Hierarchically Interpenetrated and Reentrant Microcellular Frameworks for Stretchable Lithium Metal Batteries.

With the rapid development of human-friendly wearable devices, energy storage components are required to have skin-like stretchability or free-form to fit closer and more comfortably to the human body. This study introduces a hierarchically interpenetrated reentrant microcellular structure combined with 2D cellular graphene/MXene/carbon nanotubes (CNTs) and 3D cellular melamine foam. This composite structure works as a stretchable framework of lithium metal composite electrodes to provide stretchability for lithium metal electrodes, which are promising as next-generation energy storage systems. The interpenetrated but independent cellular structures successfully obtain stable structural deformability from the nonconductive and deformable melamine foam, while at the same time, high electrical conductivity, lithiophilicity, and mechanical stability of the graphene/CNT/MXene network serve as a lithium deposition support during the electrodeposition of lithium. The reentrant structure is fabricated by radial compressing the hierarchical cellular structures to take advantage of the structural stretchability of the accordion-like reentrant frameworks. The lithium-deposited composite electrodes exhibit much lower overpotential during Li stripping and plating than lithium metal foil anodes and show stable electrochemical performances under 30% of mechanical strain. The reentrant microcellular electrodes offer great potential for advanced designs of lithium metal electrodes for stretchable batteries with high energy density.

Abiotic tooth enamel.

Tooth enamel comprises parallel microscale and nanoscale ceramic columns or prisms interlaced with a soft protein matrix. This structural motif is unusually consistent across all species from all geological eras. Such invariability-especially when juxtaposed with the diversity of other tissues-suggests the existence of a functional basis. Here we performed ex vivo replication of enamel-inspired columnar nanocomposites by sequential growth of zinc oxide nanowire carpets followed by layer-by-layer deposition of a polymeric matrix around these. We show that the mechanical properties of these nanocomposites, including hardness, are comparable to those of enamel despite the nanocomposites having a smaller hard-phase content. Our abiotic enamels have viscoelastic figures of merit (VFOM) and weight-adjusted VFOM that are similar to, or higher than, those of natural tooth enamels-we achieve values that exceed the traditional materials limits of 0.6 and 0.8, respectively. VFOM values describe resistance to vibrational damage, and our columnar composites demonstrate that light-weight materials of unusually high resistance to structural damage from shocks, environmental vibrations and oscillatory stress can be made using biomimetic design. The previously inaccessible combinations of high stiffness, damping and light weight that we achieve in these layer-by-layer composites are attributed to efficient energy dissipation in the interfacial portion of the organic phase. The in vivo contribution of this interfacial portion to macroscale deformations along the tooth's normal is maximized when the architecture is columnar, suggesting an evolutionary advantage of the columnar motif in the enamel of living species. We expect our findings to apply to all columnar composites and to lead to the development of high-performance load-bearing materials.

Phase Separation-Controlled Assembly of Hierarchically Porous Aramid Nanofiber Films for High-speed Lithium-Metal Batteries.

The growth of lithium (Li) dendrites reduces the lifespan of Li-metal batteries and causes safety issues. Herein, hierarchically porous aramid nanofiber separators capable of effectively suppressing the Li dendrite growth while maintaining highly stable cycle performances at high charge/discharge rates are reported. A two-step solvent exchange process combined with reprotonation-mediated self-assembly is utilized to control the bimodal porous structure of the separators. In particular, when ethanol and water are used sequentially, aramid nanofibers form hierarchical porous structures containing nanopores in macroporous polymer frameworks to yield a mechanically robust membrane with high porosity of 97% or more. The optimized samples exhibit high ionic conductivities of 1.87-4.04 mS cm-1 and high Li-ion transference numbers of 0.77-0.84 because of the ultrahigh porosity and selective affinity to anions. Li-metal symmetric cells do not show any noticeable presence of dendrites after 100 cycles, and they operate stably for more than 1500 cycles even under extreme conditions with a high current density of >20 mA cm-2 . In addition, the LiFePO4 /Li full cell retains 86.3% of its capacity after 1000 cycles at a charge rate of 30 C.

A Layer-by-Layer Assembly Route to Electroplated Fibril-Based 3D Porous Current Collectors for Energy Storage Devices.

