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Excellent ethylene selectivity in acetylene semi-hydrogenation is often obtained at the expense of activity. To break the activity-selectivity trade-off, precise control and in-depth understanding of the three-dimensional atomic structure of surfacial active sites are crucial. Here, we designed a novel Au@PdCu core-shell nanocatalyst featuring diluted and stretched Pd sites on the ultrathin shell (1.6 nm), which showed excellent reactivity and selectivity, with 100% acetylene conversion and 92.4% ethylene selectivity at 122 °C, and the corresponding activity was 3.3 times higher than that of the PdCu alloy. The atomic three-dimensional decoding for the activity-selectivity balance was revealed by combining pair distribution function (PDF) and reverse Monte Carlo simulation (RMC). The results demonstrate that a large number of active sites with a low coordination number of Pd-Pd pairs and an average 3.25% tensile strain are distributed on the surface of the nanocatalyst, which perform a pivotal function in the simultaneous improvement of hydrogenation activity and ethylene selectivity. Our work not only develops a novel strategy for unlocking the linear scaling relation in heterogeneous catalysis but also provides a paradigm for atomic 3D understanding of lattice strain in core-shell nanocatalysts.
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Nano ferroelectrics holds the potential application promise in information storage, electro-mechanical transformation, and novel catalysts but encounters a huge challenge of size limitation and manufacture complexity on the creation of long-range ferroelectric ordering. Herein, as an incipient ferroelectric, nanosized SrTiO3 was indued with polarized ordering at room temperature from the nonpolar cubic structure, driven by the intrinsic three-dimensional (3D) tensile strain. The ferroelectric behavior can be confirmed by piezoelectric force microscopy and the ferroelectric TO1 soft mode was verified with the temperature stability to 500 K. Its structural origin comes from the off-center shift of Ti atom to oxygen octahedron and forms the ultrafine head-to-tail connected 90° nanodomains about 2 to 3 nm, resulting in an overall spontaneous polarization toward the short edges of nanoparticles. According to the density functional theory calculations and phase-field simulations, the 3D strain-related dipole displacement transformed from [001] to [111] and segmentation effect on the ferroelectric domain were further proved. The topological ferroelectric order induced by intrinsic 3D tensile strain shows a unique approach to get over the nanosized limitation in nanodevices and construct the strong strain-polarization coupling, paving the way for the design of high-performance and free-assembled ferroelectric devices.
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Thermal expansion regulation by chemical decoration at a molecular level is of great technological value for materials science. Herein, we show that the spin crossover active compound Fe(pyz)Pt(CN)4 (pyz = pyrazine) shows a rare 2D negative thermal expansion (NTE) in the ab-plane. By introducing axial coordination iodine ions or reducing the framework dimension from 3D to 2D, the NTE behavior can be effectively switched to positive thermal expansion (PTE) or even zero thermal expansion (ZTE). Moreover, it is found that different spin states of Fe2+ also influence the magnitude of NTE. Compared with the low-spin (LS) sate, the high-spin (HS) state tends to enhance the magnitude of NTE. Combined in situ structural and Raman spectral analyses revealed that the NTE mainly originates from the transverse vibration of a bridging cyano group and the tailorable thermal expansion is closely related to the state of the Fe-CîN-Pt linkage. The present study shows how the rational regulation of the building unit and framework dimensions can effectively control thermal expansion behaviors. This insight can serve as guidance for designing and synthesizing novel NTE materials.
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Accurately decoding the three-dimensional atomic structure of surface active sites is essential yet challenging for a rational catalyst design. Here, we used comprehensive techniques combining the pair distribution function and reverse Monte Carlo simulation to reveal the surficial distribution of Pd active sites and adjacent coordination environment in palladium-copper nanoalloys. After the fine-tuning of the atomic arrangement, excellent catalytic performance with 98% ethylene selectivity at complete acetylene conversion was obtained in the Pd34Cu66 nanocatalysts, outperforming most of the reported advanced catalysts. The quantitative deciphering shows a large number of active sites with a Pd-Pd coordination number of 3 distributed on the surface of Pd34Cu66 nanoalloys, which play a decisive role in highly efficient semihydrogenation. This finding not only opens the way for guiding the precise design of bimetal nanocatalysts from atomic-level insight but also provides a method to resolve the spatial structure of active sites.
