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Chemical Science Jun 2024Metathesis reactions are widely used in synthetic chemistry. While state-of-the-art organic metathesis involves highly controlled processes where specific bonds are...
Metathesis reactions are widely used in synthetic chemistry. While state-of-the-art organic metathesis involves highly controlled processes where specific bonds are broken and formed, inorganic metathesis reactions are often extremely exothermic and, consequently, poorly controlled. Ternary nitrides offer a technologically relevant platform for expanding synthetic control of inorganic metathesis reactions. Here, we show that energy-controlled metathesis reactions involving a heterovalent exchange are possible in inorganic nitrides. We synthesized ZnWN by swapping Zn and Li between LiWN and ZnX (X = Br, Cl, F) precursors. The synchrotron powder X-ray diffraction and differential scanning calorimetry show that the reaction onset is correlated with the ZnX melting point and that product purity is inversely correlated with the reaction's exothermicity. Therefore, careful choice of the halide counterion (, ZnBr) allows the synthesis to proceed in a swift but controlled manner at a surprisingly low temperature for an inorganic nitride (300 °C). High resolution synchrotron powder X-ray diffraction and diffuse reflectance spectroscopy confirm the synthesis of a cation-ordered ZnWN semiconducting material. We hypothesize that this synthesis strategy is generalizable because many Li-M-N phases are known (where M is a metal) and could therefore serve as precursors for metathesis reactions targeting new ternary nitrides. This work expands the synthetic control of inorganic metathesis reactions in a way that will accelerate the discovery of novel functional ternary nitrides and other currently inaccessible materials.
PubMed: 38939135
DOI: 10.1039/d4sc00322e -
Nanoscale Advances Jun 2024Ultrasmall nanoparticles have a diameter between 1 and 3 nm at the border between nanoparticles and large molecules. Usually, their core consists of a metal, and the... (Review)
Review
Ultrasmall nanoparticles have a diameter between 1 and 3 nm at the border between nanoparticles and large molecules. Usually, their core consists of a metal, and the shell of a capping ligand with sulfur or phosphorus as binding atoms. While the core structure can be probed by electron microscopy, electron and powder diffraction, and single-crystal structure analysis for atom-sharp clusters, it is more difficult to analyze the ligand shell. In contrast to larger nanoparticles, ultrasmall nanoparticles cause only a moderate distortion of the NMR signal, making NMR spectroscopy a qualitative as well as a quantitative probe to assess the nature of the ligand shell. The application of isotope-labelled ligands and of two-dimensional NMR techniques can give deeper insight into ligand-nanoparticle interactions. Applications of one- and two-dimensional NMR spectroscopy to analyze ultrasmall nanoparticles are presented with suitable examples, including a critical discussion of the limitations of NMR spectroscopy on nanoparticles.
PubMed: 38933863
DOI: 10.1039/d4na00139g -
Pharmaceutics May 2024Acemetacin (ACM) is a new non-steroidal anti-inflammatory drug with anti-inflammatory, analgesic, and antipyretic effects. However, the poor water solubility and...
Acemetacin (ACM) is a new non-steroidal anti-inflammatory drug with anti-inflammatory, analgesic, and antipyretic effects. However, the poor water solubility and gastrointestinal side effects limit its use. Recently, the co-amorphous (CAM) strategy has attracted great interest to improve solubility for poorly water-soluble drugs, and basic amino acids have the potential to protect the gastrointestinal tract. In order to develop a highly efficient and low-toxic ACM formulation, we prepared ACM CAM systems, with basic amino acids (lysine, arginine, and histidine) as co-formers, using a cryo-milling method. The solid-state behaviors of the ACM CAM systems were characterized by polarizing light microscopy, differential scanning calorimetry, and powder X-ray diffraction. Fourier transform infrared spectroscopy and molecular docking were carried out to understand the formation mechanism. Moreover, the gastro-protective effects of ACM CAM systems were evaluated in a rat gastric ulcer model. The results demonstrated that the CAM systems improved the dissolution rates of ACM compared with the neat amorphous counterpart. Furthermore, ACM CAM systems are significantly effective in mitigating the ACM-induced gastric ulcer in rats, and the ulcer inhibition rates were almost 90%. More importantly, this study provided a useful method for mitigating drug-induced gastrointestinal damage and broadened the applications of drug-amino acid CAM systems.
