Search Results (75)

A multimethodic approach based on infrared, Raman, electron spin resonance and photoluminescence spectroscopy, absorption spectroscopy in near infrared, visible and ultraviolet regions, single-crystal X-ray diffraction as well as electron microprobe analyses was applied to the characterization of a new commensurately modulated cubic haüyne analogue with the modulation parameter of 0.2 and unit-cell parameter of 45.3629(3) Å (designated as haüyne-45Å) from the Malobystrinskoe lazurite deposit, in the Baikal Lake area, Siberia, Russia, as well as associated SO₃²⁻-bearing afghanite. Haüyne-45Å is the second member, after vladimirivanovite, of the sodalite group with a commensurately modulated structure. The average structure is based on the tetrahedral aluminosilicate sodalite-type framework with sodalite cages of different sizes. The simplified formula of haüyne-45Å is Na₆Ca_2−x(Si₆Al₆O₂₄)(SO₄²⁻,HS⁻,S₂^●−,S₄,S₃^●−,S₅²⁻)_2−y. The structural modulations of the haüyne-45Å framework are presumably related to the regular alternation of SO₄²⁻ anions with polysulfide S₂^●−, S₃^●−, S₄, and S₅²⁻ groups detected by the spectroscopic methods. Mechanisms of thermal conversions of S-bearing groups in haüyne-45Å under oxidizing and reducing conditions at temperatures up to 800 °C are studied, and their geochemical importance is discussed. Full article

The new mineral achyrophanite (K,Na)₃(Fe³⁺,Ti,Al,Mg)₅O₂(AsO₄)₅ was found in high-temperature sublimates of the Arsenatnaya fumarole at the Second scoria cone of the Northern Breakthrough of the Great Tolbachik Fissure Eruption, Tolbachik volcano, Kamchatka, Russia. It is associated with aphthitalite-group sulfates, hematite, alluaudite-group arsenates (badalovite, calciojohillerite, johillerite, nickenichite, hatertite, and khrenovite), ozerovaite, pansnerite, arsenatrotitanite, yurmarinite, svabite, tilasite, katiarsite, yurgensonite, As-bearing sanidine, anhydrite, rutile, cassiterite, and pseudobrookite. Achyrophanite occurs as long-prismatic to acicular or, rarer, tabular crystals up to 0.02 × 0.2 × 1.5 mm, which form parallel, radiating, bush-like, or chaotic aggregates up to 3 mm across. It is transparent, straw-yellow to golden yellow, with strong vitreous luster. The mineral is brittle, with (001) perfect cleavage. D_calc is 3.814 g cm^–3. Achyrophanite is optically biaxial (+), α = 1.823(7), β = 1.840(7), γ = 1.895(7) (589 nm), 2V (meas.) = 60(10)°. Chemical composition (wt.%, electron microprobe) is: Na₂O 3.68, K₂O 9.32, CaO 0.38, MgO 1.37, MnO 0.08, CuO 0.82, ZnO 0.48, Al₂O₃ 2.09, Fe₂O₃ 20.42, SiO₂ 0.12, TiO₂ 7.35, P₂O₅ 0.14, V₂O₅ 0.33, As₂O₅ 51.88, SO₃ 1.04, and total 99.40. The empirical formula calculated based on 22 O apfu is Na_1.29K_2.15Ca_0.07Mg_0.34Mn_0.01Cu_0.11Zn_0.06Al_0.44Fe³⁺_2.77Ti_1.00Si_0.02P_0.02S_0.14V_0.04As_4.90O₂₂. Achyrophanite is orthorhombic, space group P222₁, a = 6.5824(2), b = 13.2488(4), c = 10.7613(3) Å, V = 938.48(5) ų and Z = 2. The strongest reflections of the PXRD pattern [d,Å(I)(hkl)] are 5.615(59)(101), 4.174(42)(022), 3.669(31)(130), 3.148(33)(103), 2.852(43)(141), 2.814(100)(042, 202), 2.689(29)(004), and 2.237(28)(152). The crystal structure of achyrophanite (solved from single-crystal XRD data, R = 4.47%) is unique. It is based on the octahedral-tetrahedral M-T-O pseudo-framework (M = Fe³⁺ with admixed Ti, Al, Mg, Na; T = As⁵⁺). Large-cation A sites (A = K, Na) are located in the channels of the pseudo-framework. The achyrophanite structure can be described as stuffed, with the defect heteropolyhedral pseudo-framework derivative of the orthorhombic Fe³⁺AsO₄ archetype. The mineral is named from the Greek άχυρον, straw, and φαίνομαι, to appear, in allusion to its typical straw-yellow color and long prismatic habit of crystals. Full article

