Azo-Functionalized Thermoplastic Polyurethane for Light-Driven Shape Memory Materials.

Shape memory polymers have great potential in the fields of soft robotics, injectable medical devices, and as essential materials for advanced electronic devices. Herein, light-triggered shape-memory thermoplastic polyurethane (TPU) is reported using azido TPU grafted by the photoswitchable azo compound. The trans-cis transitions of the azobenzene on the side chain of the TPU induce the recoiling of the main chain, leading to shaping memory behavior. Under UV irradiation, cis-azo allows the oriented main chain to recoil to release residual stress and realize light-triggered shape memory behavior. The facile method proposed here for the preparation of azo-functionalized TPU can provide viable opportunities for soft robotics and smart TPU applications.

Circularly Polarized Light Can Override and Amplify Asymmetry in Supramolecular Helices.

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.

Controlled nucleation in evaporative crystallization using a confined-vapor driven solutal Marangoni effect.

In droplet evaporation, the onset of evaporative crystallization near a contact line is inevitable if there is a coffee-ring effect increasing the local concentration of suspended particles at the edge. In this study, we present a novel idea to control the nucleation location of surfactant crystallization by using the vapor-driven solutal Marangoni effects of a binary mixture drop in a confined chamber. Here, the evaporated volatile vapors near the droplet surface can change the local surface tension and generate a radially inward flow that suppresses the conventional coffee-ring flow (i.e., evaporatively-driven capillary flow). Using this method, we could accumulate suspended particles in the middle of the droplet. In consequence, we succeed in adjusting the nucleation location from the droplet edge to the center provided that a gel-transition process is neglected, where the crystallized material has a relatively long chain length. Here, we tested different hydrocarbon chain lengths of the surfactants (i.e., CTAB > TTAB > DTAB). We expect that the proposed idea can offer great potential for controlling the nucleation in the evaporative crystallization and its final crystalline solid morphology.

Stimulus-Responsive Tubular Conjugated Polymer 2D Nanosheets.

Creation of new two-dimensional (2D) architectures has attracted significant attention in the field of self-assembly for structural diversity and new functionalization. Although numerous 2D polymer nanosheets have been reported, 2D nanosheets with tubular channels have been unexplored. Herein, we describe a new strategy for the fabrication of stimulus-responsive conjugated polymer 2D nanosheets with hollow cavities. Amphiphilic macrocyclic diacetylenes self-assembled in an aqueous solution in a columnar manner to afford bilayered 2D nanosheets with intrinsically tubular nanochannels. UV-induced polymerization resulted in the generation of blue-colored tubular conjugated polydiacetylene 2D nanosheets. Immobilization of gold nanoparticles, fluorescence labeling with FRET phenomenon and colorimetric DNA sensing were demonstrated with these new 2D nanosheets. In addition, the free NH2 containing polymerized 2D nanosheet was utilized for conductivity behavior and grafting on graphene oxide (GO).

Fabrication of Chiral M13 Bacteriophage Film by Evaporation-Induced Self-Assembly.

Biomacromolecules are likely to undergo self-assembly and show specific collective behavior concentrated in the medium. Although the assembly procedures have been studied for unraveling their mysteries, there are few cases to directly demonstrate the collective behavior and phase transition process in dynamic systems. In the contribution, the drying process of M13 droplet is investigated, and can be successfully simulated by a doctor blade coating method. The morphologies in the deposited film are measured by atomic force microscopy and the liquid crystal phase development is captured in real time using polarized optical microscope. Collective behaviors near the contact line are characterized by the shape of meniscus curve and particle movement velocity. With considering rheological properties and flow, the resultant chiral film is used to align gold nanorods, and this approach can suggest a way to use M13 bacteriophage as a scaffold for the multi-functional chiral structures.

Generation of 2D DNA Microstructures via Topographic Control and Shearing.

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.

Evaporation-induced self-assembly of liquid crystal biopolymers.

Evaporation-induced self-assembly (EISA) is a process that has gained significant attention in recent years due to its fundamental science and potential applications in materials science and nanotechnology. This technique involves controlled drying of a solution or dispersion of materials, forming structures with specific shapes and sizes. In particular, liquid crystal (LC) biopolymers have emerged as promising candidates for EISA due to their highly ordered structures and biocompatible properties after deposition. This review provides an overview of recent progress in the EISA of LC biopolymers, including DNA, nanocellulose, viruses, and other biopolymers. The underlying self-assembly mechanisms, the effects of different processing conditions, and the potential applications of the resulting structures are discussed.