Electrical conductivity, mechanical flexibility, and large electroactive surface areas are the most important factors in determining the performance of various flexible electrodes in energy storage devices. Herein, a layer-by-layer (LbL) assembly-induced metal electrodeposition approach is introduced to prepare a variety of highly porous 3D-current collectors with high flexibility, metallic conductivity, and large surface area. In this study, a few metal nanoparticle (NP) layers are LbL-assembled onto insulating paper for the preparation of conductive paper. Subsequent Ni electroplating of the metal NP-coated substrates reduces the sheet resistance from ≈103 to <0.1 Ω sq-1 while maintaining the porous structure of the pristine paper. Particularly, this approach is completely compatible with commercial electroplating processes, and thus can be directly extended to electroplating applications using a variety of other metals in addition to Ni. After depositing high-energy MnO NPs onto Ni-electroplated papers, the areal capacitance increases from 68 to 811 mF cm-2 as the mass loading of MnO NPs increases from 0.16 to 4.31 mg cm-2 . When metal NPs are periodically LbL-assembled with the MnO NPs, the areal capacitance increases to 1710 mF cm-2 .

Anomalous dispersions of 'hedgehog' particles.

Hydrophobic particles in water and hydrophilic particles in oil aggregate, but can form colloidal dispersions if their surfaces are chemically camouflaged with surfactants, organic tethers, adsorbed polymers or other particles that impart affinity for the solvent and increase interparticle repulsion. A different strategy for modulating the interaction between a solid and a liquid uses surface corrugation, which gives rise to unique wetting behaviour. Here we show that this topographical effect can also be used to disperse particles in a wide range of solvents without recourse to chemicals to camouflage the particles' surfaces: we produce micrometre-sized particles that are coated with stiff, nanoscale spikes and exhibit long-term colloidal stability in both hydrophilic and hydrophobic media. We find that these 'hedgehog' particles do not interpenetrate each other with their spikes, which markedly decreases the contact area between the particles and, therefore, the attractive forces between them. The trapping of air in aqueous dispersions, solvent autoionization at highly developed interfaces, and long-range electrostatic repulsion in organic media also contribute to the colloidal stability of our particles. The unusual dispersion behaviour of our hedgehog particles, overturning the notion that like dissolves like, might help to mitigate adverse environmental effects of the use of surfactants and volatile organic solvents, and deepens our understanding of interparticle interactions and nanoscale colloidal chemistry.

Stretchable nanoparticle conductors with self-organized conductive pathways.

Research in stretchable conductors is fuelled by diverse technological needs. Flexible electronics, neuroprosthetic and cardiostimulating implants, soft robotics and other curvilinear systems require materials with high conductivity over a tensile strain of 100 per cent (refs 1-3). Furthermore, implantable devices or stretchable displays need materials with conductivities a thousand times higher while retaining a strain of 100 per cent. However, the molecular mechanisms that operate during material deformation and stiffening make stretchability and conductivity fundamentally difficult properties to combine. The macroscale stretching of solids elongates chemical bonds, leading to the reduced overlap and delocalization of electronic orbitals. This conductivity-stretchability dilemma can be exemplified by liquid metals, in which conduction pathways are retained on large deformation but weak interatomic bonds lead to compromised strength. The best-known stretchable conductors use polymer matrices containing percolated networks of high-aspect-ratio nanometre-scale tubes or nanowires to address this dilemma to some extent. Further improvements have been achieved by using fillers (the conductive component) with increased aspect ratio, of all-metallic composition, or with specific alignment (the way the fillers are arranged in the matrix). However, the synthesis and separation of high-aspect-ratio fillers is challenging, stiffness increases with the volume content of metallic filler, and anisotropy increases with alignment. Pre-strained substrates, buckled microwires and three-dimensional microfluidic polymer networks have also been explored. Here we demonstrate stretchable conductors of polyurethane containing spherical nanoparticles deposited by either layer-by-layer assembly or vacuum-assisted flocculation. High conductivity and stretchability were observed in both composites despite the minimal aspect ratio of the nanoparticles. These materials also demonstrate the electronic tunability of mechanical properties, which arise from the dynamic self-organization of the nanoparticles under stress. A modified percolation theory incorporating the self-assembly behaviour of nanoparticles gave an excellent match with the experimental data.

Reconfigurable chiroptical nanocomposites with chirality transfer from the macro- to the nanoscale.

