Search

2D metal nanosheets have attracted significant attention as efficient catalysts for various important chemical reactions. However, the development of metal nanosheets with controlled compositions and morphologies has been slow due to the challenges associated with synthesizing thermodynamically unfavorable 2D structures. Herein, we report a synthesis route of freestanding Pd-Ag penta-twinned nanosheets (Pd-Ag ptNSs) with distinct 5-fold twin boundaries. Through the coreduction of Ag and Pd precursors on presynthesized Pd ptNSs, Ag could be homogeneously alloyed with Pd, leading to the formation of well-defined Pd-Ag ptNSs. The promotional effects of the bimetallic composition, 2D structure, and twin boundaries on catalysis were studied by using Pd-Ag ptNS-catalyzed H 2 production from formic acid decomposition as a model reaction. Notably, the catalytic activity of the Pd-Ag ptNSs drastically outperformed those of monometallic, bimetallic, and 3D counterparts, such as Pd ptNSs, Pd-Ag nanosheets without a TB, and Pd-Ag octahedral nanocrystals, demonstrating the promising potential of the integration of twin boundaries and multiple compositions in the development of high-performance 2D nanocatalysts.

Liquid crystals (LCs) have been adopted to induce tunable physical properties that dynamically originated from their unique intrinsic properties responding to external stimuli, such as surface anchoring condition and applied electric field, which enables them to be the template for aligning functional guest materials. We fabricate the fiber array from the electrically modulated (in-plain) nematic LC template using the chemical vapor polymerization (CVP) method. Under an electric field, an induced defect structure with a winding number of -1/2 contains a periodic zigzag disclination line. It is known that LC defect structures can trap the guest materials, such as particles and chemicals. However, the resulting fibers grow along the LC directors, not trapped in the defects. To show the versatility of our platform, nanofibers are fabricated on patterned electrodes representing the alphabets 'CVP.' In addition, the semifluorinated moieties are added to fibers to provide a hydrophobic surface. The resultant orientation-controlled fibers will be used in controllable smart surfaces that can be used in sensors, electronics, photonics, and biomimetic surfaces.

DNA is an anisotropic, water-attracting, and biocompatible material, an ideal building block for hydrogel. The alignment of the anisotropic DNA chains is essential to maximize hydrogel properties, which has been little explored. Here, we present a method to fabricate the anisotropic DNA hydrogel that allows precise control for the polymerization process of photoreactive cationic monomers. Scanning ultraviolet light enables the uniaxial alignment of DNA chains through the polymerization-induced diffusive mass flow using a concentration gradient. While studying anisotropic mechanical properties and orientation recovery according to the DNA chain alignment direction, we demonstrate the potential of directionally controlled DNA hydrogels as smart materials.

Recent years have shown the need for trustworthy, unclonable, and durable tokens as proof of authenticity for a large variety of products to combat the economic cost of counterfeits. An excellent solution is physical unclonable functions (PUFs), which are intrinsically random objects that cannot be recreated, even if illegitimate manufacturers have access to the same methods. We propose a robust and simple way to make pixelated PUFs through the deposition of a random mixture of fluorescent colloids in a predetermined lattice using capillarity-assisted particle assembly. As the encoding capacity scales exponentially with the number of deposited particles, we can easily achieve encoding capacities above 10 700 for sub millimeter scale samples, where the pixelated nature of the PUFs allows for easy and trustworthy readout. Our method allows for the PUFs to be transferred to, and embedded in, a range of transparent materials to protect them from environmental challenges, leading to improved stability and robustness and allowing their implementation for a large number of different applications.

Metal-organic frameworks (MOFs) represent crystalline materials constructed from combinations of metal and organic units to often yield anisotropic porous structures and physical properties. Postsynthetic methods to align the MOF crystals in bulk remain scarce yet tremendously important to fully utilize their structure-driven intrinsic properties. Herein, we present an unprecedented composite of liquid crystals (LCs) and MOFs and demonstrate the use of nematic LCs to dynamically control the orientation of MOF crystals with exceptional order parameters (as high as 0.965). Unique patterns formed through a facile multidirectional alignment of MOF crystals exhibit polarized fluorescence with the fluorescence intensity of a pattern dependent on the angle of a polarizer, offering potential use in various optical applications such as an optical security label. Further, the alignment mechanism indicates that the method is applicable to numerous combinations of MOFs and LCs, which include UV polymerizable LC monomers used to fabricate free-standing composite films.

