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.

Assembly Structure Formation in Bulk and Ultrathin Films of Poly(substituted methylene) Having an Azobenzene Side Chain.

The density of the side chain introduced to a polymer main chain greatly influences the properties and functions of the polymer. This work first reports on the packing structure and properties at an interface of a poly(substituted methylene) where an azobenzene side chain is introduced at every carbon atom in the main chain (C1PAz). The structure and properties are compared with those of a conventional vinyl polymer [poly(methacrylate)] possessing an identical side-chain structure (C2PAz). The packing structure in the bulk state analyzed by X-ray measurements revealed that C1PAz adopts a highly ordered rectangular unit cell structure, whereas C2PAz shows a less ordered lamellar one. Langmuir film balance experiments indicated that both polymers with the trans-azobenzene give essentially the identical 2D side-chain occupying area on water, which agrees well with the smectic B (hexatic packing) model based on the X-ray data. Upon transfer onto a solid substrate, only C1PAz shows a conformational transformation to a spread bilayer-type layer, most probably due to conformational frustration stemming from the crowding of the side chains. This study proposes new insights into the effects of side-chain density on the self-assembly and photoreaction of azobenzene-containing polymers, which are expected to expand the possibilities of polymer design for various applications.

Influence of Humidity on Layer-by-Layer Growth and Structure in Coordination Networks.

Metal-organic frameworks (MOFs) are promising materials because of their high designability of pores and functionalities. Especially, MOF thin films and their properties have been investigated toward applications in nanodevices. Typically, MOF thin films are fabricated by using a bottom-up method such as layer-by-layer (LbL) growth in air. Because the water molecules can coordinate and be replaced with organic linkers during synthesis, humidity conditions will be expected to influence the LbL growth processes. In this study, we fabricated MOF thin films composed of Zn2+, tetrakis-(4-carboxyphenyl)-porphyrin (TCPP), and 4,4'-bipyridyl (bpy) at 10 and 40% relative humidity (RH) conditions. Then, we investigated the humidity effects on chemical compositions of TCPP and bpy, periodic structure, orientation, and surface morphology. At high RH, coordination replacement of water with the organic linkers becomes more competitive than that at low RH, resulting in a different TCPP/bpy composition ratio between the two RH conditions. Also, more frequent coordination replacements of water with the organic linkers at high RH led to the formation of phases other than that observed at low RH, loss of growth orientation, and rough surface. The findings clarified the importance of controlling the RH condition during LbL growth to obtain the desired coordination networks.

Synthesis of thermo-responsive polymer gels composed of star-shaped block copolymers by copper-catalyzed living radical polymerization and click reaction.

In recent times, there has been a significant surge in research interest surrounding thermo-responsive water-soluble polyacrylamides, primarily due to their intriguing capability to undergo significant solubility changes in water. These polymers exhibit the remarkable ability to shift from a soluble to an insoluble state in response to temperature variations. The capacity of these polymers to dynamically respond to temperature changes opens up exciting avenues for designing smart materials with tunable properties, amplifying their utility across a spectrum of scientific and technological applications. Researchers have been particularly captivated by the potential applications of thermo-responsive water-soluble polyacrylamides in diverse fields such as drug delivery, gene carriers, tissue engineering, sensors, catalysis, and chromatography separation. This study reports the construction and functionalization of polymer gels consisting of a polymer network of polyacrylamide derivatives with nano-sized structural units. Specifically, thermo-responsive polymer gels were synthesized by combining well-defined star-shaped polymers composed of polyacrylamide derivatives with a multifunctional initiator and linking method through a self-accelerating click reaction. The polymerization system employed a highly living approach, resulting in polymer chains characterized by narrow molecular weight distributions. The method's high functionality facilitated the synthesis of a temperature-responsive block copolymer gel composed of N-isopropyl acrylamide (NIPA) and N-ethyl acrylamide (NEAA). The resulting polymer gel, comprising star-shaped block copolymers of NIPA and NEAA, showcases smooth volume changes with temperature jumps.

This approach's versatility was showcased by creating networks using widely-used vinyl polymers. It can generate various functional and nearly ideal gels and elastomers, allowing for investigating fundamental aspects of polymer networks.

Induction of Highly Ordered Liquid Crystalline Phase of an Azobenzene Side Chain Polymer by Contact with 4'-Pentyl-4-cyanobiphenyl: An In Situ Study.

