A Novel Design of Multi‐Mechanoresponsive and Mechanically Strong Hydrogels

A newly developed polyacrylamide‐co ‐methyl acrylate/spiropyran (SP) hydrogel crosslinked by SP mechanophore demonstrates multi‐stimuli‐responsive and mechanically strong properties. The hydrogels not only exhibit thermo‐, photo‐, and mechano‐induced color changes, but also achieve super‐strong mechanical properties (tensile stress of 1.45 MPa, tensile strain of ≈600%, and fracture energy of 7300 J m^?2). Due to a reversible structural transformation between spiropyran (a ring‐close) and merocyanine (a ring‐open) states, simple exposure of the hydrogels to white light can reverse color changes and restore mechanical properties. The new design approach for a new mechanoresponsive hydrogel is easily transformative to the development of other mechanophore‐based hydrogels for sensing, imaging, and display applications.     

Printing 1D Assembly Array of Single Particle Resolution for Magnetosensing

Magnetosensing is a ubiquitous ability for many organism species in nature. 1D assembly, especially that arranged in single‐particle‐resolution regulation, is able to sense the direction of magnetic field depending on the enhanced dipolar interaction in the linear orientation. Inspired by the magnetosome structure in magnetotactic bacteria, a 1D assembly array of single particle resolution with controlled length and well‐behaved configuration is prepared via inkjet printing method assisted with magnetic guiding. In the fabrication process, chains in a “tip‐to‐tip” regulation with the desired number of particles are prepared in a confined tiny inkjet‐printed droplet. By adjusting the receding angle of the substrate, the assembled 1D morphology is kept/deteriorated depending on the pinning/depinning behavior during ink evaporation, which leads to the formation of well‐behaved 1D assembly/aggregated dot assembly. Owing to the high‐aspect‐ratio characteristic of the assembled structure, the as‐prepared 1D arrays can be used for magnetic field sensing with anisotropic magnetization M_///M_⊥ up to 6.03.     

Polysaccharide-based magnetically responsive polyelectrolyte hydrogels for tissue engineering applications

Polysaccharide-based bionanocomposite hydrogels with functional nanomaterials were used in biomedical applications.Self-organization of xanthan gum and chitosan in the presence of iron oxide magnetic nanoparticles(Fe_3O_4MNPs)allowed us to form magnetically responsive polyelectrolyte complex hydrogels(MPECHs)via insitu ionic complexation using D-(+)-glucuronic acid?-lactone as a green acidifying agent.Characterization confirmed the successful formation of(and structural interactions within)the MPECH and good porous structure.The rheological behavior and compressive properties of the PECH and MPECH were measured.The results indicated that the incorporation of Fe_3O_4MNPs into the PECH greatly improved mechanical properties and storage modulus(G’).In vitro cell culture of NIH3T3 fibroblasts on MPECHs showed improvements in cell proliferation and adhesion in an external magnetic field relative to the pristine PECH.The results showed that the newly developed MPECH could potentially be used as a magnetically stimulated system in tissue engineering applications.     

Microfluidics‐Assisted Assembly of Injectable Photonic Hydrogels toward Reflective Cooling

Development of fast curing and easy modeling of colloidal photonic crystals is highly desirable for various applications. Here, a novel type of injectable photonic hydrogel (IPH) is proposed to achieve self‐healable structural color by integrating microfluidics‐derived photonic supraballs with supramolecular hydrogels. The supramolecular hydrogel is engineered via incorporating β‐cyclodextrin/poly(2‐hydroxypropyl acrylate‐co‐N‐vinylimidazole) (CD/poly(HPA‐co‐VI)) with methacrylated gelatin (GelMA), and serves as a scaffold for colloidal crystal arrays. The photonic supraballs derived from the microfluidics techniques, exhibit excellent compatibility with the hydrogel scaffolds, leading to enhanced assembly efficiency. By virtue of hydrogen bonds and host–guest interactions, a series of self‐healable photonic hydrogels (linear, planar, and spiral assemblies) can be facilely assembled. It is demonstrated that the spherical symmetry of the photonic supraballs endows them with identical optical responses independent of viewing angles. In addition, by taking the advantage of angle independent spectrum characteristics, the IPH presents beneficial effects in reflective cooling, which can achieve up to 17.4 °C in passive solar reflective cooling. The strategy represents an easy‐to‐perform platform for the construction of IPH, providing novel insights into macroscopic self‐assembly toward thermal management applications.     