Using improper wound care materials may cause impaired wound healing, which can involve scar formation and infection. Herein, we propose a facile method to fabricate a cell-alignment scaffold, which can effectively enhance cell growth and migration, leading to the reproduction of cellular arrangements and restoration of tissues. The principle is scratching a diamond lapping film that gives uniaxial nanotopography on substrates. Cells are seeded to follow the geometric cue via contact guidance, resulting in highly oriented cell alignment. Remarkable biocompatibility is also demonstrated by the high cell viability on various substrates. In vivo studies in a wound healing model in mice show that the scratched film supports directed cell guidance on the nanostructure, with significantly reduced wound areas and inhibition of excessive collagen deposition. Rapid recovery of the epidermis and dermis is also shown by histological analyses, suggesting the potential application of the scratching technique as an advanced wound dressing material for effective tissue regeneration.

We have fabricated patterned fibers using a small-molecular-weight liquid crystal (LC) and reactive mesogens (RMs) under controlled electric fields in which defect arrays are generated depending on the electrode configuration. For this, the AC electric field with interdigitated electrodes is used to develop versatile defect structures of the LC phase. Hydrophobic LC network (LCN) fibers exhibiting porous morphologies have been made by removing the LC part after the polymerization of RM. The resulting LCN fibers show a surface tension reduction characteristic compared to the neat RM film and a sticky characteristic with the water droplet, suggesting a facile way to fabricate the hydrophobic surface that can be used in microdroplet transport.

We demonstrate a facile method to fabricate a recyclable cell-alignment scaffold using nanogrooves based on sublimable liquid crystal (LC) material. Randomly and uniaxially arranged smectic LC structures are obtained, followed by sublimation and recondensation processes, which directly produce periodic nanogrooves with dimensions of a couple of hundreds of nanometers. After treatment with osmium tetroxide (OsO 4 ), the nanogroove can serve as a scaffold to efficiently induce directed cell growth without causing cytotoxicity, and it can be used repeatedly. Together, various cell types are applied to the nanogroove, proving the scaffold's broad applicability. Depending on the nanotopography of the LC structures, cells exhibit different morphologies and gene expression patterns, compared to cells on standard glass substrates, according to microscopic observation and qPCR. Furthermore, cell sheets can be formed, which consist of oriented cells that can be repeatedly formed and transferred to other substrates, while maintaining its organization. We believe that our cell-aligning scaffold may pave the way for the soft material field to bioengineering, which can involve fundamentals in cell behavior and function, as well as applications for regenerative medicine.

Manufacturing an economically viable, efficient commercial thermoelectric (TE) module is essential for power generation and refrigeration. However, mediocre TE properties, lack of good mechanical stability of the material, and significant difficulties involved in the manufacturing of large-scale powder as well as bulk samples hinder the potential applications of the modules. Herein, an economically feasible single-step water atomization (WA) is employed to synthesize BST powder (2 kg) by Cu doping within a short time and consolidated into large-scale bulk samples (500 g) for the first time with a diameter of 50 mm and a thickness of about 40 mm using spark plasma sintering (SPS). The incorporation of Cu into BST greatly boosts the carrier concentration, leading to a significant increase in electrical conductivity, and inhibits the bipolar thermal conductivity by 73%. Synchronously, the lattice contribution (κ L ) is greatly reduced by the effective scattering of phonons by comprising fine-grain boundaries and point defects. Therefore, the peak ZT is shifted to the mid-temperature range and obtained a maximum of ∼1.31 at 425 K and a ZT ave of 1.24 from 300 to 500 K for the BSTCu 0.05 sample, which are considerably greater than those of the bare BST sample. Moreover, the maximum compressive mechanical strength of large-size samples manufactured by the WA-SPS process is measured as 102 MPa, which is significantly higher than commercial zone melting samples. The thermoelectric module assembled with WA-SPS-synthesized BSTCu 0.05 and commercial n-type BTS material manifests an outstanding cooling performance (-19.4 °C), and a maximum output power of 6.91 W is generated at Δ T ∼ 200 K. These results prove that the BSTCu x samples are eminently suitable for the fabrication of industrial thermoelectric modules.

