A Neutrophil-Inspired Supramolecular Nanogel for Magnetocaloric-Enzymatic Tandem Therapy.

Neutrophils can responsively release reactive oxygen species (ROS) to actively combat infections by exogenous stimulus and cascade enzyme catalyzed bio-oxidation. A supramolecular nanogel is now used as an artificial neutrophil by enzymatic interfacial self-assembly of peptides (Fmoc-Tyr(H2 PO3 )-OH) with magnetic nanoparticles (MNPs) and electrostatic loading of chloroperoxidase (CPO). The MNPs within the nanogel can elevate H2 O2 levels in cancer cells under programmed alternating magnetic field (AMF) similar to the neutrophil activator, and the loaded CPO within protective peptides nanolayer converts the H2 O2 into singlet oxygen (1 O2 ) in a sustained manner for neutrophil-inspired tumor therapy. As a proof of concept study, both the H2 O2 and 1 O2 in cancer cells increase stepwise under a programmed alternating magnetic field. An active enzyme dynamic therapy by magnetically stimulated oxygen stress and sustained enzyme bio-oxidation is thus shown with studies on both cells and animals.

DNA nanostructures constructed with multi-stranded motifs.

Earlier studies in DNA self-assembly have foretold the feasibility of building addressable nanostructures with multi-stranded motifs, which is fully validated in this study. In realizing this feasibility in DNA nanotechnology, a diversified set of motifs of modified domain lengths is extended from a classic type. The length of sticky ends can be adjusted to form different dihedral angles between the matching motifs, which corresponds to different connecting patterns. Moreover, the length of rigidity core can also be tuned to result in different dihedral angles between the component helices of a certain motif therefore different numbers of component helices. The extended set of motifs is used for self-assembly of complex one dimensional, two dimensional and three dimensional structures.

Hierarchical Assembly of DNA Nanostructures Based on Four-Way Toehold-Mediated Strand Displacement.

Because of its attractive cost and yield, hierarchical assembly, in which constituent structures of lower hierarchy share a majority of components, is an appealing approach to scale up DNA self-assembly. A few strategies have already been investigated to combine preformed DNA nanostructures. In this study, we present a new hierarchical assembly method based on four-way toehold-mediated strand displacement to facilitate the combination of preformed DNA structural units. Employing such a method, we have constructed a series of higher-order structures composed of 5, 7, 9, 11, 13, and 15 preformed units respectively.

Self-Assembly of Wireframe DNA Nanostructures from Junction Motifs.

Wireframe frameworks have been investigated for the construction of complex nanostructures from a scaffolded DNA origami approach; however, a similar framework is yet to be fully explored in a scaffold-free "LEGO" approach. Herein, we describe a general design scheme to construct wireframe DNA nanostructures entirely from short synthetic strands. A typical edge of the resulting structures in this study is composed of two parallel duplexes with crossovers on both ends, and three, four, or five edges radiate out from a certain vertex. By using such a self-assembly scheme, we produced planar lattices and polyhedral objects.

Exponential growth and selection in self-replicating materials from DNA origami rafts.

Self-replication and evolution under selective pressure are inherent phenomena in life, and but few artificial systems exhibit these phenomena. We have designed a system of DNA origami rafts that exponentially replicates a seed pattern, doubling the copies in each diurnal-like cycle of temperature and ultraviolet illumination, producing more than 7 million copies in 24 cycles. We demonstrate environmental selection in growing populations by incorporating pH-sensitive binding in two subpopulations. In one species, pH-sensitive triplex DNA bonds enable parent-daughter templating, while in the second species, triplex binding inhibits the formation of duplex DNA templating. At pH 5.3, the replication rate of species I is  ∼1.3-1.4 times faster than that of species II. At pH 7.8, the replication rates are reversed. When mixed together in the same vial, the progeny of species I replicate preferentially at pH 7.8; similarly at pH 5.3, the progeny of species II take over the system. This addressable selectivity should be adaptable to the selection and evolution of multi-component self-replicating materials in the nanoscopic-to-microscopic size range.

