Search Results (5,806)

Co- and Ni-doped mullite–spinel ceramics were synthesized via a sol–gel method followed by high-temperature sintering in order to investigate the influence of dopant type on the phase evolution, microstructure, and optical properties. X-ray diffraction analysis confirmed the formation of a multiphase system consisting of mullite and spinel phases, with a residual amorphous fraction, the amount of which decreases with increasing temperature. FTIR and Raman spectroscopy indicate progressive structural ordering of both spinel and aluminosilicate networks during thermal treatment, with differences in crystallization behavior between Co- and Ni-containing system. UV–Vis spectroscopy revealed characteristic absorption bands arising from d–d electronic transitions of Co²⁺ and Ni²⁺ ions in the ceramic matrix, reflecting differences in their local coordination environments and optical behavior. Colorimetric analysis showed that Co-doped samples exhibit intense blue coloration, whereas Ni-doped ceramics display greenish-blue hues. The temperature-dependent evolution of the L*, a*, and b* parameters correlate with structural changes. The results suggest that the type of additive influences the phase evolution and optical response in mullite–spinel ceramics, in agreement with structural and spectroscopic analyses. Full article

Cubane-type iron–sulfur clusters play central roles in biological nitrogen fixation, where precise redox regulation governs multi-electron transfer processes. However, how heterometal centers and terminal ligands cooperatively modulate the electronic structure and redox behavior of such clusters remains insufficiently understood. Herein, we report a systematic study on a series of cubane-type [MoFe₃S₃N] clusters as structural mimics of nitrogenase cofactors. Using [(Tp*)MoFe₃S₃(μ₃-NSiMe₃)Cl₃]⁻ as a common precursor, thiolate (RS⁻; R = Me, Et, Ph) and N-heterocyclic carbene (NHC^R; R = Me, Et, iPr) ligands were introduced to probe ligand effects under an invariant cluster framework. All complexes were fully characterized by single-crystal X-ray diffraction and electrochemical measurements. Combined with previously reported tungsten analogues, a direct comparison reveals that both heterometal identity (Mo vs. W) and terminal ligand environment significantly influence local electron density and intermetallic redox cooperativity. Notably, strong σ-donating NHC ligands and heavier heterometal centers induce distinct modulation patterns, highlighting their synergistic roles. This work provides a unified platform for disentangling metal- and ligand-driven effects and offers feasible strategies for the rational tuning of redox properties in heterometallic Fe–S clusters. Full article

Single-crystal diamond (SCD) is an ideal substrate material for semiconductor devices due to its extremely wide bandgap and exceptionally high thermal conductivity. However, diamond’s extreme hardness and chemical inertness pose challenges for the fabrication of ultra-smooth surfaces. Traditional polishing processes are not only inefficient but also prone to introducing subsurface defects, which severely degrade device performance. To address the above issues, this study proposes a hybrid polishing process combining reactive ion etching (RIE) surface modification with chemical mechanical polishing (CMP), which enables low-loss atomic-level processing of SCD. The study found that RIE treatment induces lattice disorder on the diamond surface, forming a sp²-hybridized amorphous carbon-modified layer. Compared to the sp³ structure of native diamond, this modified layer has lower hardness and is easier to remove. We conducted the verification of the optimized process using high-quality single-crystalline diamond (SCD) samples with an initial surface roughness Ra of 0.68 nm. Under the optimized RIE parameters (substrate bias power: 200 W, etching time: 600 s, gas flow ratio of Ar:O₂:CF₄ = 40:50:10), the surface roughness Ra was reduced to as low as 0.35 nm after 2 h of CMP treatment. Furthermore, systematic characterization of the SCD’s as-received surface, RIE-modified surface, and CMP-treated surface was performed using Raman spectroscopy and X-ray photoelectron spectroscopy (XPS), elucidating the “etching modification–mechanical removal” polishing mechanism. Full article

