In Situ Programmable, Active, and Interactive Crystallization by Localized Polymerization.

Additive manufacturing has sought active and interactive means of creating predictable structures with diverse materials. Compared to such active manufacturing tools, current crystallization strategies remain in statistical and passive programs of crystals via macroscale thermodynamic controllers, commonly lacking active means to intervene in crystal growth in a spatiotemporal manner. Herein, a strategy toward active and interactive programming and reprogramming of crystals, realized by real-time tangible feedback on growing crystals by delicately controlling the degree of in-situ, localized photopolymerization of polymeric structures via additive manufacturing is presented.

Polymorphic Self-Assembly with Procedural Flexibility for Monodisperse Quaternary Protein Structures of DegQ Enzymes.

As large molecular tertiary structures, some proteins can act as small robots that find, bind, and chaperone target protein clients, showing the potential to serve as smart building blocks in self-assembly fields. Instead of using such intrinsic functions, most self-assembly methodologies for proteins aim for de novo-designed structures with accurate geometric assemblies, which can limit procedural flexibility. Here, a strategy enabling polymorphic clustering of quaternary proteins, exhibiting simplicity and flexibility of self-assembling paths for proteins in forming monodisperse quaternary cage particles is presented.

Chiroptical Synaptic Heterojunction Phototransistors Based on Self-Assembled Nanohelix of π-Conjugated Molecules for Direct Noise-Reduced Detection of Circularly Polarized Light.

High-performance chiroptical synaptic phototransistors are successfully demonstrated using heterojunctions composed of a self-assembled nanohelix of a π-conjugated molecule and a metal oxide semiconductor. To impart strong chiroptical activity to the device, a diketopyrrolopyrrole-based π-conjugated molecule decorated with chiral glutamic acid is newly synthesized; this molecule is capable of supramolecular self-assembly through noncovalent intermolecular interactions. In particular, nanohelix formed by intertwinded fibers with strong and stable chiroptical activity in a solid-film state are obtained through hydrogen-bonding-driven, gelation-assisted self-assembly.

Surface Rh-Boosted Photoelectrochemical Water Oxidation of α-FeO by Reduced Overpotential in the Rate-Determining Step.

The photoelectrochemical behavior of Rh cluster-deposited hematite (α-FeO) photoanodes (α-FeO@Rh) was investigated. The interactions between Rh clusters and α-FeO nanorods were elucidated both experimentally and computationally. A facile UV-assisted solution casting deposition method allowed the deposition of 2 nm Rh clusters on α-FeO.

Dimensional Control of Highly Anisotropic and Transparent Conductive Coordination Polymers for Solution-Processable Large-Scale 2D Sheets.

Controlling the dimensional aspect of conductive coordination polymers is currently a key scientific interest. Herein, solution-based dimension control strategies are proposed for copper chloride thiourea (CuCl-TU) coordination polymers that enable centimeter-scale, 2D nanosheet formation for use as transparent electrodes. Despite the wide bandgap of CuCl-TU polymers (4.

Block copolymer gyroids for nanophotonics: significance of lattice transformations.

A gyroid crystal possesses a peculiar structural feature that can be conceptualized as a triply periodic surface with a constant mean curvature of zero. The exotic optical properties such as the photonic bandgap and optical chirality can emerge from this three-dimensional (3D) morphological feature. As such, gyroid crystals have been considered as the promising structures for photonic crystals and optical metamaterials.

Electrochemical Nitrogen Reduction Kinetics on a Copper Sulfide Catalyst for NH Synthesis at Low Temperature and Atmospheric Pressure.

We studied the electrochemical synthesis of NH on Fe-CuS/C catalysts in an alkaline aqueous solution under ambient conditions. The metal chalcogenide catalyst is active in the nitrogen reduction reaction (NRR) for approximately 45 min with an NH production yield of 16 μg h cm at -0.4 , while it decomposes to CuO.

Design of DNA Origami Diamond Photonic Crystals.

Self-assembled photonic crystals have proven to be a fascinating class of photonic materials for nonabsorbing structural colorizations over large areas and in diverse relevant applications, including tools for on-chip spectrometers and biosensors, platforms for reflective displays, and templates for energy devices. The most prevalent building blocks for the self-assembly of photonic crystals are spherical colloids and block copolymers (BCPs) because of the generic appeal of these materials, which can be crafted into large-area 3D lattices. However, because of the intrinsic limitations of these structures, these two building blocks are difficult to assemble into a direct rod-connected diamond lattice, which is considered to be a champion photonic crystal.

Copper-Halide Polymer Nanowires as Versatile Supports for Single-Atom Catalysts.

Single-atom catalysts are heterogeneous catalysts with atomistically dispersed atoms acting as a catalytically active center, and have recently attracted much attention owing to the minimal use of noble metals. However, a scalable and inexpensive support that can stably anchor isolated atoms remains a challenge due to high surface energy. Here, copper-halide polymer nanowires with sub-nanometer pores are proposed as a versatile support for single-atom catalysts.

Highly tumor-specific DNA nanostructures discovered by in vivo screening of a nucleic acid cage library and their applications in tumor-targeted drug delivery.