Nanostructures with chiral geometries exhibit strong polarization rotation. However, achieving reversible modulation of chirality and polarization rotation in device-friendly solid-state films is difficult for rigid materials. Here, we describe nanocomposites, made by conformally coating twisted elastic substrates with films assembled layer-by-layer from plasmonic nanocolloids, whose nanoscale geometry and rotatory optical activity can be reversibly reconfigured and cyclically modulated by macroscale stretching, with up to tenfold concomitant increases in ellipticity. We show that the chiroptical activity at 660 nm of gold nanoparticle composites is associated with circular extinction from linear effects. The polarization rotation at 550 nm originates from the chirality of nanoparticle chains with an S-like shape that exhibit a non-planar buckled geometry, with the handedness of the substrate's macroscale twist determining the handedness of the S-like chains. Chiroptical effects at the nexus of mechanics, excitonics and plasmonics open new operational principles for optical and optoelectronic devices from nanoparticles, carbon nanotubes and other nanoscale components.

Branched Aramid Nanofibers.

Interconnectivity of components in three-dimensional networks (3DNs) is essential for stress transfer in hydrogels, aerogels, and composites. Entanglement of nanoscale components in the network relies on weak short-range intermolecular interactions. The intrinsic stiffness and rod-like geometry of nanoscale components limit the cohesive energy of the physical crosslinks in 3DN materials. Nature realizes networked gels differently using components with extensive branching. Branched aramid nanofibers (BANFs) mimicking polymeric components of biological gels were synthesized to produce 3DNs with high efficiency stress transfer. Individual BANFs are flexible, with the number of branches controlled by base strength in the hydrolysis process. The extensive connectivity of the BANFs allows them to form hydro- and aerogel monoliths with an order of magnitude less solid content than rod-like nanocomponents. Branching of nanofibers also leads to improved mechanics of gels and nanocomposites.

Chiral templating of self-assembling nanostructures by circularly polarized light.

The high optical and chemical activity of nanoparticles (NPs) signifies the possibility of converting the spin angular momenta of photons into structural changes in matter. Here, we demonstrate that illumination of dispersions of racemic CdTe NPs with right- (left-)handed circularly polarized light (CPL) induces the formation of right- (left-)handed twisted nanoribbons with an enantiomeric excess exceeding 30%, which is ∼10 times higher than that of typical CPL-induced reactions. Linearly polarized light or dark conditions led instead to straight nanoribbons. CPL 'templating' of NP assemblies is based on the enantio-selective photoactivation of chiral NPs and clusters, followed by their photooxidation and self-assembly into nanoribbons with specific helicity as a result of chirality-sensitive interactions between the NPs. The ability of NPs to retain the polarization information of incident photons should open pathways for the synthesis of chiral photonic materials and allow a better understanding of the origins of biomolecular homochirality.

Coordination Assembly of Discoid Nanoparticles.

Supramolecular chemistry utilizes coordination bonds to assemble molecular building blocks into a variety of sophisticated constructs. However, traditional coordination assemblies are based on organic compounds that have limited ability to transport charge. Herein, we describe coordination assembly of anisotropic FeS2 pyrite nanoparticles (NPs) that can facilitate charge transport. Zn(2+) ions form supramolecular complexes with carboxylate end-groups on NP surface, leading to multiparticle sheets with liquid-crystal-like organization. Conductivity and Hall carrier mobility of the p-type layered semiconductor films with Zn(2+) coordination bridging exceed those known for coordination compounds, some by several orders of magnitude. The nanoscale porosity of the assembled sheets combined with fast hole transport leads to high electrocatalytic activity of the NP films. The coordination assembly of NPs embraces the versatility of several types of building blocks and opens a new design space for self-organized materials combining nanoscale and supramolecular structural motifs.

Chiral plasmonic nanostructures on achiral nanopillars.