A cheap, environmentally friendly, easily scalable post-treatment of Na-ZSM-5 (Si/Al molar ratio = 20 or 30) via electron-beam irradiation to produce hierarchical H-ZSM-5 as a propylene-increasing fluid catalytic cracking additive was performed. Higher specific surface areas and highly accessible porous systems were obtained among the irradiated samples. A combination of ²⁷Al, ¹H magic angle spinning nuclear magnetic resonance and NH₃-temperature-programmed desorption methods showed that upon irradiation, some of the framework’s tetrahedral Al atoms were removed as non-framework Al atoms via flexible coordination with Si-OH groups (either framework or non-framework defects), thus increasing the H-ZSM-5 acidity and stability during hydrothermal dealumination. The enhanced selectivity and stability toward propylene production over the irradiated H-ZSM-5 samples were attributed to the integration of the reserved population of medium acid sites into the highly accessible hierarchical network. N₂ adsorption–desorption isotherm data showed that the Si-rich H-ZSM-5 samples possessed an obvious ink-bottle-shaped micro-mesopore network and a greater degree of disordered orientation of the straight pore systems toward the exterior surfaces. Micro-activity test data suggested that with an increasing Si/Al ratio, the H-ZSM-5 additives lost some extent of their cracking activity due to the constricted hierarchical pore network toward the exterior surface but gained more stability and selectivity for propylene due to the reserved medium acid sites. Full article

It is significant to search for ultrasensitive and accurate testing technology for point-of-care monitoring of common diseases at home; for example, monitoring the Aβ-42 level at any time is crucial for patients suffering from Alzheimer’s disease. However, accurately monitoring the Aβ-42 level in serum is often thwarted by the challenges in sensitivity and specificity due to the multiplicated contaminations and intricated biofluid environments. Here, we develop a graphene field-effect transistor (G-FET) sensor modified with a type of rigid DNA framework aptamer—tetrahedral DNA nanostructure (TDN) for Aβ-42 detection in serum. The Aβ-42 specific aptamer combined with the rigid tetrahedral nanostructure achieves higher binding affinity and better specificity and anti-fouling ability. The detectable concentration reaches 5 × 10⁻¹⁸ mol L⁻¹ in serum, lower than most other assay approaches. Moreover, the sensor rapidly detects the Aβ-42 level in 6 supernatant samples from mice blood within 5 min and achieves high accuracy. This sensitive and specific method enabled by the DNA tetrahedron G-FET sensor has great potential in the monitoring of Alzheimer’s disease and other diseases. Full article

Spinel ferrites have emerged as fascinating materials, not just for their diverse functionalities, but for the dynamic structural transformations they undergo under varying conditions. These phase transitions, often subtle yet deeply influential, play a pivotal role in tuning their electronic, magnetic, and vibrational properties. At the heart of this complexity lies the versatile arrangement of divalent and trivalent cations between the tetrahedral (A) and octahedral (B) sites, giving rise to a rich spectrum of magnetic interactions, charge dynamics, and lattice responses. This intricate cation interplay makes spinel ferrites a playground for exploring structure–property relationships in advanced functional materials. In this study, we investigated the structural, vibrational, and magnetic properties of Cd ferrite using advanced hybrid functionals (B3LYP, HSE06, and PBE0). Our calculations reveal that the normal spinel phase is the most stable configuration, with minimal energy differences between spin arrangements (~0.005–0.008 eV) and slightly larger differences when including zero-point energy (~0.023 eV). All the investigated structures exhibit a semiconducting nature, with band gaps varying depending on the spin arrangements. The IR and Raman spectra highlight the influence of spin ordering on vibrational modes. The simulations of the Raman spectra demonstrate that both the frequencies and intensities of the Raman peaks strongly depend on the magnetic ordering. The present theoretical study offers a consistent framework for assigning vibrational modes, which may help resolve ambiguities and contribute to a deeper understanding of the vibrational properties of Cd ferrite. These findings provide a robust foundation for further experimental and computational exploration of this material. Full article