Circularly polarized light (CPL) is an inherently chiral entity and is considered one of the possible deterministic signals that led to the evolution of homochirality. While accumulating examples indicate that chirality beyond the molecular level can be induced by CPL, not much is yet known about circumstances where the spin angular momentum of light competes with existing molecular chiral information during the chirality induction and amplification processes. Here we present a light-triggered supramolecular polymerization system where chiral information can both be transmitted and nonlinearly amplified in a "sergeants-and-soldiers" manner. While matching handedness with CPL resulted in further amplification, we determined that opposite handedness could override molecular information at the supramolecular level when the enantiomeric excess was low. The presence of a critical chiral bias suggests a bifurcation point in the homochirality evolution under random external chiral perturbation. Our results also highlight opportunities for the orthogonal control of supramolecular chirality decoupled from molecular chirality preexisting in the system.

A photonic lattice is an efficient platform for optically exploring quantum phenomena. However, its fabrication requires high costs and complex procedures when conventional materials, such as silicon or metals, are used. Here, we demonstrate a simple and cost-effective fabrication method for a reconfigurable chiral photonic lattice of the helical nanofilament (HNF) liquid crystal (LC) phase and diffraction grating showing wavelength-dependent diffraction with a rotated polarization state. Furthermore, the UV-exposed areas of the HNF film having chiral characteristics act as optical building blocks that induce resonant intensity modulation in the reflectance and transmittance modes and the optical rotation of the linear polarization. Our photonic lattice of the HNF can be an efficient platform for a chirality-embedded photonic lattice at a low cost.

We fabricate the bio-organic field-effect transistor (BOFET) with the DNA-perylene diimide (PDI) complex, which shows unusual chiroptical and electrical functionalities. DNA is used as the chirality-inducing scaffold and the charge-injection layer. The shear-oriented film of the DNA-PDI complex shows how the large-area periodic molecular orientation and the charge transport are related, generating drastically different optoelectronic properties at each DNA/PDI concentration. The resultant BOFET reveals chiral structures with a high charge carrier mobility, photoresponsivity, and photosensitivity, reaching 3.97 cm 2 V -1 s -1 , 1.18 A W -1 , and 7.76 × 10 3 , respectively. Interestingly, the BOFET enables the definitive response under the handedness of circularly polarized light with a high dissymmetry factor of approximately +0.14. This work highlights the natural chirality and anisotropy of DNA material and the electron conductivity of organic semiconducting molecules to be mutually used in significant chiro-optoelectronic functions as an added ability to the traditional OFET.

Multiscale hierarchical nano- and microstructures of amyloid fibrils are fabricated by evaporation-induced self-assembly combined with topographic surface patterning techniques. The continuous stick-and-slip motion induces uniaxial alignment of amyloid fibrils characterized by high orientational order during the drying process. The optical textures of the resultant amyloid aggregates are directly observed by polarized optical microscopy (POM) and atomic force microscopy (AFM). The resulting fiber structure can be tuned by varying the width of the topographic pattern, e.g. , the microchannel width, inducing different separation between the deposited amyloid fibers on the glass substrate. Additionally, amyloid fibrils are decorated with gold nanoparticles to produce conductive microwires showing good conductivity (∼10 -3 S/m). The finely controlled deposited amyloid fibers presented here can show a way to use naturally-abundant biomaterials for practical applications such as nanowires and sensors.

The arrangement of mesogenic units determines mechanical response of the liquid crystal polymer network (LCN) film to heat. Here, we show an interesting approach to programming three-dimensional patterns of the LCN films with periodic topological defects generated by applying an electric field. The mechanical properties of three representative patterned LCN films were investigated in terms of the arrangement of mesogenic units through tensile testing. Remarkably, it was determined that LCN films showed enhanced toughness and ductility as defects increased in a given area, which is related to the elastic modulus mismatch that mitigates crack propagation. Our platform can also be used to modulate the frictional force of the patterned LCN films by varying the temperature, which can provide insight into the multiplex mechanical properties of LCN films.