Enormous efforts have been made to harness nanoparticles showing extravasation around tumors for tumor-targeted drug carriers. Owing to the complexity of in vivo environments, however, it is very difficult to rationally design a nanoconstruct showing high tumor specificity. Here, we show an approach to develop tumor-specific drug carriers by screening a library of self-assembled nucleic acid cages in vivo.

Soft self-assembly of Weyl materials for light and sound.

Soft materials can self-assemble into highly structured phases that replicate at the mesoscopic scale the symmetry of atomic crystals. As such, they offer an unparalleled platform to design mesostructured materials for light and sound. Here, we present a bottom-up approach based on self-assembly to engineer 3D photonic and phononic crystals with topologically protected Weyl points.

Multiscale Phase Separations for Hierarchically Ordered Macro/Mesostructured Metal Oxides.

Porous architectures play an important role in various applications of inorganic materials. Several attempts to develop mesoporous materials with controlled macrostructures have been reported, but they usually require complicated multiple-step procedures, which limits their versatility and suitability for mass production. Here, a simple approach for controlling the macrostructures of mesoporous materials, without templates for the macropores, is reported.

A Generalized Crystallographic Description of All Tellurium Nanostructures.

Despite tellurium being less abundant in the Earth's crust than gold, platinum, or rare-earth elements, the number of industrial applications of tellurium has rapidly increased in recent years. However, to date, many properties of tellurium and its associated compounds remain unknown. For example, formation mechanisms of many tellurium nanostructures synthesized so far have not yet been verified, and it is unclear why tellurium can readily transform to other compounds like silver telluride by simply mixing with solutions containing silver ions.

Long-term efficient organic photovoltaics based on quaternary bulk heterojunctions.

A major impediment to the commercialization of organic photovoltaics (OPVs) is attaining long-term morphological stability of the bulk heterojunction (BHJ) layer. To secure the stability while pursuing optimized performance, multi-component BHJ-based OPVs have been strategically explored. Here we demonstrate the use of quaternary BHJs (q-BHJs) composed of two conjugated polymer donors and two fullerene acceptors as a novel platform to produce high-efficiency and long-term durable OPVs.

Label-free bacterial detection using polydiacetylene liposomes.

Polydiacetylene (PDA) liposomes were prepared to selectively capture target released from bacteria. Specific interplay between released-surfactin and PDA resulted in a conformal change in the structure of PDA, highlighting the potential of indirect interactions between bacteria and PDA in the construction of new label-free bacterial sensors.

Direct access to hierarchically porous inorganic oxide materials with three-dimensionally interconnected networks.

Hierarchically porous oxide materials have immense potential for applications in catalysis, separation, and energy devices, but the synthesis of these materials is hampered by the need to use multiple templates and the associated complicated steps and uncontrollable mixing behavior. Here we report a simple one-pot strategy for the synthesis of inorganic oxide materials with multiscale porosity. The inorganic precursor and block copolymer are coassembled into an ordered mesostructure (microphase separation), while the in situ-polymerized organic precursor forms organic-rich macrodomains (macrophase separation) around which the mesostructure grows.

Linking experiment and theory for three-dimensional networked binary metal nanoparticle-triblock terpolymer superstructures.

Controlling superstructure of binary nanoparticle mixtures in three dimensions from self-assembly opens enormous opportunities for the design of materials with unique properties. Here we report on how the intimate coupling of synthesis, in-depth electron tomographic characterization and theory enables exquisite control of superstructure in highly ordered porous three-dimensional continuous networks from single and binary mixtures of metal nanoparticles with a triblock terpolymer. Poly(isoprene-block-styrene-block-(N,N-dimethylamino)ethyl methacrylate) is synthesized and used as structure-directing agent for ligand-stabilized platinum and gold nanoparticles.

Hierarchical porous polymer scaffolds from block copolymers.

Hierarchical porous polymer materials are of increasing importance because of their potential application in catalysis, separation technology, or bioengineering. Examples for their synthesis exist, but there is a need for a facile yet versatile conceptual approach to such hierarchical scaffolds and quantitative characterization of their nonperiodic pore systems. Here, we introduce a synthesis method combining well-established concepts of macroscale spinodal decomposition and nanoscale block copolymer self-assembly with porosity formation on both length scales via rinsing with protic solvents.

Predicting chiral nanostructures, lattices and superlattices in complex multicomponent nanoparticle self-assembly.

"Bottom up" type nanoparticle (NP) self-assembly is expected to provide facile routes to nanostructured materials for various, for example, energy related, applications. Despite progress in simulations and theories, structure prediction of self-assembled materials beyond simple model systems remains challenging. Here we utilize a field theory approach for predicting nanostructure of complex and multicomponent hybrid systems with multiple types of short- and long-range interactions.

A 3D optical metamaterial made by self-assembly.

Optical metamaterials have unusual optical characteristics that arise from their periodic nanostructure. Their manufacture requires the assembly of 3D architectures with structure control on the 10-nm length scale. Such a 3D optical metamaterial, based on the replication of a self-assembled block copolymer into gold, is demonstrated.