The orientation of liquid crystal (LC) molecules is significantly governed by solid interfaces and free surfaces, and a variety of functional materials have been developed using these properties. Although LC materials are already in industrial use, particularly for LC display panels, various studies have been conducted in recent years to better grasp the interface behavior of LC molecules. In this work, we succeeded in in situ observations of induction of higher ordered LC phases at the interface between a side-chain LC azobenzene polymer film with a thickness of ∼400 nm and a low-molecular-mass nematic LC, 4'-pentyl-4-cyanobiphenyl of 35 µm thickness, using small-angle X-ray scattering measurements and polarized optical microscopy. It is revealed that the two different mesogens cooperatively form hybrid higher ordered smectic LC phases probably through weak electron transfer immediately after interfacial contact. The induction process consists of three stages in terms of dynamic structure evolutions. Upon UV irradiation, the hybrid smectic LC structure diminished. This study provides new insights into the behavior of LC molecules near the alignment film on the solid substrate.

Effect of the Poly(ethylene glycol) Diacrylate (PEGDA) Molecular Weight on Ionic Conductivities in Solvent-Free Photo-Cross-Linked Solid Polymer Electrolytes.

To obtain safe, high-performance Li-ion batteries, the development of electrolytes with high impact resistance and high ionic conductivity is important. Ionic conductivity at room temperature has been improved by using poly(ethylene glycol) (PEG) diacrylate (PEGDA) to form three-dimensional (3D) networks and solvated ionic liquids. However, the effects of the molecular weight of PEGDA on ionic conductivities and the relationship between ionic conductivities and network structures of cross-linked polymer electrolytes have not been discussed in detail. In this study, the dependence of the ionic conductivity of photo-cross-linked PEG solid electrolytes on the molecular weight of the PEGDA was evaluated. X-ray scattering (XRS) gave detailed information about the dimensions of 3D networks formed by the photo-cross-linking of PEGDA, and the effects of the network structures on the ionic conductivities were discussed.

Optically Transparent and Color-Stable Elastomer with Structural Coloration under Elongation.

Optically transparent and colored elastomers with high toughness are expected to play an important role in the construction of advanced medical materials, wearable displays, and soft robots. In this study, we found that composite elastomers consisting of amorphous SiO2 particles homogeneously dispersed in high concentrations within a biocompatible acrylic polymer network exhibit optical transparency and bright structural colors. In the composite elastomers, the system in which the SiO2 particles form a colloidal amorphous array hardly changes its structural color hue despite deformation due to elongation. Furthermore, the composite elastomer of the SiO2 particles with the acrylic polymer network also results in high mechanical toughness. In summary, we have shown that the elastomer that exhibits fade-resistant structural coloration formed from safe materials can combine stable coloration and mechanical strength independent of their shape. This is expected to have new potential in future technologies to support our daily life.

Induced Smectic E Phase in a Binary Blend of Side-Chain Liquid Crystalline Polymers.

Two liquid crystalline polymers containing an azobenzene or cyanobiphenyl mesogenic side chain that adopt smectic A phases are mechanically mixed at 1:1 mesogen molar ratio at an isotropic phase temperature and then cooled. The resultant binary polymer mixture behaves like a single component as revealed by polarized microscopy observation and differential scanning calorimetry, indicating that the binary mixture forms a fully compatible polymer blend. Moreover, the simple polymer blend unexpectedly leads to a higher-ordered smectic E phase where a herringbone structure is formed with restricted mesogen axis rotation. These results suggest a specific intermolecular interaction between the two mesogens, thereby inducing unusual compatibilized polymer blends and the most ordered liquid crystal (LC) phase.

Donor-π-Acceptor-Type Fluorinated Tolane Containing a Semifluoroalkoxy Chain as a Condensed-Phase Luminophore.

Photoluminescent liquid-crystalline (PLLC) molecules, which can easily tune the PL behavior through the crystal (Cry)-LC phase transition, have attracted significant attention. Previously, we have demonstrated that the incorporation of a semifluoroalkoxy chain into π-conjugated mesogen is a promising approach for developing PLLC molecules with PL and SmA LC characteristics. We focused on the LC and PL characteristics of the molecules induced by the semifluoroalkoxy chain and fluorinated tolanes in the condensed phase. In this study, we developed cyano- or ethoxycarbonyl-terminated donor-π-acceptor-type fluorinated tolanes containing a semifluoroalkoxy flexible chain. The cyano-terminated fluorinated tolanes exhibited intense light-blue photoluminescence in the crystalline phase and did not exhibit any LC phase. In contrast, blue photoluminescence in the ethoxycarbonyl-terminated analogs was slightly weak; however, they exhibited Cry-SmA phase transition during the heating and cooling processes. The PL intensity of the ethoxycarbonyl-terminated fluorinated tolanes significantly decreased in the SmA phase; however, their PL colors changed during the Cry-SmA phase transition. This indicates that the developed tolanes are promising temperature-dependent PL materials, such as PL thermosensors or PL thermometers.