PubMed: 38931867
DOI: 10.3390/pharmaceutics16060745 -
The Grafting of Hydroxyaromatic Organics within Layered Perovskites via a Microwave-Assisted Method.Molecules (Basel, Switzerland) Jun 2024A new series of inorganic-organic hybrid perovskite materials were prepared by microwave-assisted grafting reactions. Simple carboxylic acids, acetic acid, and propionic...
A new series of inorganic-organic hybrid perovskite materials were prepared by microwave-assisted grafting reactions. Simple carboxylic acids, acetic acid, and propionic acid, as well as hydroxyaromatic carboxylic acids, 3,5-dihydroxy benzoic acid (DBA), 5-hydroxyisophthalic acid (HPA), 4-hydroxybenzoic acid (HBA), and 4-hydroxy-4-biphenyl carboxylic acid (HBCA), were reacted with the Dion-Jacobson double-layered perovskite, HLaNbO and its alcoxy derivatives. Grafting was found to not occur with simple carboxylic acids, while those molecules with hydroxyls were all attached to the perovskite interlayers. Reactivity of the hydroxyaromatic carboxylic acids varied with the different layered perovskite hosts where reactions with HLaNbO did not occur, and those with n-propoxy-LaNbO were limited; the greatest extent of reactivity was seen with n-decoxy-LaNbO. This is attributed to the larger interlayer spacing available for the insertion of the various hydroxyaromatic carboxylic acid compounds. The loading exhibited by the grafting species was less than that seen with well-known long-chain alkoxy grafting groups. It is expected that the width of the molecules contributes to this where, due to the benzyl groups, the interlayer volume of the grafted moieties occupies a larger horizontal fraction, therefore minimizing the loading to the below half. X-ray powder diffraction and transmission electron microscopy studies found that grafting of the n-decoxy-LaNbO intermediates with the series of hydroxyaromatics resulted in a reduction in crystallinity along with a disruption of the layer structure. Raman data on the series show little variation in local structure except for HBCA, where there appears to be a lengthening of the Nb-O apical linkage and a possible reduction in the distortion of inner-layer NbO octahedra. The optical properties of the hydroxyaromatic carboxylic acid grafted perovskites were also investigated using diffuse-reflectance UV-Vis spectroscopy. The band gaps of DBA, HPA, and HBA were found to be similar to the parent (E ≈ 3.4 eV), while the HBCA was significantly less by ca. 0.6 eV. This difference is attributed to electron withdrawal from the perovskite block to the HBCA ligand, leading to a lower band gap for the HBCA compound. The methods described herein allow for the formation of a new series of inorganic-organic hybrid materials where the products are of interest as precursors to more complex architectures as well as models for band gap modification of metal oxide photocatalysts.
PubMed: 38930953
DOI: 10.3390/molecules29122888 -
Molecules (Basel, Switzerland) Jun 2024Using physical vapor deposition (PVD) technology, GeSe nanowires were successfully fabricated by heating GeSe powder at temperatures of 500 °C, 530 °C, 560 °C, 590...
Using physical vapor deposition (PVD) technology, GeSe nanowires were successfully fabricated by heating GeSe powder at temperatures of 500 °C, 530 °C, 560 °C, 590 °C, and 620 °C. The microstructure, crystal morphology, and chemical composition of the resulting materials were thoroughly analyzed employing methods like Scanning Electron Microscopy (SEM), X-ray Diffraction (XRD), plus Raman Spectroscopy. Through a series of photoelectric performance tests, it was discovered that the GeSe nanowires prepared at 560 °C exhibited superior properties. These nanowires not only possessed high crystalline quality but also featured uniform diameters, demonstrating excellent consistency. Under illumination at 780 nm, the GeSe nanowires prepared at this temperature showed higher dark current, photocurrent, and photoresponsivity compared to samples prepared at other temperatures. These results indicate that GeSe nanomaterials hold substantial potential in the field of photodetection. Particularly in the visible light spectrum, GeSe nanomaterials exhibit outstanding light absorption capabilities and photoresponse.