The catalytic performance of α-diiminonickel complexes is highly sensitive to structural modifications in their ligand frameworks. In this study, a series of unsymmetrical 2,3-bis(arylimino)butane-nickel complexes featuring ortho-2,6-dibenzhydryl groups as sterically demanding motifs and para-methyl groups as electron-donating enhancers were proposed and synthesized. These nickel complexes were thoroughly characterized using FTIR, elemental analysis, and single-crystal X-ray diffraction (for Ni4 and Ni5), revealing deviations from ideal tetrahedral geometry. Upon activation with Et₂AlCl, these complexes demonstrated exceptional ethylene polymerization activity, achieving a remarkable value of 13.67 × 10⁶ g PE mol⁻¹ (Ni) h⁻¹ at 20 °C. Notably, even at 80 °C, the nickel complexes maintained a high activity of 1.97 × 10⁶ g PE mol⁻¹ (Ni) h⁻¹, showcasing superiority compared to previously reported unsymmetrical 2,3-bis(arylimino)butane-nickel complexes. The resulting polyethylenes exhibited ultra-high molecular weights (M_w: 3.33–19.47 × 10⁵ g mol⁻¹) and tunable branching densities (84–217/1000C), which were effectively controlled by polymerization temperature. Moreover, the mechanical properties of the polyethylenes, including tensile strength (σ_b = 0.74–16.83 MPa), elongation at break (ε_b = 271–475%), and elastic recovery (SR = 42–74%), were finely tailored by optimizing molecular weight, crystallinity, and branching degree. The prepared polyethylenes displayed outstanding elastic recovery, a hallmark of high-performance thermoplastic elastomers, making them promising candidates for advanced material applications. Full article

Herein, we proposed a versatile G-quadruplex (G4)-tetrahedral DNA framework (G4-TDF) nanostructure functionalized origami microfluidic paper-based device (μPADs) for fluorescence detection of K⁺ by lighting up thioflavin T (ThT). In this work, TDF provided robust structural support for G-rich sequence in well-defined orientation and spacing to ensure high recognition efficiency, enabling sensitive fluorescence sensing on origami μPAD. After introducing ThT, the G-rich sequences extended from TDF vertices formed a parallel G4 structure, showing weak fluorescence signal output. Upon the presence of target K⁺, this parallel G4 structure transitioned to antiparallel G4 structure, leading to a significantly increase in fluorescence signal of ThT. Benefiting from the outstanding fluorescence enhancement characteristic of the G4 structure for ThT and excellent specificity of the G4 structure to K⁺ plus satisfactory recognition efficiency with the aid of TDF, this origami paper-based fluorescence sensing strategy exhibited an impressive detection limit as low as 0.2 mM with a wide range of 0.5–5.5 mM. This innovative G4-TDF fluorescence sensing was applied for the first time on μPAD, providing a simple, effective, and rapid method for K⁺ detection in human serum with significant potential for clinical diagnostics. Full article

Innovative magnetic techniques are pivotal for advancing mineral exploration. This study presents a self-structural constraint (SSC) method that jointly inverts aeromagnetic and gradient data to resolve high-resolution magnetic susceptibility models for concealed ores. The SSC framework integrates gradient structures from multi-component data as mutual constraints, enhancing signal differentiation and noise suppression. Unstructured tetrahedral grids and Poisson-derived analytical expressions address complex terrains, enabling robust inversions. Synthetic tests show SSC improves resolution by 40%–60% over conventional methods and resists 10% Gaussian noise. Applied to gold exploration in western Henan, China, SSC delineated concealed ore bodies (300–2000 m depth) along NE- and NW-trending faults, correlating with andesite-hosted magnetic anomalies. Combined with volcanic facies analysis, magma migration through these faults provided metallogenic materials and structural traps. The SSC-derived 3D model identified new drill targets, bridging geophysical imaging with geological processes. This advancement enhances the detection of deep, structurally controlled mineralization, offering a transformative tool for resource discovery. Full article

This work presents the synthesis and characterization of materials that contain Sn metal clusters formed by ligands of trimesic acid (Sn-BTC) or 5-sulfobenzene-1,3-dicarboxylic acid (Sn-H₃-5-SIP). These catalysts were used to convert levulinic acid with ethanol to produce ethyl levulinate under mild reaction conditions. The characterization results confirmed that Sn is mainly present in the cassiterite crystalline phase with a tetragonal rutile structure in octahedral and tetrahedral coordination in the materials. The assembly of trimesic acid (a hard base) with metal species (Sn) results in the formation of acid and thermally stable metal–organic frameworks. The use of 5-sulfobenzene-1,3-dicarboxylic acid instead of trimesic acid in the synthesis incorporates sulfonic groups in the material, enhancing the total acidity of the Sn-H₃-5-SIP catalyst compared to the Sn-BTC material. The Sn-H₃-5-SIP catalyst exhibited the highest catalytic activity when converting levulinic acid with ethanol, resulting in a turnover frequency (TOF) of 0.0495 s⁻¹, which is a 50% increase compared to the TOF of the Sn-BTC catalyst (0.0329 s⁻¹). This result can be attributed to its higher concentration of acid sites (2.23 ± 0.05 mmol H⁺/g_cat) and specific area (139 m²/g). Thus, materials containing tin metal clusters and sulfonic groups are promising materials that could be used as catalysts for synthesizing ethyl levulinate under mild reaction conditions. Full article