On-Demand Crack Formation on DNA Film via Organic Solvent-Induced Dehydration.

Crack is found on the soil when severe drought comes, which inspires the idea to rationalize patterning applications using dried deoxyribonucleic acid (DNA) film. DNA is one of the massively produced biomaterials in nature, showing the lyotropic liquid crystal (LC) phase in highly concentrated conditions. DNA nanostructures in the hydrated condition can be orientation controlled, which can be extended to make dryinginduced cracks. The controlled crack generation in oriented DNA films by inducing mechanical fracture through organic solvent-induced dehydration (OSID) using tetrahydrofuran (THF) is explored. The corresponding simulations show a strong correlation between the long axis of DNA due to the shrinkage during the dehydration and in the direction of crack propagation. The cracks are controlled by simple brushing and a 3D printing method. This facile way of aligning cracks will be used in potential patterning applications.

Paintable Physical Unclonable Functions using DNA.

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.

Plasmonic metasurfaces of cellulose nanocrystal matrices with quadrants of aligned gold nanorods for photothermal anti-icing.

Cellulose nanocrystals (CNCs) are intriguing as a matrix for plasmonic metasurfaces made of gold nanorods (GNRs) because of their distinctive properties, including renewability, biodegradability, non-toxicity, and low cost. Nevertheless, it is very difficult to precisely regulate the positioning and orientation of CNCs on the substrate in a consistent pattern. In this study, CNCs and GNRs, which exhibit tunable optical and anti-icing capabilities, are employed to manufacture a uniform plasmonic metasurface using a drop-casting technique. Two physical phenomena-(i) spontaneous and rapid self-dewetting and (ii) evaporation-induced self-assembly-are used to accomplish this. Additionally, we improve the CNC-GNR ink composition and determine the crucial coating parameters necessary to balance the two physical mechanisms in order to produce thin films without coffee rings. The final homogeneous CNC-GNR film has consistent annular ring patterns with plasmonic quadrant hues that are properly aligned, which enhances plasmonic photothermal effects. The CNC-GNR multi-array platform offers above-zero temperatures on a substrate that is subcooled below the freezing point. The current study presents a physicochemical approach for functional nanomaterial-based CNC control.

On-Demand Aligned DNA Hydrogel Via Light Scanning.

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.

Field-induced orientational switching produces vertically aligned Ti3C2Tx MXene nanosheets.

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.

CT comparison of visual and computerised quantification of coronary stenosis according to plaque composition.

OBJECTIVE: To compare the diagnostic performance of computerised quantification with visual assessment for the detection of significant coronary stenosis using MDCT, and to determine the impact of plaque composition on diagnostic procedure. METHODS: We retrospectively evaluated 1564 coronary segments of 127 patients who underwent 64-slice MDCT and quantitative coronary angiography (QCA). The lesions were analysed with both methods of visual assessment and computerised quantification using an automatic vessel contour detection tool, and the results were compared with the QCA results. Plaques detected with MDCT were classified as calcified, mixed, and non-calcified according to plaque composition. RESULTS: The sensitivity and PPV of visual assessment (computerised quantification) were 95% (86%) and 76% (81%), respectively. Bland-Altman analysis demonstrated a mean difference of -5.2 ± 21.6% for all lesions, 2.2 ± 23.7 for calcified plaques, and -12.0 ± 17.2% for non-calcified plaques. The correlation coefficients and limits of agreement between CTA and QCA were 0.48 and ± 46.5% (0.74 and ± 33.7%) in the lesions with calcified plaques (non-calcified plaques). CONCLUSIONS: The computerised quantification decreases the sensitivity due to underestimation of non-calcified plaques compared with visual assessment, and had a poorer correlation and a larger limit of agreement in the lesions with calcified plaque compared with non-calcified plaques.

Hierarchically Fabricated Amyloid Fibers via Evaporation-Induced Self-Assembly.

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.

Orientation Control of Semiconducting Polymers Using Microchannel Molds.

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.

Microstructure arrays of DNA using topographic control.

DNA is a common biomaterial in nature as well as a good building block for producing useful structures, due to its fine feature size and liquid crystalline phase. Here, we demonstrate that a combination of shear-induced flow and microposts can be used to create various kinds of interesting microstructure DNA arrays. Our facile method provides a platform for forming multi-scale hierarchical orientations of soft- and biomaterials, using a process of simple shearing and controlled evaporation on a patterned substrate. This approach enables potential patterning applications using DNA or other anisotropic biomaterials based on their unique structural characteristics.