Shrinking rates of polymer gels composed of star-shaped polymers of N-isopropylacrylamide and dimethylacrylamide copolymers: the effect of dimethylacrylamide on the crosslinking network.

Thermoresponsive polymer gels can be applied as culture beds for cell sheets, drug release agents for drug delivery, and sensing materials. In general, the shrinkage behavior of thermoresponsive polymer gels is complex, and they may require much longer times than swelling to reach thermodynamically stable shrinkage states. This slow volume change during shrinkage is often a drawback in using reversible changes in polymer gel volumes with changing temperature for applications such as those described above, and attempts have been made to improve the shrinkage rates of polymer gels. However, using the conventional method results in a low density of the three-dimensional crosslinked network comprising the polymer gel, which weakens the mechanical properties of the polymer gel. In this study, we investigated the effects of monomer arrangement and composition for star-shaped polymers composed of N-isopropylacrylamide and N,N-dimethylacrylamide on the shrinkage behavior of gels comprising star-shaped polymers with the aim of increasing their shrinkage rates without reducing the network densities of the temperature-responsive polymer gels. Based on selective network decomposition by methanolysis and SAXS measurements, the network structures of the obtained spherical gels were found to be more homogeneous than those of polymer gels obtained by conventional free radical polymerization. These gels exhibited reversible volume changes in water, with low-temperature swelling and high-temperature shrinkage. The rates of volume changes from a high temperature shrunken state to a low temperature swollen one were almost the same for all gels. However, the rates of volume changes from low-temperature swollen states to high-temperature shrunken states varied greatly depending on the compositions and sequences of monomers that made up the polymer networks. We confirmed that the introduction of more than 20% DMA as a block copolymer in the network suppressed phase separation and formation of a skin layer and the water inside the polymer gel drained smoothly to the outside, which resulted in an increase in the shrinkage speed.

Solvent- and Light-Sensitive AIEE-Active Azo Dye: From Spherical to 1D and 2D Assemblies.

Fluorescent molecular assembly systems provide an exciting platform for creating stimuli-responsive nano- and microstructured materials with optical, electronic, and sensing functions. To understand the relationship between (i) the plausible molecular structures preferentially adopted depending on the solvent polarity (such as N,N-dimethylformamide [DMF], tetrahydrofuran [THF], and toluene), (ii) the resulting spectroscopic features, and (iii) self-assembled nano-, micro-, and macrostructures, we chose a sterically crowded triangular azo dye (3Bu) composed of a polar molecular core and three peripheral biphenyl wings. The chromophore changed the solution color from yellow to pink-red depending on the solvent polarity. In a yellow DMF solution, a considerable amount of the twisted azo form could be kept stable with the help of favorable intermolecular interactions with the solvent molecules. By varying the concentration of the DMF solution, the morphology of self-assembled structures was transformed from nanoparticles to micrometer-sized one-dimensional (1D) structures such as sticks and fibers. In a pink-red toluene solution, the periphery of the central ring became more planar. The resulting significant amount of the keto-hydrazone tautomer grew into micro- and millimeter-sized 1D structures. Interestingly, when THF-H2O (1:1) mixtures were stored at a low temperature, elongated fibers were stacked sideways and eventually developed into anisotropic two-dimensional (2D) sheets. Notably, subsequent exposure of visible-light-irradiated sphere samples to solvent vapor resulted in reversible fluorescence off↔on switching accompanied by morphological restoration. These findings suggest that rational selection of organic dyes, solvents, and light is important for developing reusable fluorescent materials.

Formation of High-Density Brush of Liquid Crystalline Polymer Block Associated with Dewetting Process on Amorphous Polymer Film.