Chirality of plasmonic films can be strongly enhanced by three-dimensional (3D) out-of-plane geometries. The complexity of lithographic methods currently used to produce such structures and other methods utilizing chiral templates impose limitations on spectral windows of chiroptical effects, the size of substrates, and hence, further research on chiral plasmonics. Here we demonstrate 3D chiral plasmonic nanostructures (CPNs) with high optical activity in the visible spectral range based on initially achiral nanopillars from ZnO. We made asymmetric gold nanoshells on the nanopillars by vacuum evaporation at different inclination and rotation angles to achieve controlled symmetry breaking and obtained both left- and right-rotating isomers. The attribution of chiral optical effects to monolithic enantiomers made in this process was confirmed by theoretical calculations based on their geometry established from scanning electron microscope (SEM) images. The chirality of the nanoshells is retained upon the release from the substrate into a stable dispersion. Deviation of the incident angle of light from normal results in increase of polarization rotation and chiral g-factor as high as -0.3. This general approach for preparation of abiological nanoscale chiral materials can be extended to other out-of plane 3D nanostructures. The large area films made on achiral nanopillars are convenient for sensors, optical devices, and catalysis.

Highly Water-Dispersed and Stable Deinoxanthin Nanocapsule for Effective Antioxidant and Anti-Inflammatory Activity.

Introduction: Deinoxanthin (DX), a carotenoid, has excellent antioxidant and anti-inflammatory properties. However, owing to its lipophilicity, it is unfavorably dispersed in water and has low stability, limiting its application in cosmetics, food, and pharmaceuticals. Therefore, it is necessary to study nanoparticles to increase the loading capacity and stability of DX. Methods: In this study, DX-loaded nanocapsules (DX@NCs) were prepared by nanoprecipitation by loading DX into nanocapsules. The size, polydispersity index, surface charge, and morphology of DX@NCs were confirmed through dynamic light scattering and transmission electron microscopy. The loading content and loading efficiency of DX in DX@NCs were analyzed using high-performance liquid chromatography. The antioxidant activity of DX@NCs was evaluated by DPPH assay and in vitro ROS. The biocompatibility of DX@NCs was evaluated using an in vitro MTT assay. In vitro NO analysis was performed to determine the effective anti-inflammatory efficacy of DX@NCs. Results: DX@NCs exhibited increased stability and antioxidant efficacy owing to the improved water solubility of DX. The in situ and in vitro antioxidant activity of DX@NCs was higher than that of unloaded DX. In addition, it showed a strong anti-inflammatory effect by regulating the NO level in an in vitro cell model. Conclusion: This study presents a nanocarrier to improve the water-soluble dispersion and stability of DX. These results demonstrate that DX@NC is a carrier with excellent stability and has a high potential for use in cosmetic and pharmaceutical applications owing to its antioxidant and anti-inflammatory effects.

Hierarchically manufactured chiral plasmonic nanostructures with gigantic chirality for polarized emission and information encryption.

Chiral metamaterials have received significant attention due to their strong chiroptical interactions with electromagnetic waves of incident light. However, the fabrication of large-area, hierarchically manufactured chiral plasmonic structures with high dissymmetry factors (g-factors) over a wide spectral range remains the key barrier to practical applications. Here we report a facile yet efficient method to fabricate hierarchical chiral nanostructures over a large area (>11.7 × 11.7 cm2) and with high g-factors (up to 0.07 in the visible region) by imparting extrinsic chirality to nanostructured polymer substrates through the simple exertion of mechanical force. We also demonstrate the application of our approach in the polarized emission of quantum dots and information encryption, including chiral quick response codes and anti-counterfeiting. This study thus paves the way for the rational design and fabrication of large-area chiral nanostructures and for their application in quantum communications and security-enhanced optical communications.

Anisotropic Alignment of Bacterial Nanocellulose Ionogels for Unconventionally High Combination of Stiffness and Damping.

Ionogels are emerging materials for advanced electrochemical devices; however, their mechanical instability to external stresses has raised concerns about their safety. This study reports aligned bacterial nanocellulose (BC) ionogel films swelled with the model ionic liquid (IL) of 1-ethyl-3-methylimidazolium tetrafluoroborate (EMImBF4) for an unprecedented combination of high stiffness and high energy dissipation without significant loss of ionic conductivity. The aligned BC ionogel films are prepared through wet-state stretching methods, followed by drying and swelling by ILs. The aligned ionogel films exhibit significantly improved dynamic mechanical properties, overcoming the mechanical conventional limit of traditional materials by 2.0 times at 25 °C and by a maximum of 4.0 times at 0 °C. Additionally, the same samples exhibit relatively high ionic conductivities of 0.16 mS cm-1 at 20 °C and 0.45 mS cm-1 at 60 °C with storage moduli over 10 GPa. The synergistic effect of the mechanical reinforcements by alignment of the BC nanofibers and the plasticizing effects by ILs could be attributed to the significant enhancement of dynamic mechanical properties and the retention of ionic conductivities. These results will lead to a deeper understanding of the material design for mechanically superior ionogel systems with increasing demands for advanced electronic and electrochemical devices.

