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Property optimization through orientation control of metal-organic framework (MOF) crystals that exhibit anisotropic crystal structures continues to garner tremendous interest. Herein, an electric field is utilized to post-synthetically control the orientation of conductive layered Cu3(HHTP)2 (HHTP = 2,3,6,7,10,11-hexahydroxytriphenylene) crystals dispersed in an electronically insulating poly(ethylene glycol) diacrylate (PEGDA) oligomer matrix. Optical and electrical measurements are performed to investigate the impact of the electric field on the alignment of Cu3(HHTP)2 crystals and the formation of aggregated microstructures, which leads to an ≈5000-fold increase in the conductivity of the composite. Notably, the composite thin-films containing aligned Cu3(HHTP)2 crystals exhibit significant conductivity of ≈10-3 S cm-1 despite the low concentration (≈1 wt.%) of conductive Cu3(HHTP)2. The use of an electric field to align Cu3(HHTP)2 crystals can rapidly generate various desired patterns that exhibit on-demand tunable collective charge transport anisotropy. The findings provide valuable insights toward the manipulation and utilization of conductive MOFs with anisotropic crystal structures for various applications such as adhesive electrical interconnects and microelectronics.
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Developing inorganic-organic composite polymers necessitates a new strategy for effectively controlling shape and optical properties while accommodating guest materials, as conventional polymers primarily act as carriers that transport inorganic substances. Here, a universal approach is introduced utilizing mesoporous liquid crystal polymer particles (MLPs) to fabricate inorganic-organic composites. By leveraging the liquid crystal phase, morphology and optical properties are precisely controlled through the molecular-level arrangement of the host, here monomers. The controlled host material allows the synthesis of inorganic particles within the matrix or accommodation of presynthesized nano-inorganic particles, all while preserving the intrinsic properties of the host material. This composite material surpasses the functional capabilities of the polymer alone by sequentially integrating one or more inorganic materials, allowing for the incorporation of multiple functionalities within a single polymer particle. Furthermore, this approach effectively mitigates the drawbacks associated with guest materials resulting in a substantial enhancement of composite performance. The presented approach is anticipated to hold immense potential for various applications in optoelectronics, catalysis, and biosensing, addressing the evolving demands of the society.
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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 10700 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.
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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.
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ADN , Hidrogeles , Hidrogeles/farmacología , Materiales Biocompatibles , AnisotropíaRESUMEN
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.
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Controversy over artwork's authenticity is ongoing despite numerous technologies for copyright protection. Artists should build their own ways to protect the authority, but these are still open to piracy. Here, a platform is proposed for developing anticounterfeiting labels based on physical unclonable functions (PUFs), in an artist-friendly manner, brushstrokes. Deoxyribonucleic acid (DNA), which is natural, biocompatible, and eco-friendly, can be applied as a paint that shows entropy-driven buckling instability of the liquid crystal phase. Brushed and wholly dried DNA exhibits line-shaped zig-zag textures with inherent randomness as a source of the PUF, and its primary performance and reliability are systematically examined. This breakthrough enables the utilization of these drawings in a wider range of applications.
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Cristales Líquidos , Reproducibilidad de los Resultados , Entropía , ADNRESUMEN
HYPOTHESIS: Colloidal particles in nematic liquid crystals (LCs) are of high interest for self-assembly of soft matter systems. When two free particles approach within a uniaxially-oriented nematic LC, an elastic force is generated due to the distorted nematic director configuration around them, allowing particles to self-assemble by an attractive force. We hypothesize that if particles are immobilized, repulsive forces emerge instead, causing the deflection of the interacting defects to compensate for the energy increase. EXPERIMENTS: We fabricated tailored arrays of spherical silica microparticles via capillarity-assisted particle assembly (CAPA) to investigate the interactions of defects as a function of particle separation. By transferring the particle arrays from the CAPA templates to a glass substrate, we studied interacting boojum defect textures within thin LC films sandwiched between two substrates using polarized optical microscopy (POM). FINDINGS: We observed deflected boojum defects on arrays of fixed silica particles, confirming our hypothesis that the elastic repulsive force between the particles affects the defect orientation. The nematic director configuration is reconstructed by Landau-de Gennes q-tensor modeling, and simulated POM images are obtained by the Jones-Matrix method. Our results provide a new platform for controlling defect interactions and pave the way for future work to study topology and implement new defect based applications in LC films.
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The planar spin glass pattern is widely known for its inherent randomness, resulting from the geometrical frustration. As such, developing physical unclonable functions (PUFs)-which operate with device randomness-with planar spin glass patterns is a promising candidate for an advanced security systems in the upcoming digitalized society. Despite their inherent randomness, traditional magnetic spin glass patterns pose considerable obstacles in detection, making it challenging to achieve authentication in security systems. This necessitates the development of facilely observable mimetic patterns with similar randomness to overcome these challenges. Here, a straightforward approach is introduced using a topologically protected maze pattern in the chiral liquid crystals (LCs). This maze exhibits a comparable level of randomness to magnetic spin glass and can be reliably identified through the combination of optical microscopy with machine learning-based object detection techniques. The "information" embedded in the maze can be reconstructed through thermal phase transitions of the LCs in tens of seconds. Furthermore, incorporating various elements can enhance the optical PUF, resulting in a multi-factor security medium. It is expected that this security medium, based on microscopically controlled and macroscopically uncontrolled topologically protected structures, may be utilized as a next-generation security system.