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Zero thermal expansion (ZTE) alloys with high mechanical response are crucial for their practical usage. Yet, unifying the ZTE behavior and mechanical response in one material is a grand obstacle, especially in multicomponent ZTE alloys. Herein, we report a near isotropic zero thermal expansion (αl = 1.10 × 10-6 K-1, 260-310 K) in the natural heterogeneous LaFe54Co3.5Si3.35 alloy, which exhibits a super-high toughness of 277.8 ± 14.7 J cm-3. Chemical partition, in the dual-phase structure, assumes the role of not only modulating thermal expansion through magnetic interaction but also enhancing mechanical properties via interface bonding. The comprehensive analysis reveals that the hierarchically synergistic enhancement among lattice, phase interface, and heterogeneous structure is significant for strong toughness. Our findings pave the way to tailor thermal expansion and obtain prominent mechanical properties in multicomponent alloys, which is essential to ultra-stable functional materials.
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Overcoming thermal quenching is generally essential for the practical application of luminescent materials. It has been recently found that frameworks with negative thermal expansion (NTE) could be a promising candidate to engineer unconventional luminescence thermal enhancement. However, the mechanism through which luminescence thermal enhancement can be well tuned remains an open issue. In this work, enabled by altering ligands in a series of UiO-66 derived Eu-based metal-organic frameworks, it was revealed that the changes in the thermal expansion are closely related to luminescence thermal enhancement. The NTE of the aromatic ring part favors luminescence thermal enhancement, while contraction of the carboxylic acid part plays the opposite role. Modulation of functional groups in ligands can change the thermal vibration of aromatic rings and then achieve luminescence thermal enhancement in a wide temperature window. Our findings pave the way to manipulate the NTE and luminescence thermal enhancement based on ligand engineering.
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A cubic metal exhibiting zero thermal expansion (ZTE) over a wide temperature window demonstrates significant applications in a broad range of advanced technologies but is extremely rare in nature. Here, enabled by high-temperature synthesis, we realize tunable thermal expansion via magnetic doping in the class of kagome cubic (Fd-3m) intermetallic (Zr,Nb)Fe2. A remarkably isotropic ZTE is achieved with a negligible coefficient of thermal expansion (+0.47 × 10-6 K-1) from 4 to 425 K, almost wider than most ZTE in metals available. A combined in situ magnetization, neutron powder diffraction, and hyperfine Mössbauer spectrum analysis reveals that interplanar ferromagnetic ordering contributes to a large magnetic compensation for normal lattice contraction upon cooling. Trace Fe-doping introduces extra magnetic exchange interactions that distinctly enhance the ferromagnetism and magnetic ordering temperature, thus engendering such an ultrawide ZTE. This work presents a promising ZTE in kagome metallic materials.
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Metallic phase (1T) MoS2 has been regarded as an ideal catalytic material for the hydrogen evolution reaction (HER) due to its high active site density and favorable electrical conductivity. However, the preparation of 1T-phase MoS2 samples requires tough reaction conditions and 1T-MoS2 has poor stability under alkaline conditions. In this work, 1T-MoS2/NiS heterostructure catalysts grown in situ on carbon cloth were prepared by a simple one-step hydrothermal method. The obtained MoS2/NiS/CC combines the advantages of high active site density and a self-supporting structure, achieving stable 77% metal phase (1T) MoS2. The combination of NiS and 1T-MoS2 enhances the intrinsic activity of MoS2 while the electrical conductivity is improved. These advantages enable the 1T-MoS2/NiS/CC electrocatalyst to have a low overpotential of 89 mV (@10 mA cm-2) and a small Tafel slope of 75 mV dec-1 under alkaline conditions and provide a synthetic strategy of stable 1T-MoS2-based electrocatalysts for the HER by a heterogeneous structure.