Self-assembly of fully addressable DNA nanostructures from double crossover tiles.

DNA origami and single-stranded tile (SST) are two proven approaches to self-assemble finite-size complex DNA nanostructures. The construction elements appeared in structures from these two methods can also be found in multi-stranded DNA tiles such as double crossover tiles. Here we report the design and observation of four types of finite-size lattices with four different double crossover tiles, respectively, which, we believe, in terms of both complexity and robustness, will be rival to DNA origami and SST structures.

Drainage of a thin liquid film between hydrophobic spheres: boundary curvature effects.

We investigate theoretically the drainage of a thin liquid film confined between two hydrophobic spheres. Such a problem has been considered in Vinogradova's seminal work, emphasizing the role of slippage. However, it does not include the boundary curvature effects, which may become especially important when the slip lengths are comparable to the sphere radii. We present a reformulation of the hydrodynamic boundary conditions, with the boundary curvature effects fully taken into account. It is shown that such effects not only renormalize the effective slip lengths but also give new contributions to the pressure and drag force, neglected so far. We focus on the symmetric case of two identical spheres with the same radii and slip lengths and obtain analytical expressions for the pressure as well as the drag force. The boundary curvature corrections to the drag force are analyzed and found to be more important for more hydrophobic spheres. The implications of our results are discussed for the coagulation processes of colloids and measurements of surface forces or slip lengths with the drainage technique.

Integrated Pristine van der Waals Homojunctions for Self-Powered Image Sensors.

Van der Waals junctions hold significant potentials for various applications in multifunctional and low-power electronics and optoelectronics. The multistep device fabrication process usually introduces lattice mismatch and defects at the junction interfaces, which deteriorate device performance. Here the layer engineering synthesis of van der Waals homojunctions consisting of 2H-MoTe2 with asymmetric thickness to eliminate heterogenous interfaces and thus obtain clean interfaces is reported. Experimental results confirm that the homostructure nature gives rise to the formation of pristine van der Waals junctions, avoiding chemical disorders and defects. The ability to tune the energy bands of 2H-MoTe2 continuously through layer engineering enables the creation of adjustable built-in electric field at the homojunction boundaries, which leads to the achievement of self-powered photodetection based on the obtained 2H-MoTe2 films. Furthermore, the successful integration of 2H-MoTe2 homojunctions into an image sensor with 10 × 10 pixels, brings about zero-power consumption and near-infrared imaging functions. The pristine van der Waals homojunctions and effective integration strategies shed new insights into the development of large-scale application for two-dimensional materials in advanced electronics and optoelectronics.

Ionic liquids as electrolytes in aluminum electrolysis.

Herein, the characteristics, research progress, and application prospects of ionic liquid-based electrolytic aluminum deposition are reviewed and analyzed in comparison with the Hall-Héroult method. The reaction conditions and production procedures of this material are discussed alongside the problems ionic liquids face in the electrolytic aluminum industry. Ionic liquid-based electrolytic aluminum deposition realizes the electrolytic aluminum reaction at low temperatures, achieving a reaction energy consumption close to the theoretical minimum value. The reaction also avoids harmful CO2 or HF emissions, demonstrating a green and environmental-friendly approach to the production of electrolytic aluminum. In the future, in-depth work on the implementation of ionic liquid electrolytes should be carried out, establishing the necessary technical criteria and laying the foundation for the integration of this approach.

Anisotropic wetting on checkerboard-patterned surfaces.