Recognition of 3D Chiral Microenvironments for Myoblast Differentiation.

Cell chirality plays a critical role in the linkage between molecular chirality and the asymmetrical biological functions of body organs. However, enantioselective interactions between cell chirality and the extracellular environment are not yet fully understood. In this study, we investigated the effects of structurally chiral extracellular microenvironments on cellular alignments and differentiations. Twisted wrinkle-shaped chiral micropatterns were prepared using biaxial and asymmetric buckling methods, wherein structural handedness was determined from the orientation of the tilt angle between the first and second microwrinkles. Myoblasts were separately cultured on two enantiomeric chiral micropatterns in a mirror-reflected shape. Cells cultured on the left-handed chiral micropatterns preferred alignments along the direction of the second microwrinkle, with a relatively deeper valley than that of the first microwrinkle. The aligned cells on the left-handed pattern showed higher differentiation rates, as assessed by fusion indices and marker protein expression levels, than those cultured on right-handed chiral micropatterns. These results suggest that myoblasts exhibit enantioselective recognition of structurally chiral microenvironments, which can promote cellular alignments and differentiation.

Intrinsically Stretchable and Printable Lithium-Ion Battery for Free-Form Configuration.

For next-generation wearable and implantable devices, energy storage devices should be soft and mechanically deformable and easily printable on any substrate or active devices. Herein, we introduce a fully stretchable lithium-ion battery system for free-form configurations in which all components, including electrodes, current collectors, separators, and encapsulants, are intrinsically stretchable and printable. The stretchable electrode acquires intrinsic stretchability and improved interfacial adhesion with the active materials via a functionalized physically cross-linked organogel as a stretchable binder and separator. Intrinsically stretchable current collectors are fabricated in the form of nanocomposites consisting of a matrix with excellent barrier properties without swelling in organic electrolytes and nanostructure-controlled multimodal conductive fillers. Due to structural and materials freedoms, we successfully fabricate several types of stretchable lithium-ion battery that reliably operates under various stretch deformations with capacity and rate capability comparable with a nonstretchable battery over 2.5 mWh cm-2 at 0.5 C, even under high mass loading conditions over 10 mg cm-2, including stacked configuration, direct integration on both sides of a stretch fabric, and application of various electrode materials and electrolytes. Especially, our stretchable battery printed on a stretch fabric also exhibits high performance and stretch/long-term stabilities in the air even with wearing and pulling.

High-performance electrified hydrogel actuators based on wrinkled nanomembrane electrodes for untethered insect-scale soft aquabots.

Hydrogels have diverse chemical properties and can exhibit reversibly large mechanical deformations in response to external stimuli; these characteristics suggest that hydrogels are promising materials for soft robots. However, reported actuators based on hydrogels generally suffer from slow response speed and/or poor controllability due to intrinsic material limitations and electrode fabrication technologies. Here, we report a hydrogel actuator that operates at low voltages (<3 volts) with high performance (strain > 50%, energy density > 7 × 105 joules per cubic meter, and power density > 3 × 104 watts per cubic meter), surpassing existing hydrogel actuators and other types of electroactive soft actuators. The enhanced performance of our actuator is due to the formation of wrinkled nanomembrane electrodes that exhibit high conductivity and excellent mechanical deformation through capillary-assisted assembly of metal nanoparticles and deswelling-induced wrinkled structures. By applying an electric potential through the wrinkled nanomembrane electrodes that sandwich the hydrogel, we were able to trigger a reversible and substantial electroosmotic water flow inside a hydrogel film, which drove the controlled swelling of the hydrogel. The high energy efficiency and power density of our wrinkled nanomembrane electrode-induced actuator enabled the fabrication of an untethered insect-scale aquabot integrated with an on-board control unit demonstrating maneuverability with fast locomotion speed (1.02 body length per second), which occupies only 2% of the total mass of the robot.