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Rapid progress in modern technologies demands zero thermal expansion (ZTE) materials with multi-property profiles to withstand harsh service conditions. Thus far, the majority of documented ZTE materials have shortcomings in different aspects that limit their practical utilization. Here, we report on a superior isotropic ZTE alloy with collective properties regarding wide operating temperature windows, high strength-stiffness, and cyclic thermal stability. A boron-migration-mediated solid-state reaction (BMSR) constructs a salient "plum pudding" structure in a dual-phase Er-Fe-B alloy, where the precursor ErFe10 phase reacts with the migrated boron and transforms into the target Er2Fe14B (pudding) and α-Fe phases (plum). The formation of such microstructure helps to eliminate apparent crystallographic texture, tailor and form isotropic ZTE, and simultaneously enhance the strength and toughness of the alloy. These findings suggest a promising design paradigm for comprehensive performance ZTE alloys.
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The insight into the three-dimensional configuration of ferroelectric ordering in ferroelectric nanomaterials is motivated by the application of the development of functional nanodevices and the structural designing. However, the atomic deciphering of the spatial distribution of ordered structure remains challenging for the limitation of dimension and probing techniques. In this paper, a neutron pair distribution function (nPDF) was utilized to analyze the spontaneous polarization distribution of zero-dimensional PbTiO3 nanoparticles in three dimensions, via the application of reverse Monte Carlo (RMC) modeling. The comprehensive identification with transmission electron microscopy verified the linear characteristics of polarization along the c-axis in the main body, while electric polarization distribution on the surface was enhanced abnormally. In addition, the correlation of dipole vectors extending to three unit cells below the surface is retained. This work shows an application of the micro/macroscale information to effectively decode the polarization structure of nanoferroelectrics, providing new views of designing nanoferroelectric devices.
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Lipids affect cartilage growth, injury, and regeneration in diverse ways. Diet and metabolism have become increasingly important as the prevalence of obesity has risen. Proper lipid supplementation in the diet contributes to the preservation of cartilage function, whereas excessive lipid buildup is detrimental to cartilage. Lipid metabolic pathways can generate proinflammatory substances that are crucial to the development and management of osteoarthritis (OA). Lipid metabolism is a complicated metabolic process involving several regulatory systems, and lipid metabolites influence different features of cartilage. In this review, we examine the current knowledge about cartilage growth, degeneration, and regeneration processes, as well as the most recent research on the significance of lipids and their metabolism in cartilage, including the extracellular matrix and chondrocytes. An in-depth examination of the involvement of lipid metabolism in cartilage metabolism will provide insight into cartilage metabolism and lead to the development of new treatment techniques for metabolic cartilage damage.
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Cartilagem Articular , Cartilagem Articular/metabolismo , Condrócitos/metabolismo , Metabolismo dos Lipídeos , Lipídeos , RegeneraçãoRESUMO
The revelation of the atomic 3D structure of sub-5 nm bimetal nanocatalysts challenges the limitations of conventional methods. Notably, the identification of the cooperative relationship between the active sites and nearby coordination environment during catalytic reactions depends on the stereo distribution of local phases and chemical composition within a short range. As a model nanocatalyst in our investigation, we studied the ordered PtFe bimetals in hydrogen evolution reactions (HER). By combining pair distribution functions with reverse Monte Carlo, local-range phase symmetry, chemical composition, and atom distribution were determined. The segregation of local phase segments as disordered Pt-rich A1 and Pt3Fe L12 phases can be attributed to the marked improvement of HER activity and stability in Pt56Fe44. Following the etching of the outermost-surface Fe, the remaining disordered segregation offered a large number of active Pt sites for discharge and electrochemical desorption reactions. It resulted in local-bonding Pt pairs that made it easier for adsorbed hydrogen atoms to recombine. The current research will provide structural insight into the local range for bimetal nanocatalysts and be valuable for the creation of new, low-cost nanocatalysts.
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Zero thermal expansion (ZTE) alloys as dimensionally stable materials are usually challenged by harsh environmental erosion, since ZTE and corrosion resistance are generally mutually exclusive. Here, a high-performance alloy, Zr0.8 Ta0.2 Fe1.7 Co0.3 , is reported, that shows isotropic ZTE behavior (αl = 0.21(2) × 10-6 K-1 ) in a wide temperature range of 5-360 K, high corrosion resistance in a seawater-like solution compared with classic Invar and stainless Invar, and excellent cyclic thermal and structural stabilities. Such stabilities are attributed to the cubic symmetry, the controllable magnetic order, and the spontaneously formed passive film with Ta and Zr chemical modifications. The results are evidenced by X-ray/neutron diffraction, microscopy, spectroscopy, and electrochemistry investigations. Such multiple stabilities have the potential to broaden the robust applications of ZTE alloys, especially in marine services.