The understanding of polymer dewetting on solid surfaces is significant in both fundamental polymer physics and practical film technologies. When liquid crystalline (LC) polymers are dewetted, LC ordering is involved in the dewetting process. Here, we report on the characteristic dewetting processes of a diblock copolymer composed of a cyanobiphenyl side chain liquid crystalline polymer (SCLCP) block connected with polystyrene (PS) taking place on a PS base film. Thin films of the block copolymer were prepared by the water-floating method onto the PS film, and the dewetting process is observed in a softened state above the glass transition temperature of the PS. At the smectic A phase temperature of the SCLCP block, the dewetted surface layer generated a flat unique fingering pattern leading to a monolayered (two-dimensional) high-density LC polymer brush through the LC ordering. The important role of the anchoring PS block on the base PS film surface is suggested for the formation of highly stretched LC polymer brush. Above the isotropization temperature, in contrast, ordinary three-dimensional droplet morphologies with smooth round edges were observed. By photo-cross-linking the base PS film, the lateral diffusion rate was significantly reduced. This can be applied to an entropy-driven morphology patterning via dewetting. The polymer brush formation and its spatial controls are expected to provide new opportunities for the modification strategies of polymer surfaces.

Synthesis and Field-Effect Transistor Application of π-Extended Lactam-Fused Conjugated Oligomers obtained by Tandem Direct Arylation.

Five π-extended lactam-fused conjugated oligomers (5FO, 5FS, 4FPO, 4FPS, and R-4FPO) were synthesized by the tandem direct arylation. The intermolecular oxidative direct arylation was applied in the second step. These conjugated oligomers had fine-tuned FMO energies predictable by the theoretical calculation and excellent thermal stabilities. 4FPO and 4FPS bearing tetrafluoropyridine exhibited lower LUMO energy levels (-3.20 eV and -3.39 eV, respectively) compared with others. Based on the X-ray crystallography, 4FPO was found to have a herringbone crystal packing and a considerably large electron transfer integral value (137 meV). 4FPO-based bottom-gate, bottom-contact FET device demonstrated an electron mobility of 5.2×10-3  cm2 V-1 s-1 as a result of an edge-on alignment on the SiO2 substrate.

Structural Monitoring of the Onset of Excited-State Aromaticity in a Liquid Crystal Phase.

Aromaticity of photoexcited molecules is an important concept in organic chemistry. Its theory, Baird's rule for triplet aromaticity since 1972 gives the rationale of photoinduced conformational changes and photochemical reactivities of cyclic π-conjugated systems. However, it is still challenging to monitor the dynamic structural change induced by the excited-state aromaticity, particularly in condensed materials. Here we report direct structural observation of a molecular motion and a subsequent packing deformation accompanied by the excited-state aromaticity. Photoactive liquid crystal (LC) molecules featuring a π-expanded cyclooctatetraene core unit are orientationally ordered but loosely packed in a columnar LC phase, and therefore a photoinduced conformational planarization by the excited-state aromaticity has been successfully observed by time-resolved electron diffractometry and vibrational spectroscopy. The structural change took place in the vicinity of excited molecules, producing a twisted stacking structure. A nanoscale torque driven by the excited-state aromaticity can be used as the working mechanism of new photoresponsive materials.

Photo-Responsive Soft Ionic Crystals: Ion-Pairing Assemblies of Azobenzene Carboxylates.

This report delineates the design and synthesis of negatively charged azobenzene derivatives that form photo-responsive ion-pairing assemblies. The azobenzene carboxylates possessing aliphatic chains were prepared as photo-responsive anions that promote the formation of ion-pairing dimension-controlled assemblies, including mesophases, when used in conjunction with a tetrabutylammonium (TBA) cation. The photo-responsive properties of the ion pairs and the precursory carboxylic acids in the bulk state were examined by polarized optical microscopy (POM) and X-ray diffraction (XRD), demonstrating that liquid crystal (LC)-liquid and crystal-liquid phase transitions occurred, depending on the number and lengths of the aliphatic chains of each assembly. An ion pair exhibited photo-induced crystal-crystal phase transitions upon switching between two irradiation wavelengths (365/436 nm).

Metal-Organic Coordination Network Thin Film by Surface-Induced Assembly.

The growth of metal-organic coordination network thin films on surfaces has been pursued extensively and intensively to manipulate the molecular arrangement. For this study, the oriented multilayer thin films based on porphyrinic nanoarchitecture were synthesized toward metal-organic coordination networks using surface-induced assembly (SIA). Nanoscale molecular thin films were prepared at room temperature using cobalt(II) ion and porphyrin building blocks as precursors. Stepwise growth with a highly uniform layer was characterized using UV-vis, AFM, IR, and XPS studies. The grazing incidence small-angle X-ray scattering and X-ray reflectivity results remarkably suggested a periodic structure in in-plane direction with constant and high mass density (ca. 1.5 g/cm(3)) throughout the multilayer formation. We propose that orientation of the porphyrin macrocycle plane with a hexagonal packed model by single anchoring mode was tilted approximately 60° with respect to the surface substrate. It is noteworthy that the well-organized structure of porphyrin-based macrocyclic framework on the amine-terminated surface substrate can be achieved efficiently using a simple SIA approach under mild synthetic conditions. The synthesized thin film provides a different structure from that obtained using bulk synthesis. This result suggests that the SIA technique can control not only the film thickness but also the structural arrangement on the surface. This report of our research provides insight into the ordered porphyrin-based metal-organic coordination network thin films, which opens up opportunities for exploration of unique thin film materials for diverse applications.