This investigation focused on isoniazid (INH)—saccharin (SAC) salts. One hydrate and one anhydrous INH-SAC salt form were synthesized and characterized spectroscopically by Raman and infrared spectroscopy. Solvent (methanol, acetone, acetonitrile)-assisted synthesis in the presence of water, or in water, resulted in production of the monohydrated form of the salt (MH: (INH+H)⁺/(SAC–H)⁻.H₂O). The anhydrous form (A: (INH+H)⁺/(SAC–H)⁻) was obtained using the same synthesis method but in the absence of water or, together with the hydrate, in the presence of traces of water. Differential scanning calorimetry studies revealed that the hydrate can be converted into the anhydrous form of the salt upon heating, with the latter melting at a T_m (onset) of 131.7 ± 0.5 °C. Melting was followed by a reaction between isoniazid and saccharin leading to saccharin ring opening and formation of a new covalent hydrazide–amide derivative, via nucleophilic acyl substitution at the saccharin carbonyl. The newly formed adduct, 2-[2-(pyridine-4-carbonyl)hydrazine-1-carbonyl] benzene-1-sulfonamide, melts at T_m (onset) = 204.4 ± 0.5 °C. The crystal structures of the hydrate and of the anhydrous form were determined by single-crystal X-ray diffraction, and the dominant intermolecular interactions in the crystalline INH-SAC salts were evaluated using Hirshfeld surface analysis. To complement the experimental results, density functional theory (DFT) calculations were performed both on relevant isolated structural units and on the two salts, employing fully periodic DFT methods. Full article

To reveal the varieties and color genesis of emerald-green tourmaline crystals from Tanzania, a systematic study was conducted using conventional gemological tests, X-ray diffraction, Fourier-transform infrared spectroscopy, polarized ultraviolet–visible spectroscopy (UV–vis), X-ray photoelectron spectroscopy (XPS), low-temperature photoluminescence (PL) spectroscopy, and electron probe microanalysis (EPMA). The results indicate that the tourmaline is dravite. Its UV–vis absorption spectrum shows strong broad absorption bands at approximately 436 and 600 nm, with a pronounced transmission at 520 nm, which directly accounts for its emerald green color. Obvious polarized absorption was observed along and perpendicular to the c-axis. XPS and PL results confirm that chromium is present in the samples in the form of Cr³⁺. EPMA compositional analysis indicated a low Cr₂O₃ content of 0.804 wt.%; combined with crystal structural properties and spectral responses, these results suggest that Cr³⁺ preferentially occupies the Y site in the crystal structure and that d–d electronic transitions represent the underlying mechanism of its color formation. This study comprehensively illustrated the mineralogical and spectral properties of Cr-bearing dravite, providing fundamental data for further research on its genesis and gemological application. Full article

This study reports the preparation of a nanocomposite using a black cumin surface as a carbon framework on which zinc oxide-doped manganese ferrite nanoparticles were deposited and grown. A simple precipitation method was used to prepare the nanocomposite. The resulting composite was characterized using various characterization analyses such as FTIR, XRD, EDX, SEM, TEM, and TGA. The composite surface was highly conformed with functional groups, and the nanocomposite was formed due to electrostatic and non-electrostatic interactions between the carbon framework and the nanoparticles. X-ray analysis revealed a crystalline structure with crystal sizes up to 45 nm. Microscopic images revealed the surface morphology, confirming the irregular distribution of particles within the composite. The resulting composite material was used for adsorption application. The composite material was tested for the removal of Congo red dye from water. It was found that under optimal conditions, a dose of 2 g per liter of absorbent removed nearly 100% of dye from a 10 mL volume of 10 mg per liter Congo red solution within 90 min and 7 pH. A monolayer adsorption was confirmed by the isotherm analysis. The monolayer adsorption capacity for the present study was ~13.0 mg per gram. The adsorption kinetics suggested the fitting of pseudo-second order. Based on the findings, it was concluded that the chemical mechanism was responsible for the present adsorption process. The regeneration study demonstrates the stability of current adsorbent up to two cycles only. This nanocomposite is the first of its kind which promotes the creation of nanocomposites in the future by using natural materials and reduces the dependency on activated carbon. Full article