The control of molecular orientation and ordering of liquid crystal (LC) organic semiconductor (OSC) for high-performance and thermally stable organic thin-film transistors is investigated. A liquid crystalline molecule, 2-(4-dodecyl thiophenyl)[1]dibenzothiopheno[6,5- b :6',5'- f ]-thieno[3,2- b ]thiophene (C12-Th-DBTTT) is synthesized, showing the highly ordered smectic X (SmX) phase, demonstrating molecular reorganization via thermal annealing. The resulting thermally evaporated polycrystalline film and solution-sheared thin film show high charge carrier mobilities of 9.08 and 27.34 cm 2 V -1 s -1 , respectively. Atomic force microscopy and grazing-incidence X-ray diffraction analyses prove that the random SmA 1 -like structure (smectic monolayer) is reorganized to the highly ordered SmA 2 -like structure (smectic bilayer) of C12-Ph-DBTTT at the crystal-SmX transition temperature region. Because of the strong intermolecular interactions between rigid DBTTT cores, the thin film devices of C12-Th-DBTTT show excellent thermal stability up to 300 °C, indicating that LC characterization of conventional OSC materials can obtain high electrical performance as well as superior thermal durability.

Directed self-assembly (DSA) of block copolymer (BCP) thin films is of particular interest in nanoscience and nanotechnology due to its superior ability to form various well-aligned nanopatterns. Herein, nanoscratch-DSA is introduced as a simple and scalable DSA strategy allowing highly aligned BCP nanopatterns over a large area. A gentle scratching on the target substrate with a commercial diamond lapping film can form uniaxially aligned nanoscratches. As applied in BCP thin films, the nanoscratch effectively guides the self-assembly of overlying BCPs and provides highly aligned nanopatterns along the direction of the nanoscratch. The nanoscratch-DSA is not material-specific, allowing more versatile nanofabrication for various functional nanomaterials. In addition, we demonstrate that the nanoscratch-DSA can be utilized as a direction-controllable and area-selective nanofabrication method.

The molecular orientation of organic semiconductors (OSCs) is of fundamental importance to anisotropic electrical behavior as well as superior properties in practical applications. Here, a simple and effective method is demonstrated to fabricate highly oriented semiconducting polymers, poly(3-hexylthiophene) (P3HT) and poly{[ N , N '-bis(2-octyldodecyl)-1,4,5,8-naphthalenediimide-2,6-diyl]- alt -5,5'-(2,2'-bithiophene)} (P(NDI2OD-T2)), by mass transfer effect under microchannel molds by diffusion and convection. Furthermore, parallel or perpendicular molecular arrangements relative to the channel direction were achieved by varying the widths of the microchannels, which are directly observed using polarized optical microscopy and two-dimensional grazing-incidence X-ray diffraction experiments. The method could enable the fabrication of organic field-effect transistors that exhibit anisotropic electrical properties indicating inter- or intrachain charge transport. The resulting platform will provide a simple approach for multidirectional orientations of anisotropic OSCs.

A bilayer dichroic-doped liquid crystal (BDLC) film is fabricated via the uniaxial alignment method and a photopolymerization process. It is found to be useful in dichroic color filters, dual-mode circular polarizers, and chirality detectors. Two kinds of dichroic films with different absorbing wavelengths are cross-stacked to show various colors and contrasts depending on the polarization direction of the incident linearly polarized light, which is comparable with the conventional single-layer dichroic dye-doped (SDLC) film that only shows the contrast difference. This platform can be used in many other applications beyond the applications presented in this study, such as multicolor holograms, optical signal encryption, and electrically tunable devices.

Since organic pollutants in water resources have raised concerns on aquatic ecosystems and human health, mechanical machines such as a nanopump for rapid and efficient removal of pollutants from water with regeneration properties remains a challenge. Here, a pH-responsive artificial pump from left-handed porous tubules into right-handed solid fibers was presented by the self-assembly of bent-shaped aromatic amphiphiles. The bent-shaped amphiphile with a pH-sensitive segment was demonstrated in aromatic hexameric macrocycles, which could contract into dimeric disks. Such a switchable aromatic pore with superhydrophobicity was well-suited for an efficient removal and controlled release of organic pollutants from water through pulsating motion. The removal efficiency is found to be 78% for ethinyloestradiol and 82% for bisphenol. Additionally, the pumping accompanied by chiral inversion was endowed with a rapid removal and convenient regenerable ability. The inflation from right-handed solid fibers into left-handed tubules for efficient removal pollutants was remarkably promoted by (-)-acidic enantiomer of malic acid, whereas the contraction with full desorption of pollutants was incisively responsive to alkaline with (+)-conformation. The kinetically regulable porous device with a chiral recognition will provide a promising platform for the construction of rapid responsible machine for sewage treatment.