A series of surfaces with microscale checkerboard patterns consisting of continuous central lines and discontinuous lateral lines were fabricated. The surface wetting properties of these checkerboard patterns were found to be anisotropic. The central continuous lines were found to have a strong influence on the dynamic wetting properties and moving trajectories of the water droplets. The droplets move more easily in the direction parallel to the central continuous lines and less easily in the direction perpendicular to the central continuous lines. Meanwhile, the droplets' moving path tends to incline toward the central continuous lines from a tilting direction. When the microsurface was modified with a layer of nanowire, the surface wettability was found to be isotropic and superhydrophobic.

UNIQUIMER 3D, a software system for structural DNA nanotechnology design, analysis and evaluation.

A user-friendly software system, UNIQUIMER 3D, was developed to design DNA structures for nanotechnology applications. It consists of 3D visualization, internal energy minimization, sequence generation and construction of motif array simulations (2D tiles and 3D lattices) functionalities. The system can be used to check structural deformation and design errors under scaled-up conditions. UNIQUIMER 3D has been tested on the design of both existing motifs (holiday junction, 4 x 4 tile, double crossover, DNA tetrahedron, DNA cube, etc.) and nonexisting motifs (soccer ball). The results demonstrated UNIQUIMER 3D's capability in designing large complex structures. We also designed a de novo sequence generation algorithm. UNIQUIMER 3D was developed for the Windows environment and is provided free of charge to the nonprofit research institutions.

A replicable tetrahedral nanostructure self-assembled from a single DNA strand.

We report the design and construction of a nanometer-sized tetrahedron from a single strand of DNA that is 286 nucleotides long. The formation of the tetrahedron was verified by restriction enzyme digestion, Ferguson analysis, and atomic force microscopy (AFM) imaging. We further demonstrate that synthesis of the tetrahedron can be easily scaled up through in vivo replication using standard molecular cloning techniques. We found that the in vivo replication efficiency of the tetrahedron is significantly higher in comparison to in vitro replication using rolling-circle amplification (RCA). Our results suggest that it is now possible to design and replicate increasingly complex, single-stranded DNA nanostructures in vivo.

DNA nanostructures from double-C-shaped motifs with controllable twist and curvature.

We demonstrate twist and curvature engineering in DNA nanostructures from the scaffold-free approach. The DNA 'LEGO' bricks adopted in this study are double-C-shaped motifs, and extended nanostructures are constructed to visualize the structural details of twist or curvature. By systematically deleting and inserting base pairs at certain domains of the component motifs, we are able to study various levels of the twist and curvature of the resulting nanostructures comprehensively.

Hybrid Anatase/Rutile Nanodots-Embedded Covalent Organic Frameworks with Complementary Polysulfide Adsorption for High-Performance Lithium-Sulfur Batteries.

The shuttling effect of polysulfides species seriously deteriorates the performance of Li-S batteries, representing the major obstacle for their practical use. However, the exploration of ideal cathodes that can suppress the shuttling of all polysulfides species is challenging. Herein, we propose an ingenious and effective strategy for constructing hybrid-crystal-phase TiO2/covalent organic framework (HCPT@COF) composites where hybrid anatase/rutile TiO2 nanodots (10 nm) are uniformly embedded in the interlayers of porous COFs. The synthesis was realized via a multiple-step reaction relay accompanying by a pseudo-topotactic transformation of three-dimensional layered structures from 1,4-dicyanobenzene monomer-embedded Ti-intermediate networks to HCPT nanodots-embedded COF frameworks. The HCPT@COF/S cathodes show superior comprehensive performance such as high specific capacity, long cycling stability, and remarkable rate capability for Li-S batteries, owing to the complementary anchoring effect of hybrid anatase/rutile TiO2 in the HCPT@COF composite, which is evidenced by substantial characterizations including X-ray photoelectron spectroscopy and density functional theory calculations.

Nanoinitiator for enzymatic anaerobic polymerization and graft enhancement of gelatin-PAAM hydrogel.