M-type hexaferrites are widely used in magnetic applications, and tailoring their properties via aliovalent substitution requires a detailed understanding of charge compensation and cation distribution. In this work, Mg²⁺/M⁴⁺ (M = Zr, Hf) co-substituted BaFe₁₂O₁₉ was synthesized via Na₂CO₃ flux and comprehensively characterized by wavelength-dispersive X-ray spectroscopy, powder and single-crystal X-ray diffraction, Rietveld refinement, X-ray absorption near-edge structure, and magnetic measurements. Increasing substitution levels x, y in BaFe_12−x−yMg_xM_yO₁₉ result in increasing lattice parameters and decreasing the room-temperature magnetic parameters saturation magnetization, remanence, and coercivity, while remanence and coercivity increase at low temperatures. Secondary phases form for nominal substitution ≥ 1. Zr⁴⁺ and Hf⁴⁺ preferentially occupy the 4f₂ site, whereas Mg²⁺ is distributed over multiple sites, as indicated by polyhedral volume analysis. Wavelength-dispersive X-ray spectroscopy confirms homogeneous elemental distribution within individual crystals but reveals significant variation in substitution levels within batches. The maximum degree of substitution for the tetravalent metals was y ≈ 1.2–1.7, with lower Mg incorporation of x ≈ 0.9–1.1. Charge compensation was found to be partially achieved via vacancy formation, while minor Fe²⁺ contributions cannot be excluded. Full article

RelA/SpoT homologue family enzymes participate in controlling the cellular levels of the alarmone (p)ppGpp, thereby activating the stringent response and promoting survival under stress conditions. These proteins contain an N-terminal catalytic domain and a C-terminal regulatory domain. They catalyze both the synthesis of ppGpp/pppGpp from ATP and GDP/GTP and their hydrolysis to GDP/GTP and pyrophosphate. Here, we report the crystal structure of the N-terminal domain of Rel from Streptococcus equisimilis in complex with pppGpp at 3.2 Å resolution. The asymmetric unit contains a dimer with asymmetric ligation: pppGpp occupies only the synthetase site in one monomer, whereas in the other monomer, it is bound in both the hydrolase and synthetase sites. The two monomers exhibit distinct conformational states, with pronounced rearrangements of the flexible loops surrounding the binding pockets, including the α2/α3 and α8/α9 loops that act as steric gates. Molecular dynamics simulations support the dual binding arrangement and reveal additional probable transient binding sites, including a region in the linker between hydrolase and synthetase subdomains. These findings provide a structural framework for understanding how pppGpp binding modulates the opposing catalytic activities of bifunctional Rel enzymes and suggest possible mechanisms for (p)ppGpp-mediated autoregulation. Full article

Wittichenite (Cu₃BiS₃) was synthesized by mechanical alloying (MA) followed by hot pressing (HP), and its phase evolution, thermal stability, charge transport behavior, and thermoelectric performance were systematically examined. X-ray diffraction analysis of the MA powders revealed broadened diffraction peaks, indicating reduced crystallinity and refined crystallite size. After HP consolidation, a well-defined single-phase orthorhombic wittichenite structure was obtained. These results demonstrate that the mechanically induced solid-state synthesis was effectively initiated during MA and subsequently completed through crystallization, defect relaxation, and densification during HP. The MA–HP processed specimens exhibited high relative densities of 94–98% of the theoretical value and a homogeneous microstructure without detectable compositional segregation or grain-boundary enrichment, confirming the formation of a structurally and chemically stable single-phase bulk material. Thermal analysis identified a reversible polymorphic phase transition from P2₁2₁2₁ to Pnma at low temperature, followed by structural relaxation and the onset of partial decomposition at higher temperatures, indicating that Cu₃BiS₃ retains structural integrity below 700 K, which defines the relevant operating window for thermoelectric evaluation. The samples exhibited p-type semiconducting behavior, with electrical conductivity increasing with temperature due to thermally activated hole transport and showing an additional enhancement across the structural transition region. The Seebeck coefficient remained positive over the entire temperature range and decreased gradually with increasing temperature, consistent with semiconductor transport characteristics. The thermal conductivity remained low at 0.30–0.38 W·m⁻¹·K⁻¹, with a negligible electronic contribution, confirming that heat transport is dominated by lattice phonon scattering. As a result of the combined increase in electrical conductivity and intrinsically low thermal conductivity, the dimensionless figure of merit (ZT) increased continuously with temperature and reached 0.17 at 673 K. These results demonstrate that the MA–HP route provides an effective and scalable strategy for producing phase-pure Cu₃BiS₃ with controlled microstructure and reproducible thermoelectric performance. Full article