Developing easy and customizable strategies for the directional structure modulation of multicomponent nanosystems to influence and optimize their properties are a paramount but challenging task in nanoscience. Here, we demonstrate highly controlled eccentric off-center positioning of metal-core in metal@silica core-shells by utilizing an in situ generated biphasic silica-based intraparticle solid-solid interface. In the synthetic strategy, by including Ca 2+ -ions in silica-shell and successive oxidative and reductive annealing at high temperature, a unique hairline-biphasic interface is evolved via the heat-induced concentric radial segregation of calcium silicate phase at the interior and normal silica phase at the exterior of core-shell, which can effectively arrest the outwardly migrating metal-core within rubbery calcium silicate phase, affording various eccentric core-shells, where core-positions are flexibly controlled by the annealing time and amounts of initially added Ca 2+ -ions. In the structure-property correlation study, the strategy allows fine-tuning of dipolar interaction-based blocking temperatures and magnetic anisotropies of different eccentric core-shells as the function of variable off-center distance of magnetic core without changing the overall size of nanoparticles. This work demonstrates the discovery and potential application of biphasic solid-solid media interface in controlling the heat-induced migration of metal nanocrystals and opens the avenues for exploiting the rarely studied high-temperature solid-state nanocrystal conversion chemistry and migratory behavior for directional nanostructure engineering.

Electron donor (D)-acceptor (A)-type conjugated polymers (CPs) have emerged as promising semiconductor candidates for organic field-effect transistors. Despite their high charge carrier mobilities, optimization of electrical properties of D-A-type CPs generally suffers from complicated post-deposition treatments such as high-temperature thermal annealing or solvent-vapor annealing. In this work, we report a high-mobility diketopyrrolopyrrole-based D-A-type CP nanowires, self-assembled by a simple but very effective solvent engineering method that requires no additional processes after film deposition. In situ grown uniform nanowires at room temperature were shown to possess distinct edge-on chain orientation that is beneficial for lateral charge transport between source and drain electrodes in FETs. FETs based on the polymer nanowire networks exhibit impressive hole mobility of up to 4.0 cm 2 V -1 s -1 . Moreover, nanowire FETs showed excellent operational stability in high temperature up to 200 °C because of the strong interchain interaction and alignment.

One of the alluring aspects of liquid crystals (LCs) is their readily controllable self-assembly behavior, leading to comprehension of complex topological structures and practical patterning applications. Here, we report on manipulating various kinds of topological defects by adopting an imprinted polymer-based soft microchannel that simultaneously imposes adjustable surface anchoring, confinement, and uniaxial alignment. Distinctive molecular orientation could be achieved by varying the surface anchoring conditions at the sidewall polymer and the rubbing directions on the bottom layer. On this pioneering platform, a common LC material, 8CB (4'-n-octyl-4-cyano-biphenyl), was placed where various topological defect domains were generated in a periodic arrangement. The experimental results showed that our platform can change the packing behavior and even the shape of topological defects by varying the rubbing condition. We believe that this facile tool to modulate surface boundary conditions combined with topographic confinement can open a way to use LC materials in potential optical and patterning applications.

Structural coloration using plasmonic particles has received substantial attention due to its robust, permanent, and scalable characteristics across the full color range. In this study, a plasmonic structure based on a porous anodic aluminum oxide (AAO) film coated with a metallic film was fabricated. Colors were varied by changing the refractive index, which was achieved with a convolution with nanopores of AAO film and an infiltrated liquid crystal (LC) material. LC molecules confined in the porous AAO film were uniformly aligned, and they exhibited pore-size-dependent colors because of the specific refractive index. The thermal phase transition of the LC material in the nanopores changed the effective refractive index, switching the reflected colors, and the LC-infiltrated AAO remained stable over a month. We believe LC materials can extend the use of rigid conventional plasmonic structures from simple sensor applications to multifunctional uses such as color printing, writing pens, and displays.