Thermal Responsive Photonic Crystal Achieved through the Control of Light Path Guided by Phase Transition

Responsive photonic crystal is widely considered in the field of anti‐counterfeiting and information encryption because of their structural color changes caused by external stimulation. However, the response signal is usually achieved by adjusting the periodic lattice constant based on Bragg's law with volume changes. Thus, it is a great challenge to achieve the response of photonic crystals by non‐array parameter control. Herein, novel thermal responsive photonic crystal (TRPC) with low angle dependent structural color is fabricated by introducing poly(ethylene glycol) into the structure of low angle dependent SnO₂ inverse opal. The response is achieved through the control of light path guided by phase transition and the significant volume change caused by the change of traditional array parameters can be effectively avoided. Meanwhile, the low angle dependent structural color of TRPC can effectively reduce the interference of observation angle change to response signal caused by external thermal stimulation. Patterned responsive photonic crystals with temperature gradient response are easily obtained by combining confinement self‐assembly and direct template method, and the patterns can be presented and hidden by the control of light path, showing great potential in anti‐counterfeiting and information encryption fields.     

Hierarchical Micro‐ and Mesoporous Zn‐Based Metal–Organic Frameworks Templated by Hydrogels: Their Use for Enzyme Immobilization and Catalysis of Knoevenagel Reaction

Encapsulation of enzymes in metal–organic frameworks (MOFs) is often obstructed by the small size of the orifices typical of most reported MOFs, which prevent the passage of larger‐size enzymes. Here, the preparation of hierarchical micro‐ and mesoporous Zn‐based MOFs via the templated emulsification method using hydrogels as a template is presented. Zinc‐based hydrogels featuring a 3D interconnecting network are first produced via the formation of hydrogen bonds between melamine and salicylic acid in which zinc ions are well distributed. Further coordination with organic linkers followed by the removal of the hydrogel template produces hierarchical Zn‐based MOFs containing both micropores and mesopores. These new MOFs are used for the encapsulation of glucose oxidase and horseradish peroxidase to prove the concept. The immobilized enzymes exhibit a remarkably enhanced increased operational stability and enzymatic activity with a k_cat/k_m value of 85.68 mm s^–1. This value is 7.7‐fold higher compared to that found for the free enzymes in solution, and 2.7‐fold higher than enzymes adsorbed on conventional microporous MOFs. The much higher catalytic activity of the mesoporous conjugate for Knoevenagel reactions is demonstrated, since the large pores enable easier access to the active sites, and compared with that observed for catalysis using microporous MOFs.     

Remote Magnetic Nanoparticle Manipulation Enables the Dynamic Patterning of Cardiac Tissues

The ability to manipulate cellular organization within soft materials has important potential in biomedicine and regenerative medicine; however, it often requires complex fabrication procedures. Here, a simple, cost-effective, and one-step approach that enables the control of cell orientation within 3D collagen hydrogels is developed to dynamically create various tailored microstructures of cardiac tissues. This is achieved by incorporating iron oxide nanoparticles into human cardiomyocytes and applying a short-term external magnetic field to orient the cells along the applied field to impart different shapes without any mechanical support. The patterned constructs are viable and functional, can be detected by T₂*-weighted magnetic resonance imaging, and induce no alteration to normal cardiac function after grafting onto rat hearts. This strategy paves the way to creating customized, macroscale, 3D tissue constructs with various cell-types for therapeutic and bioengineering applications, as well as providing powerful models for investigating tissue behavior.     

A Magnetic‐Field Guided Interface Coassembly Approach to Magnetic Mesoporous Silica Nanochains for Osteoclast‐Targeted Inhibition and Heterogeneous Nanocatalysis

1D core–shell magnetic materials with mesopores in shell are highly desired for biocatalysis, magnetic bioseparation, and bioenrichment and biosensing because of their unique microstructure and morphology. In this study, 1D magnetic mesoporous silica nanochains (Fe₃O₄@nSiO₂@mSiO₂ nanochain, Magn‐MSNCs named as FDUcs‐17C) are facilely synthesized via a novel magnetic‐field‐guided interface coassembly approach in two steps. Fe₃O₄ particles are coated with nonporous silica in a magnetic field to form 1D Fe₃O₄@nSiO₂ nanochains. A further interface coassembly of cetyltrimethylammonium bromide and silica source in water/n‐hexane biliquid system leads to 1D Magn‐MSNCs with core–shell–shell structure, uniform diameter (≈310 nm), large and perpendicular mesopores (7.3 nm), high surface area (317 m² g^?1), and high magnetization (34.9 emu g^?1). Under a rotating magnetic field, the nanochains with loaded zoledronate (a medication for treating bone diseases) in the mesopores, show an interesting suppression effect of osteoclasts differentiation, due to their 1D nanostructure that provides a shearing force in dynamic magnetic field to induce sufficient and effective reactions in cells. Moreover, by loading Au nanoparticles in the mesopores, the 1D Fe₃O₄@nSiO₂@mSiO₂‐Au nanochains can service as a catalytically active magnetic nanostirrer for hydrogenation of 4‐nitrophenol with high catalytic performance and good magnetic recyclability.     

