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Until recently, mesoporous silica (MPS) particles have been successfully used in various biomedical applications including drug delivery. In the past decades, the research on MPS shifted sharply to gene delivery owing to its biocompatible, mesoporous structure that allows for loading oligonucleotides, shielding in the bloodstream, and delivering them to patient cells’ cytoplasm to stop cells’ genetic transcription. Until now, researchers faced several unique challenges and MPS, as oligonucleotide vectors, could not reach the clinical stage. In this study, material-related challenges were endeavored to overcome by a combined particle synthesis/oligo-loading strategy. DNA-encapsulated silica/polyethylene glycol (PEG) hybrid xerogels were synthesized at one step, via sol–gel technique. The xerogels were grinded into particles and characterized by X-ray diffraction, scanning electron microscopy, ultraviolet–visible spectroscopy, Fourier transform infrared spectroscopy, and gas adsorption analysis. The results demonstrated that uniform oligo-loaded silica/PEG hybrid xerogels could be synthesized without surface modification. Oligonucleotides were encapsulated inside the whole porous network, rather than attached only to particle surfaces as such in the conventional route. The results showed that PEG incorporation led to formation of monolithic xerogels, which could be grinded into spherical particles (557 ± 110 nm) with well-defined edges. Due to grinding, PEG chains were present both in the interior and on the surface of the particles. 10% PEG incorporation into silica precursor (tetraethyl orthosilicate) increased the resistance of DNA-encapsulated silica against protein degradation. In the overall sol–gel-derived silica/PEG hybrid materials were revealed as potential candidates for gene delivery applications such as RNA interference therapies.
Perovskite chalcogenides are gaining substantial interest as an emerging class of semiconductors for optoelectronic applications. High-quality samples are of vital importance to examine their inherent physical properties. We report the successful crystal growth of the model system, BaZrS3 and its Ruddlesden–Popper phase Ba3Zr2S7 by a flux method. X-ray diffraction analyses showed the space group of Pnma with lattice constants of a = 7.056(3) Å, b = 9.962(4) Å, and c = 6.996(3) Å for BaZrS3 and P42/mnm with a = 7.071(2) Å, b = 7.071(2) Å, and c = 25.418(5) Å for Ba3Zr2S7. Rocking curves with full width at half maximum of 0.011° for BaZrS3 and 0.027° for Ba3Zr2S7 were observed. Pole figure analysis, scanning transmission electron microscopy images, and electron diffraction patterns also establish the high quality of the grown crystals. The octahedral tilting in the corner-sharing octahedral network is analyzed by extracting the torsion angles.
A series of xLiMn0.5Fe0.5PO4–yLi3V2(PO4)3/C (x:y= 4:1, 3:1, 2:1, 1:1, 1:2, and 1:3) composite cathode materials for lithium-ion batteries are successfully prepared by the rheological phase reaction method. The structures, morphologies, and electrochemical properties of these composite materials are studied. The results indicate that xLiMn0.5Fe0.5PO4–yLi3V2(PO4)3/C composites are composed of LiMn0.5Fe0.5PO4 and Li3V2(PO4)3 phases and mutual doping exists. The initial discharge capacities, initial Coulombic efficiencies, and capacity retentions of composites increase but then decline with the increase of Li3V2(PO4)3 content. All the composites show higher capacity retentions than LiMn0.5Fe0.5PO4/C and Li3V2(PO4)3/C single phases except LMFP–3LVP/C. The composite material of x:y= 1:1 exhibits remarkably superior electrochemical performance than the single phases and other composites both in discharge capacity and cycle performance, delivering the initial discharge capacity of 148.2 mA h/g (2.0–4.5 V) and 170.1 mA h/g (2.0–4.8 V) at 0.1 C. And the corresponding capacity retentions are 98.0 and 90.4% after 100 cycles, respectively.
The phase evolution of reactive radio frequency (RF) magnetron sputtered Cr0.28Zr0.10O0.61 coatings has been studied by in situ synchrotron X-ray diffraction during annealing under air atmosphere and vacuum. The annealing in vacuum shows t-ZrO2 formation starting at ∼750–800 °C, followed by decomposition of the α-Cr2O3 structure in conjunction with bcc-Cr formation, starting at ∼950 °C. The resulting coating after annealing to 1140 °C is a mixture of t-ZrO2, m-ZrO2, and bcc-Cr. The air-annealed sample shows t-ZrO2 formation starting at ∼750 °C. The resulting coating after annealing to 975 °C is a mixture of t-ZrO2 and α-Cr2O3 (with dissolved Zr). The microstructure coarsened slightly during annealing, but the mechanical properties are maintained, with no detectable bcc-Cr formation. A larger t-ZrO2 fraction compared with α-Cr2O3 is observed in the vacuum-annealed coating compared with the air-annealed coating at 975 °C. The results indicate that the studied pseudo-binary oxide is more stable in air atmosphere than in vacuum.