Lyotropic chromonic liquid crystals (LCLCs) have been extensively studied because of the interesting structural characteristics of the linear aggregation of their plank-shaped molecules in aqueous solvents. We report a simple method to control the orientation of LCLCs such as Sunset Yellow (SSY), disodium cromoglycate (DSCG), and DNA by varying pulling speed of the top substrate and temperatures during shear flow induced experiment. Crystallized columns of LCLCs are aligned parallel and perpendicular to the shear direction, at fast and slow pulling speeds of the top substrate, respectively. On the basis of this result, we fabricated an orthogonally patterned film that can be used as an alignment layer for guiding rodlike liquid crystals (LCs) to generate both twisted and planar alignments simultaneously. Our resulting platform can provide a facile method to form multidirectional orientation of soft materials and biomaterials in a process of simple shearing and evaporation, which gives rise to potential patterning applications using LCLCs due to their unique structural characteristics.

Manipulation of nanomaterials such as nanoparticles (NPs) and nanorods (NRs) to make clusters is of significant interest in material science and nanotechnology due to the unusual collective opto-electric properties in such structures that cannot be found in the individual NPs. This work demonstrates an effective way to arrange NP clusters (NPCs) to make the desired arrays based on removable and NP-guidable liquid crystalline template using sublimation and reconstruction phenomenon. The position of the NPCs is precisely controlled by the defect structure of the liquid crystal (LC), namely toric focal conic domains (TFCDs), during thermal annealing to construct the LC and corresponding NPC structures. As a proof of concept, the surface-enhanced Raman scattering (SERS) activity of a fabricated array of gold nanorod (GNR) clusters is measured and shown to have highly sensitive detection characteristics essential for potential sensing applications.

Photonic crystals (PCs) have recently attracted considerable attention, with much effort devoted to photonic bandgap (PBG) control for varying the reflected color. Here, fabrication of a modulated one-dimensional (1D) anodic aluminum oxide (AAO) PC with a periodic porous structure is reported. The PBG of the fabricated PC can be reversibly changed by switching the ultraviolet (UV) light on/off. The AAO nanopores contain a mixture of photoresponsive liquid crystals (LCs) with irradiation-activated cis/trans photoisomerizable azobenzene. The resultant mixture of LCs in the porous AAO film exhibits a reversible PBG, depending on the cis/trans configuration of azobenzene molecules. The PBG switching is reliable over many cycles, suggesting that the fabricated device can be used in optical and photonic applications such as light modulators, smart windows, and sensors.

We dynamically controlled the configuration of layering structures built by smectic A liquid crystal molecules using the combination method of the microchannel confinement and the in-plane electric field to realize the linearly polarized illuminator and bistable structures. Once a mild in-plane electric field (∼30 V) is applied between polymeric walls, the layer configuration was changed from the toric focal conic domains to periodic zigzag patterns of alternatively packed focal conic domains. The transformed zigzag patterns maintained their structures even after turning off the applied electric fields, revealing the ability for use in a bistable memory device. Indeed, a strong electric field (∼100 V) can make unidirectionally aligned LC molecules along with the applied electric field via zigzag patterns, and electro-optical performance of resultant textures when the sample is mixed with fluorescent dyes was characterized to show a linearly polarized light illuminator. Our electric field in and on the confined geometries will be used in the fabrication of functional structures built by polar soft materials which can broaden applications in patterning platforms and efficient electro-optical devices in the near future.

Controlling the orientation of building blocks in soft matter on the substrate has been a big challenge in material sciences. We have controlled the molecular orientation of liquid crystal (LC) materials on the porous anodic aluminum oxide (AAO) film having hexagonal pore arrays on the top surface. In our method, anchoring conditions can be varied by changing the pore size (Dp) and the porosity (P). As a proof-of-concept, the orientation of smectic A (SmA) structure at different anchoring conditions was successfully controlled in a sandwich cell consisting of AAO and a glass substrate, which has not been successfully controlled by conventional methods.