In this work, we present a theoretical study of InPO₄ under pressure. Total-energy calculations based on density functional theory were performed to explore the crystal structure of InPO₄ in light of the recent X-ray diffraction characterization of this compound under pressure. A phase coexistence was observed above 10 GPa, involving the ambient-pressure CrVO₄-type structure and the high-pressure scheelite and zircon phases. Therefore, the previously performed analysis of InPO₄ behavior under pressure is extended by simulating X-ray spectra and interplanar distances for the three polymorphs. In addition, the elastic behavior of the three phases is analyzed to assess the elastic stability of InPO₄ under pressure and to compute the mechanical properties and elastic anisotropy. Our findings significantly extend previous experimental results on the compressibility of InPO₄, which were limited to the ambient-pressure phase. Moreover, our results unambiguously reveal a marked difference in the elastic properties of the scheelite and zircon phases under pressure, showing that the zircon phase is elastically unstable at high pressures. This suggests that the reported coexistence of phases may result from kinetic barriers or from non-hydrostatic conditions within the diamond anvil cell caused by the pressure-transmitting medium. Full article

Organic–inorganic hybrid metal halides (OIMHs), especially zero-dimensional (0D) ones, have been recognized as an excellent class of luminescent materials due to their structural diversity and tunable emission properties. In this work, using the environmentally friendly Zn(II) ion as the central metal and 1,4,7,10-tetraazacyclododecane (Cyclen) as the organic component, we successfully synthesized a novel OIMH, (H₃Cyclen)(ZnBr₄)·Br·H₂O. Single-crystal X-ray diffraction analysis reveals that (H₃Cyclen)(ZnBr₄)·Br·H₂O possesses a 0D structure, in which the [ZnBr₄]²⁻ tetrahedra are uniformly separated by the organic amine cations. This structural feature is expected to enhance the material’s stability and optimize its optoelectronic properties. Under UV lamp irradiation, (H₃Cyclen)(ZnBr₄)·Br·H₂O emits bright blue-green light. Therefore, we systematically investigated its luminescence properties. The emission mechanism was further elucidated using UV–vis absorption spectroscopy and DFT calculations. Finally, (H₃Cyclen)(ZnBr₄)·Br·H₂O was employed as a luminescent material to fabricate a white light-emitting diode (WLED), demonstrating its potential as an excellent phosphor material. Full article