Anatomy of Skyrmionic Textures in Magnetic Multilayers

Room temperature magnetic skyrmions in magnetic multilayers are considered as information carriers for future spintronic applications. Currently, a detailed understanding of the skyrmion stabilization mechanisms is still lacking in these systems. To gain more insight, it is first and foremost essential to determine the full real‐space spin configuration. Here, two advanced X‐ray techniques are applied, based on magnetic circular dichroism, to investigate the spin textures of skyrmions in [Ta/CoFeB/MgO]_n multilayers. First, by using ptychography, a high‐resolution diffraction imaging technique, the 2D out‐of‐plane spin profile of skyrmions with a spatial resolution of 10 nm is determined. Second, by performing circular dichroism in resonant elastic X‐ray scattering, it is demonstrated that the chirality of the magnetic structure undergoes a depth‐dependent evolution. This suggests that the skyrmion structure is a complex 3D structure rather than an identical planar texture throughout the layer stack. The analyses of the spin textures confirm the theoretical predictions that the dipole–dipole interactions together with the external magnetic field play an important role in stabilizing sub‐100 nm diameter skyrmions and the hybrid structure of the skyrmion domain wall. This combined X‐ray‐based approach opens the door for in‐depth studies of magnetic skyrmion systems, which allows for precise engineering of optimized skyrmion heterostructures.     

Vacancy‐Driven Gelation Using Defect‐Rich Nanoassemblies of 2D Transition Metal Dichalcogenides and Polymeric Binder for Biomedical Applications

A new approach of vacancy‐driven gelation to obtain chemically crosslinked hydrogels from defect‐rich 2D molybdenum disulfide (MoS₂) nanoassemblies and polymeric binder is reported. This approach utilizes the planar and edge atomic defects available on the surface of the 2D MoS₂ nanoassemblies to form mechanically resilient and elastomeric nanocomposite hydrogels. The atomic defects present on the lattice plane of 2D MoS₂ nanoassemblies are due to atomic vacancies and can act as an active center for vacancy‐driven gelation with a thiol‐activated terminal such as four‐arm poly(ethylene glycol)–thiol (PEG‐SH) via chemisorption. By modulating the number of vacancies on the 2D MoS₂ nanoassemblies, the physical and chemical properties of the hydrogel network can be controlled. This vacancy‐driven gelation process does not require external stimuli such as UV exposure, chemical initiator, or thermal agitation for crosslinking and thus provides a nontoxic and facile approach to encapsulate cells and proteins. 2D MoS₂ nanoassemblies are cytocompatible, and encapsulated cells in the nanocomposite hydrogels show high viability. Overall, the nanoengineered hydrogel obtained from vacancy‐driven gelation is mechanically resilient and can be used for a range of biomedical applications including tissue engineering, regenerative medicine, and cell and therapeutic delivery.     

Tunable Photonic Microspheres of Comb‐Like Supramolecules

Photonic crystals (PCs) are ideal candidates for reflective color pigments with high color purity and brightness due to tunable optical stop band. Herein, the generation of PC microspheres through 3D confined supramolecular assembly of block copolymers (polystyrene‐block‐poly(2‐vinylpyridine), PS‐b‐P2VP) and small molecules (3‐n‐pentadecylphenol, PDP) in emulsion droplets is demonstrated. The intrinsic structural colors of the PC microspheres are effectively regulated by tuning hydrogen‐bonding interaction between P2VP blocks and PDP, where reflected color can be readily tuned across the whole visible spectrum range. Also, the effects of both PDP and homopolymer (hPS) on periodic structure and optical properties of the microspheres are investigated. Moreover, the spectral results of finite element method (FEM) simulation agree well with the variation of structural colors by tuning the periodicity in PC microspheres. The supramolecular microspheres with tunable intrinsic structural color can be potentially useful in the various practical applications including display, anti‐counterfeit printing and painting.     