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Controlling the orientation of two-dimensional materials is essential to optimize or tune their functional properties. In particular, aligning MXene, a two-dimensional carbide and/or nitride material, has recently received much attention due to its high conductivity and high-density surface functional group properties that can easily vary based on its arranged directions. However, erecting 2D materials vertically can be challenging, given their thinness of few nanometres. Here, vertical alignment of Ti3C2Tx MXene sheets is achieved by applying an in-plane electric field, which is directly observed using polarised optical microscopy and scanning electron microscopy. The electric field-induced vertical alignment parallel to the applied alternating-current field is demonstrated to be reversible in the absence of a field, back to a random orientation distribution. Interdigitated electrodes with uniaxially aligned MXene nanosheets are demonstrated. These can be further modulated to achieve various patterns using diversified electrode substrates. Anisotropic electrical conductivity is also observed in the uniaxially aligned MXene nanosheet film, which is quite different from the randomly oriented ones. The proposed orientation-controlling technique demonstrates potential for many applications including sensors, membranes, polarisers, and general energy applications.
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As Internet of Things-based technologies continue to digitalize our society, the development of secure and robust identification systems against evolving adversaries remains a grave challenge. Recently, physical unclonable functions (PUFs) have garnered tremendous scientific interest due to their intrinsic randomness, which makes them difficult to counterfeit. Herein, we present a facile approach for fabricating optical PUFs using spontaneous mirror symmetry breaking of molecular self-assembly. The PUF composed of racemic helical structures that generate chiroptical signals exhibits high encoding capacity (â¼1013 000), precise recognition rate, and impressive reconfigurability. The present study demonstrates that the utilization of random symmetry breaking is a promising approach to the design of high-level security systems.
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Internet de las Cosas , FotonesRESUMEN
Topological solitons have knotted continuous field configurations embedded in a uniform background, and occur in cosmology, biology, and electromagnetism. However, real-time observation of their morphogenesis and dynamics is still challenging because their size and timescale are enormously large or tiny. Liquid crystal (LC) structures are promising candidates for a model-system to study the morphogenesis of topological solitons, enabling direct visualization due to the proper size and timescale. Here, a new way is found to rationalize the real-time observation of the generation and transformation of topological solitons using cholesteric LCs confined in patterned substrates. The experimental demonstration shows the topologically protected structures arise via the transformation of topological defects. Numerical modeling based on minimization of free energy closely reconstructs the experimental findings. The fundamental insights obtained from the direct observations pose new theoretical challenges in understanding the morphogenesis of different types of topological solitons within a broad range of scales.
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Randomness is perceived in two different extremes, in macroscopic homogeneity and local heterogeneity, but apparently far away from order. Here we show that a periodic order spontaneously arises from a binary random copolymer when self-assembly occurs in an ensemble containing > 1015 possible chain sequences. A Bernoullian distribution of hydrophilic and hydrophobic side chains grafted onto a linear backbone was constructed by random copolymerization. When the polymer chains associate in water, a sequence matching problem occurs because of the drastic heterogeneity in sequence: this is believed to generate local curvature mismatches which deviate from the ensemble-averaged interfacial curvature. Periodic folding of the self-assembled bilayer stabilizes the curvature instability as recurring hinges. Reminiscent of chain-folded lamellae found in polymer crystallization, this new liquid crystalline mesophase, characterized as bilayer-folded lamellae, manifests itself as an anisotropically alignable birefringent hydrogel with structural hierarchy across multiple length scales.
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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.
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Achiral building blocks forming achiral structures is a common occurrence in nature, while chirality emerging spontaneously from an achiral system is usually associated with important scientific phenomena. We report on the spontaneous chiral symmetry-breaking phenomena upon the topographic confinement of achiral lyotropic chromonic liquid crystals in periodically arranged micrometer scale air pillars. The anisotropic fluid arranges into chiral domains that depend on the arrangement and spacing of the pillars. We characterize the resulting domains by polarized optical microscopy, support their reconstruction by numerical calculations, and extend the findings with experiments, which include chiral dopants. Well-controlled and addressed chiral structures will be useful in potential applications like programmable scaffolds for living liquid crystals and as sensors for detecting chirality at the molecular level.
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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.
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2D DNA microstructures are fabricated by applying the shear force to the DNA solution on the microchannels. The "U"-like textures of DNA are clearly observed when the mechanical shearing is applied on the aqueous DNA sample under the topographic confinement, in which the shearing direction is perpendicular to the grooves. The optical textures of U-like microstructures are directly observed by polarized optical microscopy (POM) and laser scanning fluorescent confocal polarizing microscopy (FCPM). The DNA microstructures can be modified by varying the width, showing the multiple U-patterns along with channel direction due to the synergistic interaction between the elastic behavior of DNA chains and topographic boundary condition. The resultant microstructures can be used to align rod-like liquid crystals (LCs) to generate alternatively oriented nematic phase and tilted focal conic domains (FCDs) in the smectic A phase. It is believed that this approach can suggest a hint to use to DNA materials for organizing multiscale hierarchical structures of soft- and biomaterials.