In this paper, grandite core with Grs64±1Adr36±1Sps2 composition was crystallographically studied. This core represents zone A of the macroscopically visible five A–E zones of the optically anisotropic Grs58–64Adr36–42Sps2 grandite. The applied procedure includes the detailed analysis of the powder diffraction patterns, and the Rietveld refinements of the crystal structures in a series of 18 space groups and two mixtures, which were followed by the comparative analysis of the R-values, site occupancy factors, and the bond lengths and angles. Synthesis of all of the presented results allows us to undoubtedly conclude that studied grandite is not cubic, neither as monophase nor as multiple phases in a mixture. Namely, it was established that structural dissymmetrization occurred and that it crystallized in the disordered rhombohedral $R\bar{3}c$ or orthorhombic Fddd space groups, whereby the first one is more probable. Beside the established lower symmetry of the studied grandite, which could be treated as the primary cause, the residual strain is also not excluded as the second possible cause for its slight optical anisotropy.
Bioactive glass–ceramic powder reinforced alginate scaffold has been successfully prepared and characterized for bone tissue engineering application. Glass-ceramic (GC) particles were synthesized through a sol–gel process. Alginate scaffolds containing different weight percentages of GC were fabricated through a freeze-drying technique. The composite scaffolds were characterized for phase analysis through X-ray powder diffraction and microstructure analysis through field emission scanning electron microscopy. The swelling behavior, degradation behavior, bioactivity, cell adhesion, and osteogenic potential of the fabricated scaffolds were evaluated. Microstructural analysis showed a highly porous behavior of the scaffold having a macroporous pore size. The composite scaffolds showed good bioactivity where GC induces apatite formation. The compressive strength of the scaffold was enhanced with GC addition due to the reinforcement of the alginate matrix. In vitro cell studies revealed that the composite scaffolds promoted cell adhesion, proliferation, and osteogenesis. Fabricated scaffolds are a promising biomaterial candidate for bone substitution because of their attractive properties.
Periodic lattice materials have been studied extensively in numerous science and engineering fields. Despite the vast knowledge that has emerged, the activities have been stove-piped within individual research communities, often in isolation from those in related fields. To bring this work into a holistic framework, the present article considers the elements needed to integrate the study of lattice materials into the processing–structure–properties paradigm that underpins materials science as an academic discipline. The emphasis is on concepts of structure involving topology, morphology, and defects of lattice materials, with illustrations of structure–property relations in the context of lattice strength.
Amorphous carbon, germanium oxide, and 2-dimensional transition metal dichalcogenides grown by atomic layer deposition (ALD) are considered as promising materials for advanced nanoscale device fabrication processes and electronic devices, owing to their extraordinary characteristics. Deposition of these materials using ALD can overcome the limitations of current deposition techniques, including poor step coverage and wafer-scale uniformity, and uncontrollable stoichiometry. Despite these advantages, there has been a lack of research into these materials due to the absence of suitable precursors or optimized processes. In this review, we focus on these nonconventional materials, which have rarely been studied using ALD. The latest research progress and future outlook on these materials grown by ALD will be highlighted, with a particular focus on the applications of future nanoscale device fabrication processes and new concepts in device fabrication which could lead to a paradigm shift in electronics.
A multilevel nonvolatile memory based on an amorphous indium–gallium–zinc oxide thin-film transistor is successfully demonstrated by using an atomic layer–deposited ZnO film as a charge trapping layer. The memory device shows a much higher erasing efficiency at a negative bias, i.e., after erasing at −13 V for 1 μs, the threshold voltage shift is as large as −7.4 V. In the case of 13 V/1 μs programming (P) and −12 V/1 μs erasing (E), the device demonstrates an ON/OFF readout drain current (IDS) ratio of ∼103 after 105 s, and a large and stable ON/OFF IDS ratio of ∼106 till 104 of P/E cycles. Furthermore, multilevel memory characteristics are also demonstrated on the device, showing an IDS ratio of >102 for 4 different states. Additionally, the device also successfully demonstrates typical synaptic behaviors, such as excitatory and inhibitory postsynaptic current with different memory times at different memory states.
We deposit films of tin–calcium sulfide by atomic layer deposition (ALD) and demonstrate the metastability of this material. Rough and spiky films are obtained by using Sn and Ca precursors with different ligands, whereas compact and smooth films are obtained when the two metal sources share the same ligands. Compositional and quartz crystal microbalance results indicate that part of the underlaying SnS film is replaced and/or removed during the CaS ALD cycle during the ternary film deposition, possibly via a temperature-dependent cation exchange mechanism. The crystal structure transforms from orthorhombic to cubic as the calcium content increases. Furthermore, resistivity increases with calcium content in the alloy films, whereas optical band gap only depends weakly on Ca content. After annealing at 400 °C in an H2S environment, the cubic alloy film undergoes a phase transition into the orthorhombic phase and its resistivity also decreases. Both phenomena could be explained by phase separation of the metastable alloy.