PubMed: 38930927
DOI: 10.3390/molecules29122860 -
Materials (Basel, Switzerland) Jun 2024Barium zirconate (BaZrO, BZO), which exhibits superior mechanical, thermal, and chemical stability, has been widely used in many applications. In dentistry, BZO is used...
Barium zirconate (BaZrO, BZO), which exhibits superior mechanical, thermal, and chemical stability, has been widely used in many applications. In dentistry, BZO is used as a radiopacifier in mineral trioxide aggregates (MTAs) for endodontic filling applications. In the present study, BZO was prepared using the sol-gel process, followed by calcination at 700-1000 °C. The calcined BZO powders were investigated using X-ray diffraction and scanning electron microscopy. Thereafter, MTA-like cements with the addition of calcined BZO powder were evaluated to determine the optimal composition based on radiopacity, diametral tensile strength (DTS), and setting times. The experimental results showed that calcined BZO exhibited a majority BZO phase with minor zirconia crystals. The crystallinity, the percentage, and the average crystalline size of BZO increased with the increasing calcination temperature. The optimal MTA-like cement was obtained by adding 20% of the 700 °C-calcined BZO powder. The initial and final setting times were 25 and 32 min, respectively. They were significantly shorter than those (70 and 56 min, respectively) prepared with commercial BZO powder. It exhibited a radiopacity of 3.60 ± 0.22 mmAl and a DTS of 3.02 ± 0.18 MPa. After 28 days of simulated oral environment storage, the radiopacity and DTS decreased to 3.36 ± 0.53 mmAl and 2.84 ± 0.27 MPa, respectively. This suggests that 700 °C-calcined BZO powder has potential as a novel radiopacifier for MTAs.
PubMed: 38930384
DOI: 10.3390/ma17123015 -
Materials (Basel, Switzerland) Jun 2024Cancer is a major worldwide public health problem. Although there have already been astonishing advances in cancer diagnosis and treatment, the scientific community...
Cancer is a major worldwide public health problem. Although there have already been astonishing advances in cancer diagnosis and treatment, the scientific community continues to make huge efforts to develop new methods to treat cancer. The main objective of this work is to prepare, using a green sol-gel method with coconut water powder (CWP), a new nanocomposite with a mixture of GdFeO and ZnFeO, which has never been synthesized previously. Therefore, we carried out a structural (DTA-TG and X-ray diffraction), morphological (SEM), and magnetic (VSM and hyperthermia) characterization of the prepared samples. The prepared nanocomposite denoted a saturation magnetization of 11.56 emu/g at room temperature with a ferromagnetic behavior and with a specific absorption rate (SAR) value of 0.5 ± 0.2 (W/g). Regarding cytotoxicity, for concentrations < 10 mg/mL, it does not appear to be toxic. Although the obtained results were interesting, the high particle size was identified as a problem for the use of this nanocomposite.
PubMed: 38930318
DOI: 10.3390/ma17122949 -
Materials (Basel, Switzerland) Jun 2024This study investigated the impact of low-temperature heat treatments on the mechanical and thermophysical properties of Cu-10Sn alloys fabricated by a laser powder bed...