Self-assembly of soft materials attracts keen interest for patterning applications owing to its ease and spontaneous behavior. We report the fabrication of nanogrooves using sublimation and recondensation of liquid crystal (LC) materials. First, well-aligned smectic LC structures are obtained on the micron-scale topographic patterns of the microchannel; then, the sublimation and recondensation process directly produces nanogrooves having sub-200-nm scale. The entire process can be completed in less than 30 min. After it is replicated using an ultraviolet-curable polymer, our platform can be used as an alignment layer to control other guest LC materials.

Liquid crystal (LC) materials are currently the dominant electronic materials in display technology because of the ease of control of molecular orientation using an electric field. However, this technology requires the fabrication of two polarizers to create operational displays, reducing light transmission efficiency below 10%. It is therefore desirable to develop new technologies to enhance the light efficiency while maintaining or improving other properties such as the modulation speed of the molecular orientation. Here we report a uniaxial-oriented B7 smectic liquid crystalline film, using fluorescent bent-core LC molecules, a chemically modified substrate, and an in-plane electric field. A LC droplet under homeotropic boundary conditions of air/LC as well as LC/substrate exhibits large focal conic like optical textures. The in-plane electric field induced uniaxial orientation of the LC molecules, in which molecular polar directors are aligned in the direction of the electric field. This highly oriented LC film exhibits linearly polarized luminescence and microsecond time-scale modulation characteristics. The resultant device is both cheap and easy to fabricate and thus has great potential for electro-optic applications, including LC displays, bioimaging systems, and optical communications.

We prepared a nonchiral mixture of achiral bent-core molecules and photoresponsive rodlike liquid crystalline (LC) molecules. With the help of the isothermal photochemical nematic (N)-isotropic (Iso) phase transition of the photoresponsive rodlike LC molecules, the corresponding phase transition from a dark conglomerate BX phase to another distinguishable dark conglomerate B4 phase took place in the mixture. A large circular dichroism (CD) signal originating from supramolecular chirality was detected in the initial BX phase. On the other hand, the detected CD signal was decreased in the B4 phase after UV irradiation. Interestingly, the decreased CD signal could be reverted to the initial CD signal with visible irradiation. This chiroptical process revealed in this work was stable and reversible and thus opens up the possibility of practical applications such as rewritable optical storage.

We have investigated the various morphological changes of helical nanofilament (HNF; B4) phases in multiscale nanochannels made of porous anodic aluminum oxide (AAO) film. Single or multihelical structures could be manipulated depending on the AAO pore size and the higher-temperature phase of each molecule. Furthermore, the nanostructures of HNFs affected by the chemical affinity between the molecule and surface were drastically controlled in surface-modified nanochannels. These well-controlled hierarchical helical structures that have multidimensions can be a promising tool for the manipulation of chiral pores or the nonlinear optical applications.

We successfully fabricated the in-plane switching mode (IPS) LC display (LCD) based on a double stranded DNA (dsDNA) alignment layer. As widely known, the DNA has the right-handed double helical structure that has naturally grown grooves with a very regular period, which can be used as an alignment layer to control the orientation of liquid crystal (LC) molecules. The LC molecules on this topographical layer of DNA material align obliquely at a specific angle with respect to the direction of DNA chains, providing an instant and convenient tool for the fabrication of the IPS display compared to the conventional ways such as rubbing and mechanical shearing methods. The electro-optical performance and response time of this device were also investigated. Our result will be of great use in further exploration of the electro-optical properties of the other biomaterials.

The growth of helical filaments in the B4 liquid-crystal phase was investigated in mixtures of the bent-core and calamitic mesogens NOBOW and 8CB. Freezing-point depression led to nucleation of the NOBOW B4 phase directly from the isotropic phase in the mixtures, forming large left- and right-handed chiral domains that were easily observed in the microscope. We show that these domains are composed of homochiral helical filaments formed in a nucleation and growth process that starts from a nucleus of arbitrary chirality and continues with chirality-preserving growth of the filaments. A model that accounts for the observed local homochirality and phase coherence of the branched filaments is proposed. This model will help in providing a better understanding of the nature of the B4 phase and controlling its growth and morphology for applications, such as the use of the helical nanophase as a nanoheterogeneous medium.