As an emerging method for mildly molding polymer hydrogel bioscaffolds, the enzymatically polymerized system is mainly based on the screening of various oxidoreductases to produce radicals, but the design of multifunctional nanoinitiators to facilitate hydrogel performance remains challenging. Here, we utilize N-hydroxyimide-modified silica nanoparticles as nanoinitiators to simultaneously trigger glucose oxidase anaerobic polymerization and nanoparticle-grafting enhancement of the gelatin-polyacrylamide (PAAM) hydrogel. The enzyme-nanoinitiator system produced nitrogen radicals, which were further converted into carbon radicals via GOx-catalyzed glucose reduction, as confirmed by electron paramagnetic resonance (EPR) analysis. Our stretchable hydrogel has a 12-fold increased fracture energy relative to traditional hydrogel due to grafting enhancement by the nanoinitiator. The temperature-dependent physical crosslinking of gelatin endowed our hydrogel facile printing ability. Cytotoxicity assay and 3D cell culture demonstrated the low toxicity of our hydrogel. As the first example of the use of nanoinitiators for enzymatic polymerization, this work provides a biocompatible platform to prepare or print hydrogel bioscaffolds with the required mechanical strength.

Versatile DNA Origami Nanostructures in Simplified and Modular Designing Framework.

We introduce a simplified and modular architecture for design and construction of complex origami nanostructures. A series of basic two-dimensional and three-dimensional structures are presented. As the resulting structures can be virtually divided into blocks, modular remodeling such as translocation, contraction/extension, and bending is carried out. Structures under such a designing framework are morphable. Local conformational changes can propagate to the entire structure to reshape the global conformation.

Ultrathin Lanthanum Tantalate Perovskite Nanosheets Modified by Nitrogen Doping for Efficient Photocatalytic Water Splitting.

Ultrathin nitrogen-doped perovskite nanosheets LaTa2O6.77N0.15- have been fabricated by exfoliating Dion-Jacobson-type layered perovskite RbLaTa2O6.77N0.15. These nanosheets demonstrate superior photocatalytic activities for water splitting into hydrogen and oxygen and remain active with photon wavelengths as far as 600 nm. Their apparent quantum efficiency under visible-light illumination (λ ≥ 420 nm) approaches 1.29% and 3.27% for photocatalytic hydrogen and oxygen production, being almost 4-fold and 8-fold higher than bulk RbLaTa2O6.77N0.15. Their outstanding performance likely stems from their tiny thickness (single perovskite slab) that essentially removes bulk charge diffusion steps and extends the lifetime of photogenerated charges. Theoretical calculations reveal a peculiar 2D charge transportation phenomenon in RbLaTa2O6.77N0.15; thus, exfoliating RbLaTa2O6.77N0.15 into LaTa2O6.77N0.15- nanosheets has limited impact on charge transportation properties but significantly enhances the surface areas which contributes to more reaction sites.

Recovering thermodynamic consistency of the antitrapping model: a variational phase-field formulation for alloy solidification.

The phenomenological antitrapping phase-field model has attained much success in describing alloy solidification. The heuristically introduced antitrapping current enables removing artificial effects due to the use of large interfacial width. Nevertheless, such a model is not thermodynamically consistent and has not been fitted into a variational framework. Here we present two approaches to develop a variational phase-field model to describe patten formation in alloys. Following the principles of linear irreversible thermodynamics we build in the cross-coupling between the phase transition rate and solute diffusion current. Our formulation not only naturally incorporates the antitrapping current but also predicts the conjugated mesoscopic solute drag effect. A more general form of the antitrapping current is obtained by thin-interface analysis. Benchmark simulations on isothermal dendrite growth are carried out to show the capability of our model to quantitatively characterize the interface evolution and solute profile even with a large interface width used. Importantly, our theory also provides general insights on how to obtain the genuine dynamic coupling between nonconserved and conserved order parameters. This leads to a thermodynamically consistent generalization of the celebrated model C proposed by Hohenberg and Halperin [Rev. Mod. Phys. 49, 435 (1977)].