This article details the synthesis and structural characterization of a new metalloid germanium cluster 3 with bulky amide ligands. The cluster features a Ge₆ core stabilized by four -N(Si^tBuMe₂)₂ ligands and was obtained via reduction of the amido trichlorogermane 2 using potassium chips in toluene. Single-crystal X-ray diffraction analysis revealed that the Ge₆ core adopts a butterfly-shaped geometry with a Ge-Ge dumbbell unit, which contains two unsubstituted germanium atoms exhibiting prominent lone-pair characteristics. The Ge₆ core can also be classified as a nido cluster, with a cluster-bonding-electron count of 16, perfectly satisfying the 2n + 4 electron-counting rule. Combining the structural features of this nido cluster with the bond length distribution in the folded four-membered ring suggests that the Ge4 ring features a certain degree of electron delocalization. Additionally, two bis(amido)-substituted germylenes (4 and 6) were isolated and structurally characterized. They exhibit analogous structural features, with each germanium center adopting a two-coordinate V-shaped configuration, the Ge–N bond lengths being very similar, and the nitrogen atoms adopting a planar triangular geometry. Notably, compound 6, bearing bulkier -N(SiⁱPr₃)₂ substituents, exhibits a significantly larger N-Ge-N bond angle (120.58°) compared to the corresponding value of 113.54° observed for compound 4 with -N(Si^tBuMe₂)₂ substituents. This clearly demonstrates that the steric bulk of the substituents exerts a remarkable influence on the molecular geometry and σ-donor ability of the lone pairs on germanium centers. Full article

An unreported bicyclic sesquiterpene acid, verruculosic acid (1), was isolated together with the previously reported labdane diterpenes, (+)-agathic acid (2a) and hypoxyterpenoid A (2b), one 3-nor-2,3-seco-labdane, penioxalicin (3), and 5-carboxyphthalide (4), from a sea grass-associated fungus, Penicillium verruculosum KUFA1509. The structures of the isolated compounds were elucidated by detailed analyses of 1D and 2D NMR and HRMS data. The absolute configurations of the stereogenic carbons in 1 and 2a were established by X-ray crystallography. The crystal structure of 2a, which was obtained for the first time, was used to prove its structure and confirm its stereochemistry. The crystal structure of 3 was also obtained; however, the value of its flack parameter does not allow us to determine the absolute configuration. Compound 2b exhibited stronger inhibitory activity than the positive control, diclofenac sodium, against LPS-induced nitric oxide (NO) production in RAW264.7 macrophages, while 1 and 2a were slightly less active than the positive control. In contrast, 3 exhibited much weaker activity than 2a. Compounds 1–4 were also assayed for antibacterial activity against reference and multidrug-resistant strains, but none exhibited antibacterial activity against the tested strains. Thus, the labdane skeleton could be considered as a potential scaffold for the development of anti-inflammatory agents through NO inhibition. Full article

N-doped Li₂ZrCl_6−3xN_x chloride solid electrolytes were synthesized via a mechanochemical method, and the effects of N incorporation on crystal structure, Li local environment, and Li⁺ transport were systematically investigated. X-ray diffraction suggested that the main Li₂ZrCl₆-related diffraction features were largely retained, while N introduction induced partial structural evolution toward C2/m-related features. 7Li MAS NMR revealed that N incorporation sharpened Li resonance peaks. Among the series, Li₂ZrCl_5.7N_0.1 exhibited the highest room-temperature ionic conductivity of 1.15 mS cm⁻¹, with the lowest activation energy of 0.237 eV, demonstrating a reduced Li⁺ migration barrier. All-solid-state batteries incorporating Li₂ZrCl_5.7N_0.1 showed stable rate capability and long-term cycling, retaining 85.9% capacity after 500 cycles at 1C and 77.4% after 3000 cycles at 3C. These results suggest that appropriate N modification can tune the Li₂ZrCl₆-based structure and Li local environment, thereby improving Li⁺ transport in all-solid-state lithium batteries. This work provides a feasible strategy for improving chloride-based solid electrolytes for next-generation energy storage. Full article

4-Methyl-N-(4-methylbenzyl)-N’-(4-methylbenzylidene)benzenesulfonohydrazide was synthesized via N-alkylation. The compound was characterized by nuclear magnetic resonance (NMR) spectroscopy and mass spectrometry (MS). Its molecular structure was unambiguously established by single-crystal X-ray diffraction analysis. The comprehensive spectral and crystallographic data conclusively verify the successful synthesis and structural integrity of this newly prepared compound. Full article