The discovery of spontaneously induced chirality and enantiomeric separation in liquid crystal and soft crystal systems composed of achiral rod-shaped 4-arylbenzoate esters is described. Negligibly small circular dichroism (CD) signals are produced in the smectic A (SmA) phases of these substances, and the signals were found to increase with increasing smectic order. Since the advent of chirality occurs in freely suspended films, it is not a consequence of surface effects. Both positive and negative CD signals are observed with equal probability at different positions in these films. Vibrational CD spectroscopy and theoretical calculations are used to analyze the conformational changes that are associated with the induced chirality of the rod-shaped molecules. The results show that the phenomenon is caused by the twisting of biphenyl bond associated with the ester moiety in 4-arylbenzoate esters.

A smectic liquid crystal (LC) containing a rigid biphenyl group and semifluorinated chains exhibits a high density of toric focal conic domains (TFCDs) arranged in an ordered array when confined within a microchannel. The formation of the TFCDs is strongly influenced by the width (W) and depth (h) of the confined microchannels, most importantly, by the channel depth. We studied a broad variety of microchannels, with varying width in the range of 3-200 mum and depth in the range of 2-10 mum. The radius of the TFCDs increases with increases in the width until the saturated radius is achieved, which is determined by the depth of the channel. We used the elastic-anchoring model of TFCD formation to explain the experimental observations. The model allows one to trace the dependence of the TFCD radius on the channel depth h, to explain why the TFCDs do not form in channels that are too shallow or too narrow.

We investigated the effects of the alignment and ordering of pi-conjugated perfluorinated dendrimers containing pyrene moieties in their cores on their photoluminescence (PL) properties. The pyrene molecules are stacked in columns surrounded by aromatic and semifluorinated tails, which can be conjugated and act as chromophores. Polarized light microscopy (PLM), cross-sectional scanning electron microscopy (SEM), and atomic force microscopy (AFM) results show that variation of the cooling rate of the dendrimers produces variation in their orientation and ordering: Slow cooling (approximately <0.5 degrees C/min) of the isotropic melt in a sandwich glass cell results in a high degree of ordering and the vertical alignment of the columns on the substrate, in which the stacked pyrene molecules are oriented parallel to the surface over large areas. In contrast, rapid cooling (approximately >10 degrees C/min) leads to the planar alignment of the columns with significant disorder on the same substrate. UV-vis, PL, SEM, and AFM results show that the quenched columns with a planar orientation produce a broad emission band and a second weak shoulder, which indicates the presence of isolated molecules. However, the high degree of ordering of the columns with a vertical alignment produces a red-shift in the PL spectrum, with very few isolated molecules. By comparing two films with different alignments but similar ordering, we show that the ordering of this material has a greater influence on the PL spectrum than the alignment. This effect of the ordering of the columns was further verified by comparing the optical properties of the isolated dendrimers with those of small pi-conjugated molecules in solution and solid films.

We have investigated the surface ordering of a synthetic, asymmetric, fan-shaped dendrimer containing a carboxyl core and perfluorinated tails which was obtained by the esterification of the intermediary. X-ray diffraction patterns and transmission electron microscopy (TEM) images show the molecules self-assemble into a hexagonal, cylindrical mesophase. Surface pressure-area isotherms and Brewster angle microscopy measurements show the molecule forms a stable monolayer at the air-water interface with a single phase transition. As a condensed monolayer, the perfluorinated tails are well-packed with hexagonal symmetry with (10) spacing of approximately 0.5 nm from molecular-scale atomic force microscopy (AFM) images. Such dense molecular-scale packing has not been observed in other dendritic molecules thus far. Compared to the case of conventional dendritic molecules with alkyl tails, these molecules occupy a much smaller molecular area due to the strong microphase separation between the carboxylic core and perfluorinated tails at the air-water interface. After monolayer collapse, the irregular islands with terrace morphology are observed in contrast with conventional alkyl-terminated self-assembled dendritic molecules where irregular islands do not appear. The interfacial and internal structure of every terrace shows planar columnar morphology from AFM and TEM imaging. From these results, we discuss the stability of perfluorinated, self-assembled dendrimers on water, as well as how to generate planar morphology on a hydrophilic surface.