Search Results (23)

Pressure-induced nitrogen-rich compounds hold significant application prospects in high-energy-density materials. Utilizing first-principles calculations and swarm-intelligence structure search methods, we have identified ten new types of Gd-N compounds with different configurations, such as one-dimensional N-chains composed of N₆ rings or N₈ rings, and two-dimensional N-layers constructed of N₁₄ rings, N₁₈ rings, or N₁₈ + N₆ rings. Moreover, the predicted Gd-N compounds exhibit different magnetic properties, and a magnetic phase diagram is constructed in the pressure range of 0 to 200 GPa. Remarkably, the volumetric energy density (11.58–17.79 kJ/cm³) of Gd polynitrides with high nitrogen content, including P-1(I)-GdN₆, P-1(II)-GdN₆, R-3-GdN₈, C2mm-GdN₉, and P1-GdN₁₀, surpassed that of TNT (7.05 kJ/cm³), making them promising candidates for energetic materials. The discovery of diverse chain-like and layered structures in the GdN_x compounds highlights the role of gadolinium in inducing the diversity and complexity of nitrogen arrangements. Full article

Pore engineering is commonly used to alter the properties of metal–organic frameworks. This is achieved by incorporating different linker molecules (L) into the structure, generating isoreticular frameworks. CPO-27, also named MOF-74, is a prototypical material for this approach, offering the potential to modify the size of its one-dimensional pore channels and the hydrophobicity of pore walls using various linker ligands during synthesis. Thermal activation of these materials yields accessible open metal sites (i.e., under-coordinated metal centers) at the pore walls, thus acting as strong primary binding sites for guest molecules, including water. We study the effect of the pore size and linker hydrophobicity within a series of Ni²⁺-based isoreticular frameworks (i.e., Ni₂L, L = dhtp, dhip, dondc, bpp, bpm, tpp), analyzing their water sorption behavior and the water interactions in the confined pore space. For this purpose, we apply water vapor sorption analysis and Fourier transform infrared spectroscopy. In addition, defect degrees of all compounds are determined by thermogravimetric analysis and solution ¹H nuclear magnetic resonance spectroscopy. We find that larger defect degrees affect the preferential sorption sites in Ni₂dhtp, while no such indication is found for the other materials in our study. Instead, strong evidence is found for the formation of water bridges/chains between coordinating water molecules, as previously observed for hydrophobic porous carbons and mesoporous silica. This suggests similar sorption energies for additional water molecules in materials with larger pore sizes after saturation of the primary binding sites, resulting in more bulk-like water arrangements. Consequently, the sorption mechanism is driven by classical pore condensation through H-bonding anchor sites instead of sorption at discrete sites. Full article

The features or actuation behaviors of nature’s creatures provide concepts for the development of biomimetic soft bioactuators/robots with stimuli-responsive capabilities, design convenience, and environmental adaptivity in various fields. Mimosa pudica is a mechanically responsive plant that can convert pressure to the motion of leaves. When the leaves receive pressure, the occurrence of asymmetric turgor in the extensor and flexor sides of the pulvinus from redistributing the water in the pulvinus causes the bending of the pulvinus. Inspired by the actuation of Mimosa pudica, designing soft bioactuators can convert external stimulations to driving forces for the actuation of constructs which has been receiving increased attention and has potential applications in many fields. 4D printing technology has emerged as a new strategy for creating versatile soft bioactuators/robots by integrating printing technologies with stimuli-responsive materials. In this study, we developed a hybrid ink by combining gelatin methacryloyl (GelMA) polymers with iron oxide nanoparticles (IONs). This hybrid ION-GelMA ink exhibits tunable rheology, controllable mechanical properties, magnetic-responsive behaviors, and printability by integrating the internal metal ion-polymeric chain interactions and photo-crosslinking chemistries. This design offers the inks a dual crosslink mechanism combining the advantages of photocrosslinking and ionic crosslinking to rapidly form the construct within 60 s of UV exposure time. In addition, the magnetic-responsive actuation of ION-GelMA constructs can be regulated by different ION concentrations (0–10%). Furthermore, we used the ION-GelMA inks to fabricate a Mimosa pudica-like soft bioactuator through a mold casting method and a direct-ink-writing (DIW) printing technology. Obviously, the pinnule leaf structure of printed constructs presents a continuous reversible shape transformation in an air phase without any liquid as a medium, which can mimic the motion characteristics of natural creatures. At the same time, compared to the model casting process, the DIW printed bioactuators show a more refined and biomimetic transformation shape that closely resembles the movement of the pinnule leaf of Mimosa pudica in response to stimulation. Overall, this study indicates the proof of concept and the potential prospect of magnetic-responsive ION-GelMA inks for the rapid prototyping of biomimetic soft bioactuators/robots with untethered non-contact magneto-actuations. Full article