Variation of Residual Magnetic Field of Defective U75V Steel Subjected to Tensile Stress

Variation of the stress‐induced magnetic field of the U75V rail steel under tension was investigated in this research. Various magnetic responses were registered by a magnetometer in the elastic and plastic deformation stages, which can be explained by the microstructural changes in magnetic domains. Two types of defective specimens were also tested to correlate the stress concentration with the magnetic field. It is found that the tangential component of the magnetic field B_x is much more sensitive to local stress concentration than the normal component B_z. The tangential component B_x reaches a peak value at the rupture position, and the peak magnitude is proportional to the concentrated stress caused by the defect. This observation is different from the Q235 steel, whose tangential component B_x and the normal component B_z are equally effective. Such discrepancy might be due to that U75V fails in a more brittle pattern than the Q235 steel. The average value of the B_x along the loading axis can determine the overall stress state of the structure, while the peaks in the B_x curve tell the local stress concentration caused by cracks and dislocation.     

Piezotronic Tunneling Junction Gated by Mechanical Stimuli

Tunneling junction is used in many devices such as high‐frequency oscillators, nonvolatile memories, and magnetic field sensors. In these devices, modulation on the barrier width and/or height is usually realized by electric field or magnetic field. Here, a new piezotronic tunneling junction (PTJ) principle, in which the quantum tunneling is controlled/tuned by externally applied mechanical stimuli, is proposed. In these metal/insulator/piezoelectric semiconductor PTJs, such as Pt/Al₂O₃/p‐GaN, the height and the width of the tunneling barriers can be mechanically modulated via the piezotronic effect. The tunneling current characteristics of PTJs exhibit critical behavior as a function of external mechanical stimuli, which results in high sensitivity (≈5.59 mV MPa^?1), giant switching (>10⁵), and fast response (≈4.38 ms). Moreover, the mechanical controlling of tunneling transport in PTJs with various thickness of Al₂O₃ is systematically investigated. The high performance observed with these metal/insulator/piezoelectric semiconductor PTJs suggest their great potential in electromechanical technology. This study not only demonstrates dynamic mechanical controlling of quantum tunneling, but also paves a way for adaptive interaction between quantum tunneling and mechanical stimuli, with potential applications in the field of ultrasensitive press sensor, human–machine interface, and artificial intelligence.     

Three‐dimensional mixed‐mode (I and II) crack‐front fields in ductile thin plates — effects of T‐stress

It has been well‐established that the non‐singular T‐stress provides a first‐order estimate of geometry and loading mode (e.g. tension versus bending) effects on elastic–plastic crack‐front field under mode I loading conditions. The objective of this paper is to exam the T‐stress effect on three‐dimensional (3D) crack‐front fields under mixed‐mode (modes I and II) loading. To this end, detailed 3D small strain, elastic–plastic simulations are carried out using a 3D boundary layer (small‐scale yielding) formulation. Characteristics of near crack‐front fields are investigated for a wide range of T‐stresses (T/σ₀ = ?0.8, ?0.4, 0.0, 0.4, 0.8). The plastic zones and thickness and angular and radial variations of the stresses are studied, corresponding to two values of the remote elastic mixity parameters M_e = 0.3 and 0.7, under both low and high levels of applied loads. It is found that different T‐stresses have a significant effect on the plastic zones size and shapes, regardless of the mode mixity and load level. The thickness, angular and radial distributions of stresses are also affected markedly by T‐stress. It is important to include these effects when investigating the mixed‐mode ductile fracture failure process in thin‐walled structural components.     

Magnet–PNIPA hydrogels for bioengineering applications

Temperature-sensitive Poly (N-isopropylacrylamide), PNIPA gels were synthesized with micron-sized iron and iron oxide (Fe₃O₄) particles to investigate their viability for hyperthermia applications. Induction heating of the magnetic hydrogels with varying concentration of magnetic powder was conducted at a frequency of 375  kHz for magnetic field strength varying from 1.7 kA/m (21 Oe) to 2.5 kA/m (31.4 Oe). It was observed that the maximum temperature induced in the magnetic hydrogels increased with the concentration of magnetic particles and magnetic field strength. The PNIPA gel underwent a collapse transition at 34 °C. It was found that a 2.5 wt.% Fe₃O₄ in PNIPA composite took 260 s to be heated to 45 °C under a magnetic field strength of 1.7 kA/m, the specific absorption rate (SAR) was found to be 1.83. SAR of iron oxide was found to be higher than the SAR of iron.     