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Two-dimensional negative thermal expansion (NTE) is achieved in a tetragonal oxalate-based metal-organic framework (MOF), CdZrSr(C2O4)4, within a temperature range from 123 to 398 K [space group I4Ì m2, αa = -2.4(7) M K-1, αc = 11.3(3) M K-1, and αV = 6.4(1) M K-1]. By combining variable-temperature X-ray diffraction, a high-resolution synchrotron X-ray pair distribution function, and thermogravimetry-differential scanning calorimetry, we shows that NTE within the ab plane derives from the oriented rotation of an oxalate ligand in zigzag chains (-CdO8-ox-ZrO8-ox-)∞. That is simplified to the Zr atom rotating with an unchanged Zr···Cd distance as the radius, which also gives rise to the deformation of a hingelike connection along the c axis and results in its positive thermal expansion. By virtue of the facile and low-cost oxalate ligand, the present NTE MOF may show application prospects in the future.
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Supported atomic dispersion metals are of great interest, and the interfacial effect between isolated metal atoms and supports is crucial in heterogeneous catalysis. Herein, the behavior of single-atom Cu catalysts dispersed on CeO2 (100), (110), and (111) surfaces has been studied by DFT + U calculations. The interactions between ceria crystal planes and isolated Cu atoms together with their corresponding catalytic activities for CO oxidation are investigated. The CeO2 (100) and (111) surfaces can stabilize active Cu+ species, while Cu exists as Cu2+ on the (110) surface. Cu+ is certified as the most active site for CO adsorption, which can promote the formation of the reaction intermediates and reduce reaction energy barriers. For the CeO2 (100) surface, the interaction between CO and Cu is weak and the CO adsorbate is more likely to activate the subsurface oxygen. The catalytic performance is closely related to the binding strength of CO to the active Cu single atoms on the different subsurfaces. These results bring a significant insight into the rational design of single metal atoms on ceria and other reducible oxides.
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TLR7 and TLR8 are key members of the Toll-like receptor family, playing crucial roles in the signaling pathways of innate immunity, and thus become attractive therapeutic targets of many diseases including infections and cancer. Although TLR7 and TLR8 show a high degree of sequence homology, their biological response to small molecule binding is very different. Aiming to understand the mechanism of selective profiles of small molecule modulators against TLR7 and TLR8, we carried out molecular dynamic simulations on three imidazoquinoline derivatives bound to the receptors separately. They are Resiquimod (R), Hybrid-2 (H), and Gardiquimod (G), selective agonists of TLR7 and TLR8. Our MD trajectories indicated that in the complex of TLR7-R and TLR7-G, the two chains forming the TLR7 dimer tended to remain "open" conformation, while the rest systems maintained in the closed format. The agonists R, H, and G developed conformational deviation mainly on the aliphatic tail. Furthermore, we attempted to quantify the selectivity between TLR7 and TLR8 by binding free energies via MM-GBSA method. It showed that the three selected modulators were more favorable for TLR7 than TLR8, and the ranking from the strongest to the weakest was H, R and G, aligning well with experimental data. In the TLR7, the flexible and hydrophobic aliphatic side chain of H has stronger van der Waals interactions with V381 and F351 but only pick up interaction with one amino acid residue i.e. Y353 of TLR8. Unsurprisingly, the positively charged side chain of G has less favorable interaction with I585 of TLR7 and V573 of TLR8 explaining G is weak agonist of both TLR7 and TLR8. All three imidazoquinoline derivatives can form stable hydrogen bonds with D555 of TLR7 and the corresponding D543 of TLR8. In brief, the set of total 400ns MD studies sheds light on the potential selectivity mechanisms of agonists towards TLR7 and TLR8, indicating the van der Waals interaction as the driving force for the agonists binding, thus provides us insights for designing more potent and selective modulators to cooperate with the hydrophobic nature of the binding pocket.