We present a novel type of magnetorheological material that allows one to restructure the magnetic particles inside the finished composite, tuning in situ the viscoelasticity and magnetic response of the material in a wide range using temperature and an applied magnetic field. The polymer medium is an A-g-B bottlebrush graft copolymer with side chains of two types: polydimethylsiloxane and polystyrene. At room temperature, the brush-like architecture provides the tissue mimetic softness and strain stiffening of the elastomeric matrix, which is formed through the aggregation of polystyrene side chains into aggregates that play the role of physical cross-links. The aggregates partially dissociate and the matrix softens at elevated temperatures, allowing for the effective rearrangement of magnetic particles by applying a magnetic field in the desired direction. Magnetoactive thermoplastic elastomers (MATEs) based on A-g-B bottlebrush graft copolymers with different amounts of aggregating side chains filled with different amounts of carbonyl iron microparticles were prepared. The in situ restructuring of magnetic particles in MATEs was shown to significantly alter their viscoelasticity and magnetic response. In particular, the induced anisotropy led to an order-of-magnitude enhancement of the magnetorheological properties of the composites. Full article

This study presents a phytochemical survey of two common intertidal red algal species, Bostrychia scorpioides and Catenella caespitosa, regarding their MAA (mycosporine-like amino acid) composition, which are known as biogenic sunscreen compounds. Six novel MAAs from Bostrychia scorpioides named bostrychines and two novel MAAs from Catenella caespitosa named catenellines were isolated using a protocol which included silica gel column chromatography, flash chromatography on reversed phase material and semipreparative HPLC (High-Performance Liquid Chromatography). The structure of the novel MAAs was elucidated using NMR (Nuclear Magnetic Resonance) and HR-MS (High-Resolution Mass Spectrometry), and their absolute configuration was confirmed by ECD (Electronic Circular Dichroism). All isolated MAAs possess a cyclohexenimine scaffold, and the metabolites from B. scorpioides are related to the known MAAs bostrychines A-F, which contain glutamine, glutamic acid and/or threonine in their side chains. The new MAAs from C. caespitosa contain taurine, an amino sulfonic acid that is also present in another MAA isolated from this species, namely, catenelline. Previous and new data confirm that intertidal red algae are chemically rich in MAAs, which explains their high tolerance against biologically harmful ultraviolet radiation. Full article

Quantum fluctuations inherent in electronic systems positioned close to magnetic instabilities can lead to novel collective phenomena. One such material, $\beta$-Ti${}_6$Sn${}_5$, sits close to ferromagnetic (FM) instability and can be pushed to an itinerant FM-ordered state with only minute magnetic or non-magnetic doping. The binary nature of this compound, however, limits the tuning variables that can be applied to study any emergent physics, which are likely to be sensitive to the introduction of chemical disorder.Accordingly, we grew high-quality single crystals of a new quaternary compound Zr${}_3$V${}_3$GeSn${}_4$ from a Sn-rich self flux, and determined the structure with single-crystal X-ray diffraction. Zr${}_3$V${}_3$GeSn${}_4$ forms in an ordered derivative of the hexagonal $\beta$-Ti${}_6$Sn${}_5$ structure with Zr and V atomic positions that show no indication of site interchange. Ge likewise occupies a single unique atomic position. The V site, which would be the one most likely to give rise to any magnetic character, is located at the center of a distorted octahedron of Sn, with such octahedra arranged in face-sharing chains along the crystallographic c axis, while the chains themselves are organized in a kagome geometry. Zr${}_3$V${}_3$GeSn${}_4$ represents the second known quaternary phase within this system, suggesting that other compounds with this structure type await discovery. Full article