This study investigated the impact of low-temperature heat treatments on the mechanical and thermophysical properties of Cu-10Sn alloys fabricated by a laser powder bed fusion (LPBF) additive manufacturing (AM) process. The microstructure, phase structure, and mechanical and thermal properties of the LPBF Cu-10Sn samples were comparatively investigated under both the as-fabricated (AF) condition and after low-temperature heat treatments at 140, 180, 220, 260, and 300 °C. The results showed that the low-temperature heat treatments did not significantly affect the phase and grain structures of the Cu-10Sn alloys. Both pre- and post-treatment samples displayed consistent grain sizes, with no obvious X-ray diffraction angle shift for the α phase, indicating that atom diffusion of the Sn element is beyond the detection resolution of X-ray diffractometers (XRD). However, the 180 °C heat-treated sample exhibited the highest hardness, while the AF samples had the lowest hardness, which was most likely due to the generation of precipitates according to thermodynamics modeling. Heat-treated samples also displayed higher thermal diffusivity values than their AF counterpart. The AF sample had the longest lifetime of ~0.19 nanoseconds (ns) in the positron annihilation lifetime spectroscopy (PALS) test, indicating the presence of the most atomic-level defects.
PubMed: 38930311
DOI: 10.3390/ma17122943 -
Materials (Basel, Switzerland) Jun 2024During industrial and laboratory processes involving material grinding, the grinding media endure prolonged high-collision and friction environments, resulting in...
During industrial and laboratory processes involving material grinding, the grinding media endure prolonged high-collision and friction environments, resulting in substantial wear. Consequently, this study adopts the hot-pressing sintering technique in powder metallurgy to prepare SiC-reinforced Fe-based wear-resistant composite grinding media, aiming to increase wear performance. For this purpose, Fe with 10 wt% SiC powders were milled for the fabrication of the composite. Then, sintering was performed by hot press at 1100 °C in a furnace. Scanning electron microscopy (SEM) and X-ray diffraction were employed to investigate the microstructures and phase of SiC-reinforced Fe-based matrix composite. Subsequently, comparative performance evaluations of the newly developed grinding media and traditional chromium-based media were conducted in terms of wear rate and grinding efficiency. The wear resistance tests revealed that the SiC-reinforced composite media displayed significantly superior wear resistance across various abrasives compared to the chromium-containing alternatives. Specifically, the composite media achieved a wear rate reduction of 2.9 times against standard sand over 1 h, and 2.3 and 2.4 times against sandstone and iron slag, respectively. Moreover, extended grinding for 3 hours further enhanced these reductions to 3.1, 2.4, and 2.7 times, respectively. Additionally, efficiency assessments indicated that at a 1:1 material ratio, the composite media outperformed the chromium-containing media in grinding efficiency by 7.5%, 12.5%, and 10.3% for standard sand, sandstone, and iron slag, respectively. Further increasing the material ratio to 3:1 resulted in efficiency improvements of 7.4%, 17.5%, and 11.3%, correspondingly.
PubMed: 38930309
DOI: 10.3390/ma17122940 -
Materials (Basel, Switzerland) Jun 2024The lower valence compensation of YMnCuO ( = 0.00, 0.05, and 0.10) is prepared by the solid-state reaction, and the effects of divalent cation Cu-doping on the...
The lower valence compensation of YMnCuO ( = 0.00, 0.05, and 0.10) is prepared by the solid-state reaction, and the effects of divalent cation Cu-doping on the construction and magnetic and dielectric attributes of multiferroic YMnO are systemically researched. Powder X-ray diffraction shows YMnCuO has a single-phase hexagonal construction with a space group as the parent YMnO, and lattice parameters decrease systematically as Cu concentration increases. Using the scanning electric microscope, structure morphologies analysis shows that the mean grain size varies between 1.90 and 2.20 μm as Cu content increases. YMnCuO magnetization increases as Cu doping concentration increases, and the antiferromagnetic transition temperature declines from 71 K for = 0.00 to 58 K for = 0.10. The valence distributions of Mn ions conduce to the modified magnetic attributes. Due to Cu substitution, the dielectric loss and dielectric constant decline as frequency increases from 400 to 700 K, showing representative relaxation behaviors. Indeed, that is a thermally activated process. In addition, the peak of the dielectric loss complies with the Arrhenius law. The relaxation correlates to the dipole effect regarding carrier hopping between Mn and Mn, and also correlates to oxygen vacancies generated by Mn.
PubMed: 38930298
DOI: 10.3390/ma17122929