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Receptor 7 Toll-Like , Receptor 8 Toll-Like , Simulação de Dinâmica Molecular , Transdução de Sinais , Receptor 7 Toll-Like/metabolismo , Receptores Toll-LikeRESUMO
Osteoarthritis (OA) is a degenerative joint disease in the musculoskeletal system with a relatively high incidence and disability rate in the elderly. It is characterized by the degradation of articular cartilage, inflammation of the synovial membrane, and abnormal structure in the periarticular and subchondral bones. Although progress has been made in uncovering the molecular mechanism, the etiology of OA is still complicated and unclear. Nevertheless, there is no treatment method that can effectively prevent or reverse the deterioration of cartilage and bone structure. In recent years, in the field of pharmacology, research focus has shifted to disease prevention and early treatment rather than disease modification in OA. Biologic agents become more and more attractive as their direct or indirect intervention effects on the initiation or development of OA. In this review, we will discuss a wide spectrum of biologic agents ranging from DNA, noncoding RNA, exosome, platelet-rich plasma (PRP), to protein. We searched for key words such as OA, DNA, gene, RNA, exosome, PRP, protein, and so on. From the pharmacological aspect, stem cell therapy is a very special technique, which is not included in this review. The literatures ranging from January 2016 to August 2021 were included and summarized. In this review, we aim to help readers have a complete and precise understanding of the current pharmacological research progress in the intervention of OA from the biological aspect and provide an indication for the future translational studies.
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Super Invar (SIV), i.e., zero thermal expansion of metallic materials underpinned by magnetic ordering, is of great practical merit for a wide range of high precision engineering. However, the relatively narrow temperature window of SIV in most materials restricts its potential applications in many critical fields. Here, we demonstrate the controlled design of thermal expansion in a family of R_{2}(Fe,Co)_{17} materials (R=rare Earth). We find that adjusting the Fe-Co content tunes the thermal expansion behavior and its optimization leads to a record-wide SIV with good cyclic stability from 3-461 K, almost twice the range of currently known SIV. In situ neutron diffraction, Mössbauer spectra and first-principles calculations reveal the 3d bonding state transition of the Fe-sublattice favors extra lattice stress upon magnetic ordering. On the other hand, Co content induces a dramatic enhancement of the internal molecular field, which can be manipulated to achieve "ultrawide" SIV over broad temperature, composition and magnetic field windows. These findings pave the way for exploiting thermal-expansion-control engineering and related functional materials.
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Zero thermal expansion (ZTE) alloys possess unique dimensional stability, high thermal and electrical conductivities. Their practical application under heat and stress is however limited by their inherent brittleness because ZTE and plasticity are generally exclusive in a single-phase material. Besides, the performance of ZTE alloys is highly sensitive to change of compositions, so conventional synthesis methods such as alloying or the design of multiphase to improve its thermal and mechanical properties are usually inapplicable. In this study, by adopting a one-step eutectic reaction method, we overcome this challenge. A natural dual-phase composite with ZTE and plasticity was synthesized by melting 4 atom% holmium with pure iron. The dual-phase alloy shows moderate plasticity and strength, axial zero thermal expansion, and stable thermal cycling performance as well as low cost. By using synchrotron X-ray diffraction, in-situ neutron diffraction and microscopy, the critical mechanism of dual-phase synergy on both thermal expansion regulation and mechanical property enhancement is revealed. These results demonstrate that eutectic reaction is likely to be a universal and effective method for the design of high-performance intermetallic-compound-based ZTE alloys.
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Zero thermal expansion (ZTE) is an intriguing phenomenon by virtue of its peculiar lack of expansion and contraction with temperature. The achievement of ZTE in a metallic material is a desired but challenging task. Here we report the ZTE behavior of a single-phase metallic VB2 compound, stacking with the V and B atomic layers along the c direction (αV = 2.18 × 10-6 K-1, 5-150 K). Neutron powder diffraction demonstrates that the ZTE behavior is entangled in the direct blocking of the lattice expansion along all crystallographic directions with temperature. X-ray photoelectron spectroscopy and density functional theory calculations indicate that strong covalent binding adheres the nearest-neighbor B-B and V-B pairs, which is proposed to control the ZTE within both the basal plane and the c direction. An intimate correlation is revealed between the covalent binding and the lattice parameters. Our work indicates the opportunity to design metallic ZTE with strong chemical binding in the future.