Zero‐Field Nernst Effect in a Ferromagnetic Kagome‐Lattice Weyl‐Semimetal Co3Sn2S2

The discovery of magnetic topological semimetals has recently attracted significant attention in the field of topology and thermoelectrics. In a thermoelectric device based on the Nernst geometry, an external magnet is required as an integral part. Reported is a zero‐field Nernst effect in a newly discovered hard‐ferromagnetic kagome‐lattice Weyl‐semimetal Co₃Sn₂S₂. A maximum Nernst thermopower of ≈3 µV K^?1 at 80 K in zero field is achieved in this magnetic Weyl‐semimetal. The results demonstrate the possibility of application of topological hard magnetic semimetals for low‐power thermoelectric devices based on the Nernst effect and are thus valuable for the comprehensive understanding of transport properties in this class of materials.     

Structural anisotropy of silica hydrogels prepared under magnetic field

Birefringence measurements have been carried out on the Pb-doped silica hydrogels prepared under various magnetic fields up to 5T. The silica gels prepared at 5T were used as a medium of crystal growth of PbBr₂, whose result implied the structural anisotropy; an aligned array of crystallites was obtained by transmission electron microscopy. While the samples prepared at 0, 1, and 3T have no birefringence, we found that the samples have negative birefringence on the order of magnitude 10^− 6 as if the direction of the magnetic field is the optic axis of a uniaxal crystal. To the authors' knowledge, the birefringent silica hydrogels were obtained by gelation under magnetic field for the first time. Also, scanning microscopic light scattering experiments have been performed. The results indicate that the characteristic length distribution for birefringent samples is narrower than that for non-birefringent ones.     

Rectification effect in thin-film superconductors in small,oscillatory magnetic fields

We have observed the generation of dc voltages across super conducting films of lead and tin due to the presence of a static magnetic fieldH ₀ upon which a small, oscillatory magnetic field component is superimposed. The voltages are created without an external current passing though the samples. They change sign with a reversal of the static fieldH ₀. The voltages are related to superconductivity and seem to be caused by a nonsymmetric penetration into the specimen of the magnetic field variation. During one cycle of the magnetic field oscillation a small fraction of the total flux entering and leaving the sample appears to be pumped across the specimen in a preferential direction. The thickness of the films ranged between 0.16 and 2.5 µm. The frequency and the amplitudeH ₁ of the oscillatory field was varied from 5 to 120 kHz and from 0 to 2 G rms, respectively. The rectified voltage varies between the different samples and depends uponH ₀, ,H ₁, and the orientation of the film relative to the magnetic field. It generally shows a sharp peak near the critical magnetic field. Small rectified voltages caused by the oscillatory field were observed far above the nominal, critical magnetic fields of the films. Apparently, these voltages were associated with the film edges and the enhancement of the critical field at the edges.Based on work performed under the auspices of the U.S. Atomic Energy Commission.     

Optimization of Low‐Dimensional Components of Quasi‐2D Perovskite Films for Deep‐Blue Light‐Emitting Diodes

Compared to efficient green and near‐infrared light‐emitting diodes (LEDs), less progress has been made on deep‐blue perovskite LEDs. They suffer from inefficient domain [various number of PbX₆^? layers (n)] control, resulting in a series of unfavorable issues such as unstable color, multipeak profile, and poor fluorescence yield. Here, a strategy involving a delicate spacer modulation for quasi‐2D perovskite films via an introduction of aromatic polyamine molecules into the perovskite precursor is reported. With low‐dimensional component engineering, the n₁ domain, which shows nonradiative recombination and retarded exciton transfer, is significantly suppressed. Also, the n₃ domain, which represents the population of emission species, is remarkably increased. The optimized quasi‐2D perovskite film presents blue emission from the n₃ domain (peak at 465 nm) with a photoluminescence quantum yield (PLQY) as high as 77%. It enables the corresponding perovskite LEDs to deliver stable deep‐blue emission (CIE (0.145, 0.05)) with an external quantum efficiency (EQE) of 2.6%. The findings in this work provide further understanding on the structural and emission properties of quasi‐2D perovskites, which pave a new route to design deep‐blue‐emissive perovskite materials.     

Gd5(SixGe1–x)4: An Extremum Material

The large shear displacements of atomic layers in Gd₅(Si_xGe_1–x)₄ materials, coupled with the change of crystallographic symmetry and magnetic order, characterizes these transformations as magnetic–martensitic, which are extremely rare. The start and the end of the magnetic–martensitic transitions depends strongly on the direction of change (i.e., increasing or decreasing) of either or both the temperature and magnetic field. These profound bonding, structural, electronic, and magnetic changes, which occur in the Gd₅(Si_xGe_1–x)₄ system, bring about some extreme changes of the materials' behavior resulting in a rich variety of unusually powerful magneto‐responsive properties, such as the giant magnetocaloric effect, colossal magnetostriction, and giant magnetoresistance.