Due to the abuse of antibiotics, the sensitivity of patients to antibiotics is gradually reduced. This work develops a Fe₃O₄@SiO₂@Au/PDA nanochain which shows an interesting magnetic-field-induced improvement of its photothermal antibacterial property. First, SiO₂ was wrapped on Fe₃O₄ nanospheres assembled in a chain to form a Fe₃O₄@SiO₂ nanocomposite with a chain-like nanostructure. Then, the magnetic Fe₃O₄@SiO₂@Au/PDA nanochains were prepared using in situ redox-oxidization polymerization. Under the irradiation of an 808 nm NIR laser, the temperature rise of the Fe₃O₄@SiO₂@Au/PDA nanochain dispersion was obvious, indicating that they possessed a good photothermal effect. Originating from the Fe₃O₄, the Fe₃O₄@SiO₂@Au/PDA nanochain showed a typical soft magnetic behavior. Both the NIR and magnetic field affected the antimicrobial performance of the Fe₃O₄@SiO₂@Au/PDA nanochains. Escherichia coli and Staphylococcus aureus were used as models to verify the antibacterial properties. The experimental results showed that the Fe₃O₄@SiO₂@Au/PDA nanochains exhibited good antibacterial properties under photothermal conditions. After applying a magnetic field, the bactericidal effect was further significantly enhanced. The above results show that the material has a broad application prospect in inhibiting the growth of bacteria. Full article

We present a detailed study of the field-dependent specific heat of the bimetallic ferromagnetically coupled chain compound MnNi(NO${}_2$)${}_4$(en)${}_2$, en = ethylenediamine. For this material, which in zero field orders antiferromagnetically below $T_N=2.45$ K, small fields suppress magnetic order. Instead, in such fields, a double-peak-like structure in the temperature dependence of the specific heat is observed. We attribute this behavior to the existence of an acoustic and an optical mode in the spin-wave dispersion as a result of the existence of two different spins per unit cell. We compare our experimental data to numerical results for the specific heat obtained by exact diagonalization and Quantum Monte Carlo simulations for the alternating spin-chain model, using parameters that have been derived from the high-temperature behavior of the magnetic susceptibility. The interchain coupling is included in the numerical treatment at the mean-field level. We observe remarkable agreement between experiment and theory, including the ordering transition, using previously determined parameters. Furthermore, the observed strong effect of an applied magnetic field on the ordered state of MnNi(NO${}_2$)${}_4$(en)${}_2$ promises interesting magnetocaloric properties. Full article

It has been shown that the photonic bandgap of one-dimensional (1D) dielectric periodic thin films can vanish at the first Bragg condition for TM modes. Here, we address the case of 1D photonic crystal slabs formed by a chain of high-index dielectric particles with transversal confinement and show that the Bragg bandgap can vanish for both TE- and TM-like modes. Calculations using plane-wave expansion and finite-difference time-domain methods confirm that the PBG vanishes. PBG closure is explained as being a result of the interplay between the electric and magnetic dipole resonances of the isolated nanoparticle with Bragg resonance, as confirmed by calculating the electric and magnetic dipoles of the isolated nanobricks. This can be considered as a manifestation of the metamaterial behavior of the 1D system when using silicon as an underlying material. Our finding may have important consequences for the fields of photonic crystals and all-dielectric metamaterials. Full article