The wound repair process usually leads to a non-functioning mass of fibrotic tissue because of the oxidative imbalance of deep tissue layers. However, how to improve the penetration of active ingredients into deeper layers and regulate oxidative imbalances to create a regenerative microenvironment still remains a challenge. In this study, we designed a novel tetrahedral-framework nucleic acid (tFNA) nanozyme that could penetrate the skin/mucosa barrier as deep as 450 μm within 24 h. We also demonstrated the protective role of tFNAs on the mitochondrial structural and functional integrity and inhibition of reactive oxygen species production to repair oxidative imbalances through ERK1/2-Nrf2-HO-1 during repair processes. It was found that the proliferative state and the migration ability of postburn cells in vitro were accelerated, and the early closure of wounds in vivo was significantly promoted. This study therefore provides a promising strategy to efficiently regulate the oxidative imbalances in the deep layers of the skin during wound healing. Full article

Materials with high ion mobility are widely used in many fields of modern science and technology. Over the last 40 years, they have thoroughly changed our world. The paper characterizes the structural features of minerals and their synthetic analogs possessing this property. Special attention is paid to the ionic conductors with tetrahedral (zincite- and wurtzite-like), octahedral (ilmenite-like), and mixed (NASICON-like) frameworks. It is emphasized that the main conditions for fast ionic transport are related to the size and positions occupied by a mobile ion, their activation energy, the presence and diameter of conduction channels running inside the structure, isomorphic impurities, and other structural peculiarities. The results of the studies of solid electrolytes are dispersed in different editions, and the overview of new ideas related to their crystal structures was the focus of this paper. Full article

Sodium-ion batteries (SIBs) have emerged as a promising alternative to lithium-ion batteries (LIBs) due to the abundance and low cost of sodium resources. Cathode material plays a crucial role in the performance of sodium ion batteries determining the capacity, cycling stability, and rate capability. Na₃V₂(PO₄)₃ (NVP) is a promising cathode material due to its stable three-dimensional NASICON structure, but its discharge capacity is low and its decay is serious with the increase of cycle period. We focused on modifying NVP cathode material by coating carbon and doping Nb⁵⁺ ions for synergistic electrochemical properties of carbon-coated NVP@C as a cathode material. X-ray diffraction analysis was performed to confirm the phase purity and crystal structure of the Nb⁵⁺ doped NVP material, which exhibited characteristic diffraction peaks that matched well with the NASICON structure. Nb⁵⁺-doped NVP@C@Nb_x materials were prepared using the sol–gel method and characterized by X-ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Raman and Brunauer -Emmett-Teller (BET) analysis. First-principles calculations were performed based on density functional theory. VASP and PAW methods were chosen for these calculations. GGA in the PBE framework served as the exchange-correlation functional. The results showed the NVP unit cell consisted of six NVP structural motifs, each containing octahedral VO₆ and tetrahedral PO₄ groups to form a polyanionomer [V₂(PO₄)₃] along with the c-axis direction by PO₄ groups, which had Na1(6b) and Na2(18e) sites. And PDOS revealed that after Nb doping, the d orbitals of the Nb atoms also contributed electrons that were concentrated near the Fermi surface. Additionally, the decrease in the effective mass after Nb doping indicated that the electrons could move more freely through the material, implying an enhancement of the electron mobility. The electrochemical properties of the Nb⁵⁺ doped NVP@C@Nb cathode material were evaluated through cyclic voltammetry (CV), galvanostatic charge-discharge tests, electrochemical impedance spectroscopy (EIS), and X-ray photoelectric spectroscopy (XPS). The results showed that NVP@C@Nb_0.15 achieved an initial discharge capacity as high as 114.27 mAhg⁻¹, with a discharge capacity of 106.38 mAhg⁻¹ maintained after 500 cycles at 0.5C, and the retention rate of the NVP@C@Nb_0.15 composite reached an impressive 90.22%. NVP@C@Nb_0.15 exhibited low resistance and high capacity, enabling it to create more vacancies and modulate crystal structure, ultimately enhancing the electrochemical properties of NVP. The outstanding performance can be attributed to the Nb⁵⁺-doped carbon layer, which not only improves electronic conductivity but also shortens the diffusion length of Na⁺ ions and electrons, as well as reduces volume changes in electrode materials. These preliminary results suggested that the as-obtained NVP@C@Nb_0.15 composite was a promising novel cathode electrode material for efficient sodium energy storage. Full article

