsiloxane surface using this method will provide a new strategy to design a functional polysaccharide wall in microfluidic devices, such as mass-separators.

Photoexpansion of Biobased Polyesters: Mechanism Analysis by Time-Resolved Measurements of an Amorphous Polycinnamate Hard Film.

Cinnamate-based polyesters were synthesized, including poly(4-hydroxycinnamic acid), poly(4-hydroxy-3-methoxycinnamic acid), poly(3-hydroxycinnamic acid) (P3HCA), and hyperbranched poly(3,4-dihydroxycinnamic acid) (PdHCA). These materials were further processed into hard and dry membranes by casting and underwent photoreactions by ultraviolet (UV) light. The photodeformation behavior of the linear and hyperbranched polyester containing membranes with cinnamate derivatives in the main chain was observed macroscopically and microscopically. The PdHCA and P3HCA membranes were amorphous and exhibited photodeformations. The PdHCA surface visibly contracts, which is a typically observed phenomenon in photoresponsive polymers; however, the P3HCA surface showed a unique photoexpansion behavior. Time-resolution infrared spectroscopy of the P3HCA film revealed trans-to-cis isomerism in the polymer main chains that bent convexly as a result of photoexpansion of the UV-irradiated regions. Furthermore, photomasking created a micropattern on the P3HCA film, which supported the photoexpansion mechanism of the P3HCA film.

Interfacial self-assembly of polysaccharide rods and platelets bridging over capillary lengths.

HYPOTHESIS: Generation of long-range ordering of colloidal particles through anisotropic interactions is of growing interest in material designing. At submicron-scale, routine works use synthetic spheres or rods but the knowledge pertaining to assembly of binary combination of particles is severely restricted. Improved understanding of the fundamental aspects that drive self-assembly, can lead to robust strategies for fabrication of topographically oriented films. EXPERIMENT: The fluidical geometry of a liquid crystalline (LC) solution of polysaccharide consisting of micron-sized rod and platelet units was explored. The solutions, characterized for their rheological behavior, were evaporated from a rectangular cavity. The assembly and orientation of the units was monitored by polarizing microscopy and the interparticle capillary forces approximated mathematically. FINDINGS: The units deposited into an uninterrupted membrane upon interfacial evaporation, forming a bridge along the 8 mm gap, linking the substrates. The membrane, composed of a lamellar structure, was uniaxially oriented along the direction of the gap. The rheological estimations corroborated an extremely high value of viscosity with the presence of crosslinking junctions in this solution when compared to a solution with only rod units, capable of bridging a maximum of 1 mm. It has been demonstrated for the very first time that the presence of platelet-units contributes lateral capillary interactions and assist rod-units towards a wider, self-assembled structure.

Micro-deposition control of polysaccharides on evaporative air-LC interface to design quickly swelling hydrogels.

Uniaxial orientation is highly desirable for fabricating advanced soft materials. Liquid crystal (LC) polymer deposition was strategically manipulated at the air-LC interface, by controlling the drying temperature and initial concentration of aqueous solution of xanthan gum in a limited space. Interface-assisted orientation led to membrane-like depositions bridging the millimeter-scale gap between the substrates both, vertically and horizontally. The applicability of this approach lies in synchronization of the molecular orientation beyond their individual LC domains into the condensed state. Cross-polarized microscopy and SEM analysis correlated the orientation of the deposited polymer with the controlled mobility of xanthan gum LC domains at the evaporative interface. Subsequently, a phase diagram was prepared for the variety of oriented structures, depending upon the drying conditions. The deposited membrane behaved as an oriented hydrogel showing reversible anisotropic swelling/deswelling only along its thickness.

[Unidirectionally-oriented Membrane Formation of Supra-polysaccharides Sacran and Application to Drug Delivery System].

　The geometric structures of soft materials can be controlled on the macro-scale using interfacial or mechanical instability, e.g., fingering patterns of viscous liquid and buckling patterns of gels during swelling/deswelling. These patterns can be used as smart materials for capturing/releasing and mass-transportation applications. Here we introduce the emergence of a uniaxially oriented membrane by drying an aqueous liquid-crystalline solution, composed of megamolecular supra-polysaccharides "sacran", from a limited space. By controlling the geometries of the evaporation front, multiple nuclei emerge that grow into upright membranes with uniaxial orientation. Notably, the uniaxially orientated membrane composed of rod-like microdomains is rationally formed along the dynamic three-phase contact line. Besides, the membrane macroscopically partitions the three-dimensional cuboid cell for evaporating the aqueous solution. We envision that such a uniaxially oriented membrane can be used as soft biomaterials such as dialysis membranes with directional controllability in medical and pharmaceutical fields.

Emergence of polysaccharide membrane walls through macro-space partitioning via interfacial instability.

Living organisms in drying environments build anisotropic structures and exhibit directionality through self-organization of biopolymers. However, the process of macro-scale assembly is still unknown. Here, we introduce a dissipative structure through a non-equilibrium process between hydration and deposition in the drying of a polysaccharide liquid crystalline solution. By controlling the geometries of the evaporation front in a limited space, multiple nuclei emerge to grow vertical membrane walls with macroscopic orientation. Notably, the membranes are formed through rational orientation of rod-like microassemblies along the dynamic three-phase contact line. Additionally, in the non-equilibrium state, a dissipative structure is ultimately immobilized as a macroscopically partitioned space by multiple vertical membranes. We foresee that such oriented membranes will be applicable to soft biomaterials with direction controllability, and the macroscopic space partitionings will aid in the understanding of the space recognition ability of natural products under drying environments.

Methods for the Self-integration of Megamolecular Biopolymers on the Drying Air-LC Interface.

Living organisms that use water are always prone to drying in the environment. Their activities are driven by biopolymer-based micro- and macro-structures, as seen in the cases of moving water in vascular bundles and moisturizing water in skin layers. In this study, we developed a method for assessing the effect of aqueous liquid crystalline (LC) solutions composed of biopolymers on drying. As LC biopolymers have megamolecular weight, we chose to study polysaccharides, cytoskeletal proteins, and DNA. The observation of biopolymer solutions during drying under polarized light reveals milliscale self-integration starting from the unstable air-LC interface. The dynamics of the aqueous LC biopolymer solutions can be monitored by evaporating water from a one-side-open cell. By analyzing the images taken using cross-polarized light, it is possible to recognize the spatio-temporal changes in the orientational order parameter. This method can be useful for the characterization of not only artificial materials in various fields, but also natural living tissues. We believe that it will provide an evaluation method for soft materials in the biomedical and environmental fields.