A number of materials are studied in the field of magnetic hyperthermia. In general, the most promising ones appear to be iron oxide particle nanosystems. This is also indicated in some clinical trial studies where iron-based oxides were used. On the other hand, the type of material itself provides a number of variations on how to tune hyperthermia indicators. In this paper, magnetite nanoparticles in various forms were analyzed. The nanoparticles differed in the core size as well as in the form of their arrangement. The arrangement was determined by the nature of the surfactant. The individual particles were covered chemically by dextran; in the case of chain-like particles, they were encapsulated naturally in a lipid bilayer. It was shown that in the case of chain-like nanoparticles, except for relaxation, a contribution from magnetic hysteresis to the heating process also appears. The influence of the chosen methodology of magnetic field generation was also analyzed. In addition, the influence of the chosen methodology of magnetic field generation was analyzed. The application of a rotating magnetic field was shown to be more efficient in generating heat than the application of an alternating magnetic field. However, the degree of efficiency depended on the arrangement of the magnetite nanoparticles. The difference in the efficiency of the rotating magnetic field versus the alternating magnetic field was much more pronounced for individual nanoparticles (in the form of a magnetic fluid) than for systems containing chain nanoparticles (magnetosomes and a mix of magnetic fluid with magnetosomes in a ratio 1:1). Full article

The conducting polymer poly(2-(1H-pyrrole-1-yl)ethyl methacrylate (PPEMA) was synthesized by conventional atom transfer radical polymerization for the first time from free as well as surface-bonded alkyl bromide initiator. When grafted from the surface of carbonyl iron (CI) a substantial conducting shell on the magnetic core was obtained. Synthesis of the monomer as well as its polymer was confirmed using proton spectrum nuclear magnetic resonance (¹H NMR). Polymers with various molar masses and low dispersity showed the variability of this approach, providing a system with a tailorable structure and brush-like morphology. Successful grafting from the CI surface was elucidate by transmission electron microscopy and Fourier-transform infrared spectroscopy. Very importantly, thanks to the targeted nanometer-scale shell thickness of the PPEMA coating, the magnetization properties of the particles were negligibly affected, as confirmed using vibration sample magnetometry. Smart elastomers (SE) consisting of bare CI or CI grafted with PPEMA chains (CI-PPEMA) and silicone elastomer were prepared and dynamic mechanical properties as well as interference shielding ones were investigated. It was found that short polymer chains grafted to the CI particles exhibited the plasticizing effect, which might be interesting from the magnetorheological point of view, and more interestingly, in comparison to the neat CI-based sample, it provided enhanced electromagnetic shielding of nearly 30 dB in thickness of 500 μm. Thus, SE containing the newly synthesized CI-PPEMA hybrid particles also exhibited considerably enhanced damping factor and proper mechanical performance, which make the material highly promising from various practical application points of view. Full article

The magnetic nanochain-like material has been regards as one of the most promising electromagnetic (EM) absorbing material but remains a challenging. Herein, magnetic chain-like ferrite (included Fe₃O_4, CoFe₂O₄ and NiFe₂O₄) are successfully produced through a general solvothermal method, using PVP as the structural-liking agent. Experimental results confirm the ultimate sample possess a 3-dimensional chain-like structure which are constructed by numerous ferrite’s nanoparticles with ~60 nm in diameter. Their electromagnetic parameters can be also manipulated by such a chain structure, especially the dielectric loss, where a sharply increases can be observed on within a lower filling ratio. It greatly benefits to the EM absorbing property. In this article, the electromagnetic absorption layer made with a lower content of ferrite possess the excellent electromagnetic absorption ability, where the optimized effective absorption band was nearly 6.4 GHz under a thickness of 1.8 mm. Moreover, the filling ratio is only 30 wt%. Our method for designing of chain-like magnetic material can be helpful for producing wideband electromagnetic absorption in a low filling ratio. Full article