The restoration of endodontically treated teeth is one of the main challenges of restorative dentistry. The structure of the tooth is a complex assembly in which the materials that make it up, enamel and dentin, have very different mechanical behaviors. Therefore, finding alternative replacement materials for dental crowns in the area of restorative care isa highly significant challenge, since materials such as ceramic and zirconia have very different stress load resistance values. The aim of this study is to assess which material, either ceramic or zirconia, optimizes the behavior of a restored tooth under various typical clinical conditions and the masticatory load. A finite element analysis (FEA) framework is developed for this purpose. The 3D model of the restored tooth is input into the FEA software (Ansys Workbench R23)and meshed into tetrahedral elements. The presence of masticatory forces is considered: in particular, vertical, 45° inclined, and horizontal resultant forces of 280 N are applied on five contact points of the occlusal surface. The numerical results show that the maximum stress developed in the restored tooth including a ceramic crown and subject to axial load is about 39.381 MPa, which is rather close to the 62.32 MPa stress computed for the natural tooth; stresses of about 18 MPa are localized at the roots of both crown materials. In the case of the zirconia crown, the stresses are much higher than those in the ceramic crown, except for the 45° load direction, while, for the horizontal loads, the stress peak in the zirconia crown is almost three times as large as its counterpart in the ceramic crown (i.e., 163.24 MPa vs. 56.114 MPa, respectively). Therefore, the zirconia crown exhibits higher stresses than enamel and ceramic that could increase in the case of parafunctions, such as bruxism. The clinician’s choice between the two materials should be evaluated based on the patient’s medical condition. Full article

Herein, ordered mesoporous materials like SBA-15 and Al/SBA-15 were prepared using the pH adjustment method. Thus, these materials were developed in different pH of synthesis, from the pH adjustment method using a KCl/HCl solution and varying the Si/Al molar ratio (5, 25, and 75). All the ordered mesoporous materials were characterized by FRX, ²⁷Al NMR, SEM, XRD, N₂ adsorption/desorption, and CO₂ adsorption. From the applied method, it was possible to obtain SBA-15 and Al/SBA-15 with high mesoscopic ordering based on the XRD patterns, independent of the pH employed. From the chemical composition, the insertion of higher amounts of Al into the synthesis caused a progressive improvement in the structural and textural properties of the ordered mesoporous materials. Thus, the chosen synthesis conditions can lead to different aluminum coordination (tetrahedral and octahedral), which gives these materials a greater potential to be applied. The presence of Al in high amounts provides material with the ability to form micropores. Finally, the proposed method proved to be innovative; low-cost; less aggressive to the environment, with efficient insertion of aluminum in the framework of SBA-15 mesoporous material; and practical, based on only one step. Full article

Naturally fractured reservoirs are characterized by their complex nature due to the existence of natural fractures and fissures within the rock formations. These fractures can significantly impact the flow of fluids within the reservoir, making it difficult to predict and manage production. Therefore, efficient production from such reservoirs requires a deep understanding of the flow behavior via the integration of various geological, geophysical, and engineering data. Additionally, advanced simulation models can be used to predict reservoir behavior under different production scenarios and aid in decision making and effective management. Accordingly, this study presents a robust mathematical two-phase fluid flow model (FRACSIM) for the simulation of the flow behavior of naturally fractured reservoirs in a 3D space. The mathematical model is based on the finite element technique and implemented using the FORTRAN language within a poro-elastic framework. Fractures are represented by triangle elements, while tetrahedral elements represent the matrix. To optimize computational time, short to medium-length fractures adopt the permeability tensor approach, while large fractures are discretized explicitly. The governing equations for poro-elasticity are discretized in both space and time using a standard Galerkin-based finite element approach. The stability of the saturation equation solution is ensured via the application of the Galerkin discretization method. The 3D fracture model has been verified against Eclipse 100, a commercial software, via a well-test case study of a fractured basement reservoir to ensure its effectiveness. Additionally, the FRACSIM software successfully simulated a laboratory glass bead drainage test for two intersected fractures and accurately captured the flow pattern and cumulative production results. Furthermore, a sensitivity study of water injection using an inverted five-spot technique was tested on FRACSIM to assess the productivity of drilled wells in complex fractured reservoirs. The results indicate that FRACSIM can accurately predict flow behavior and subsequently be utilized to evaluate production performance in naturally fractured reservoirs. Full article