Spontaneous self-organization enables dielectrophoresis of small nanoparticles and formation of photoconductive microbridges.

Detailed understanding of the mechanism of dielectrophoresis (DEP) and the drastic improvement of its efficiency for small size-quantized nanoparticles (NPs) open the door for the convergence of microscale and nanoscale technologies. It is hindered, however, by the severe reduction of DEP force in particles with volumes below a few hundred cubic nanometers. We report here DEP assembly of size-quantized CdTe nanoparticles (NPs) with a diameter of 4.2 nm under AC voltage of 4-10 V. Calculations of the nominal DEP force for these NPs indicate that it is several orders of magnitude smaller than the force of the Brownian motion destroying the assemblies even for the maximum applied AC voltage. Despite this, very efficient formation of NP bridges between electrodes separated by a gap of 2 µm was observed even for AC voltages of 6 V and highly diluted NP dispersions. The resolution of this conundrum was found in the intrinsic ability of CdTe NPs to self-assemble. The species being assembled by DEP are substantially bigger than the individual NPs. DEP assembly should be treated as a process taking place for NP chains with a length of ~140 nm. The self-assembled chains increase the nominal volume where the polarization of the particles takes place, while retaining the size-quantized nature of the material. The produced NP bridges were found to be photoactive, producing photocurrent upon illumination. DEP bridges of quantum confined NPs can be used in fast parallel manufacturing of novel MEMS components, sensors, and optical and optoelectronic devices. Purposeful engineering of self-assembling properties of NPs makes possible further facilitation of the DEP and increase of complexity of the produced nano- and microscale structures.

Preprogrammed microfluidic system for parallel anti-reflection coating by layer-by-layer assembly.

Layer-by-layer (LbL) assembly is a widely used method of nanofilm coating in various technology applications; however, the coating process is typically time-consuming and labor-intensive. This study presents a microfluidic platform that performs LbL assembly in a fast, parallel, preprogrammed manner, with only water-head pressure as the driving force. The platform generates periodic sequential outflows with four solutions (TiO2 and SiO2 nanoparticle solutions and two washing solutions), and simultaneously applies 12 different conditions of coating period (0.6-4 min) and shear stress (0.7-15 dyn cm-2) for anti-reflection coating in the visual spectrum. The thickness and roughness of the coated films are well regulated at the nanoscale using shear stress, coating period, and the number of bilayers. In this way, our study reveals the substantial influence of shear stress on the relative composition of the nanoparticles and void volume in the films, thereby varying the film transmittance with a maximum value of 98%. Compared to the conventional immersive coating method, the coating duration of our method was 15 times faster. This parallel coating method is highly effective for determining optimized coating conditions.

Chiral Magneto-Optical Properties of Supra-Assembled Fe3O4 Nanoparticles.

Research on the chiral magneto-optical properties of inorganic nanomaterials has enabled novel applications in advanced optical and electronic devices. However, the corresponding chiral magneto-optical responses have only been studied under strong magnetic fields of ≥1 T, which limits the wider application of these novel materials. In this paper, we report on the enhanced chiral magneto-optical activity of supra-assembled Fe3O4 magnetite nanoparticles in the visible range at weak magnetic fields of 1.5 mT. The spherical supra-assembled particles with a diameter of ∼90 nm prepared by solvothermal synthesis had single-crystal-like structures, which resulted from the oriented attachment of nanograins. They exhibited superparamagnetic behavior even with a relatively large supraparticle diameter that exceeded the size limit for superparamagnetism. This can be attributed to the small size of nanograins with a diameter of ∼12 nm that constitute the suprastructured particles. Magnetic circular dichroism (MCD) measurements at magnetic fields of 1.5 mT showed distinct chiral magneto-optical activity from charge transfer transitions of magnetite in the visible range. For the supraparticles with lower crystallinity, the MCD peaks in the 250-550 nm range assigned as the ligand-to-metal charge transfer (LMCT) and the inter-sublattice charge transfer (ISCT) show increased intensities in comparison to those with higher crystallinity samples. On the contrary, the higher crystallinity sample shows higher MCD intensities near 600-700 nm for the intervalence charge transfer (IVCT) transition. The differences in MCD responses can be attributed to the crystallinity determined by the reaction time, lattice distortion near grain boundaries of the constituent nanocrystals, and dipolar interactions in the supra-assembled structures.