Novel porous magnetic soft materials (pMSMs) based on a poly (vinyl alcohol) (PVA) porous matrix filled with CuNi nanoparticles (NPs) of around 70 nm were synthesized. Initially, magnetic CuNi NPs were fabricated by the reduction of Ni and Cu ions with hydrazine hydrate in ethylene glycol medium in the absence of other capping agents. The pMSMs are subsequently fabricated by mixing CuNi NPs and PVA through freezing-drying process. The as-obtained pMSMs can respond to a magnetic field, i.e., the compressive modulus increase under a magnetic field of 0.23 T. The experimental results indicate that CuNi NPs can easily move to form chain-like structures under the application of a magnetic field. A combination of direct observation and finite element modeling has shown that under the influence of a magnetic field, chain-like aggregates of CuNi NPs lead to self-reinforcement of the pMSMs and, thus, to the increased compressive modulus. From a technological point of view, these materials with good magnetic responsiveness and moderate mechanical strength have potential applications in artificial muscle, soft actuators and drug release, to name a few. Full article

Neodymium-Iron-Boron (NdFeB) based permanent magnets are indispensable in today’s technology-driven society. Moreover, their use is likely to increase since they are key in clean energy applications such as wind turbines, hybrid/electric vehicles, and electric bikes. They contain critical raw materials as rare earth elements are used. Indeed, permanent magnets are considered strategic materials by the EU, and their recycling represents a potential secondary supply to decrease the import dependence. The VALOMAG project is developing a technical solution to recover rare earth (RE) based permanent magnets by dismantling end-of-life (EoL) products such as computer hard disc drives, electric motors, and generators from electric vehicles and wind turbines. It also assesses two short loop recycling technologies: Hydrogen Decrepitation (HD) or Hydrogenation–Disproportionation–Desorption–Recombination (HDDR) and strip-casting for high and medium quality magnet wastes; and hydrometallurgical processes for EoL low-quality magnets. Moreover, Life Cycle Assessment (LCA) and Process Integration with a Flowsheet simulation tool will integrate the whole recycling value chain (collection, dismantling, physical and chemical treatment options, and re-manufacturing) and assess the environmental impact and processes efficiency. A market study on the types and expected future quantities for the scrap magnets and the characterisation of the EoL magnets from hard disc drives (HDD) will be presented as preliminary results. Pre-treatment and sorting of 2.5 tons of NdFeB magnets scraps were carried out, and the two short loop recycling routes and the hydrometallurgical route are under investigation at the lab and pilot scale. The results will be used to develop a process integration and to assess the three routes through LCA. Full article

A series of novel comb-like poly(butyl acrylate)-g-poly(dimethylaminoethyl methacrylate) (PBA-g-PDMAEMA) with different side chain lengths were designed and successfully synthesized by the “first main chain then side chain” method. Infrared Spectroscopy (IR), ¹H Nuclear Magnetic Resonance (¹H NMR), and gel permeation chromatography (GPC) were used for structural confirmation and molecular weight characterization. This polymer exhibited responsive behavior from hydrophilicity to hydrophobicity under the alkaline environment of cement-based materials, with the contact angle of 105.6°, a decreased evaporation rate, and a hydrophile–lipophile balance (HLB) value. A significant internal hydrophobic effect on cement mortar was shown in the water absorption rate, which decreased by 75.2%, and a dry shrinkage-reducing rate of more than 30%. Furthermore, this polymer can effectively slow the exothermic rate, reduce the heat release, and delay the exothermic peak of cement hydration. It was interesting that these properties showed a direct correlation with the side chain length of the comb polymer. The aims of this study are to provide a new avenue to synthesize polymers with the spontaneous hydrophilicity–hydrophobicity transition in the cement system, achieving excellent internal hydrophobicity of cement-based materials, and to offer a promising alternative to resist external erosion for improving the durability and service life of cement-based materials. Full article