Free Surface Command Layer for Photoswitchable Out-of-Plane Alignment Control in Liquid Crystalline Polymer Films.

To date, reversible alignment controls of liquid crystalline materials have widely been achieved by photoreactive layers on solid substrates. In contrast, this work demonstrates the reversible out-of-plane photocontrols of liquid crystalline polymer films by using a photoresponsive skin layer existing at the free surface. A polymethacrylate containing a cyanobiphenyl side-chain mesogen adopts the planar orientation. Upon blending a small amount of azobenzene-containing side-chain polymer followed by successive annealing, segregation of the azobenzene polymer at the free surface occurs and induces a planar to homeotropic orientation transition of cyanobiphenyl mesogens underneath. By irradiation with UV light, the mesogen orientation turns into the planar orientation. The orientation reverts to the homeotropic state upon visible light irradiation or thermally, and such cyclic processes can be repeated many times. On the basis of this principle, erasable optical patterning is performed by irradiating UV light through a photomask.

Proton Conductivities of Lamellae-Forming Bioinspired Block Copolymer Thin Films Containing Silver Nanoparticles.

Size-controlled metal nanoparticles (NPs) were spontaneously formed when the amphiphilic diblock copolymers consisting of poly(vinyl catechol) and polystyrene (PVCa-b-PSt) were used as reductants and templates for NPs. In the present study, the proton conductivity of well-aligned lamellae structured PVCa-b-PSt films with Ag NPs was evaluated. We found that the proton conductivity of PVCa-b-PSt film was increased 10-fold by the addition of Ag NPs into the proton conduction channels filled with catechol moieties. In addition, the effect of humidity and the origin of proton conductivity enhancement was investigated.

Fabrication and Characterization of Cross-Linked Organic Thin Films with Nonlinear Mass Densities.

The preparation of urea (bonded) cross-linked multilayer thin films by sequential deposition of bifunctional and tetrafunctional molecular building blocks is demonstrated. Multilayer growth as a function of deposition cycles was inspected using UV-vis absorption spectroscopy. From infrared results, three characteristic infrared bands of amide I, amide II, and asymmetric νa(N-C-N) stretching confirmed the formation of polyurea networks by alternate dipping into solutions of amine and isocyanate functionality monomers. The deconvoluted component of the C 1s and N 1s spectra obtained by X-ray photoelectron spectroscopy shows clear evidence of stable polyurea networks. The enhancement of structural periodicity with film growth was demonstrated by grazing-incidence small-angle X-ray scattering measurements. The thin film near the substrate surface seems to have an amorphous structure. However, molecular ordering improves in the surface normal direction of the substrate with a certain number of deposited layers. Constant mass density was not observed with deposition cycles. The mass density increased up to 16% within deposited layers from proximate layers to those extending away from the substrate surface. This difference in the packing density might derive from the different degrees of cross-linking among layers proximate to the substrate surface and extending away from the substrate surface.

Evaluations of Mesogen Orientation in Thin Films of Polyacrylate with Cyanobiphenyl Side Chain.

The orientation behavior of mesogens in a polyacrylate with cyanobiphenyl (CB) side chain in thin films was investigated in detail by UV-vis absorption spectroscopy and grazing incidence small-angle X-ray scattering (GI-SAXS) measurements using both high-energy X-rays of Cu Kα line (λ = 0.154 nm) and low-energy synchrotron X-rays (λ = 0.539 nm). By changing the film thickness ranging 7-200 nm, it is concluded that the planar orientation is predominant for thin films with thickness below 10-15 nm. This planar mesogen orientation near the substrate surface coexists with the homeotropically aligned CB mesogens in films thicker than 30 nm. For the thinnest 7 nm film, the planar orientation is unexpectedly lost, which is in consort with a disordering of smectic layer structure. Peculiar orienting characteristics of CB mesogen are suggested, which probably stem from the tendency to form an antiparallel arrangement of mesogens due to the strong dipole moment of the terminal cyano group.