Powder Diffraction Research Articles

The potential of supramolecular synthon to develop coamorphous systems with tailored physical stability: Mechanistic insights integrating kinetics and thermodynamics

Coamorphous drug delivery systems have received increasing interest owing to their potential to improve the solubility, dissolution and bioavailability of poorly water-soluble drugs. However, the crystallization risk is one of major limitations in their application. It has been widely recognized that the coformer plays a vital role in physical stability of coamorphous formulation. Unfortunately, the screen of optimal coformer still adopts a trial-and-error method, which is time-consuming and expensive. Herein, a supramolecular synthon approach based on the interaction between functional groups, was exploited to design coamorphous systems (CMs) consisting of lurasidone hydrochloride (LH) and three coformers, saccharin (SAC), L-tryptophan (TRP), and L-cysteine hydrochloride (CYS). X-ray powder diffraction suggested the order of physical stability of the coamorphous systems was ranked as LH-CYS CM > LH-TRP CM > LH-SAC CM. The charge-assisted hydrogen bond between LH and coformer was confirmed by infrared spectroscopy and solid-state 13C NMR. Moreover, structural, electronic, and molecular interaction information, especially hydrogen bonding interactions, were quantified by theoretical calculations, including miscibility calculations, molecular dynamics simulations and quantum chemical calculations. It was revealed that LH-CYS CM exhibited the best miscibility, strongest binding energy and strongest H-bond with partially covalent character, demonstrating the significant role of supramolecular synthon in stabilizing coamorphous formulations. Interestingly, LH-TRP CM, not LH-CYS CM, exhibited the lowest molecular mobility among three coamorphous systems, which was inconsistent with their physical stability. But from thermodynamic perspective, the order of configurational entropy and physical stability of coamorphous systems was completely consistent. We shed light on the comprehensive effects of molecular mobility and configurational entropy on physical stability of coamorphous systems. Importantly, the relationship between supramolecular synthon and kinetic/thermodynamic mechanisms was also discussed, and the positive correlation between configurational entropy and intermolecular interactions was proposed in this paper. Our findings demonstrated the great potential of supramolecular synthon in designing coamorphous systems with tailored physical stability, and further provided a deeper insight into the mechanisms of physical stability of coamorphous systems.

Energy trapping to substitutional and charge compensation defects in persistent luminescent BaAl2O4:Tb3+

The holistic approach of the photoluminescence (PL), thermoluminescence (TL), and persistent luminescence properties at room temperature of BaAl2O4:Tb3+ were investigated in detail using a wide range of techniques. Materials were obtained using a solution combustion synthesis. The x-ray powder diffraction patterns of nondoped and Tb3+ doped BaAl2O4 indicated the hexagonal phase, and a Tb4O7 solid solution was observed at 4 and 5 mol% Tb doped aluminate. X-ray photoelectron spectroscopy revealed that Ba occupied one site and that Tb ions occupied this site as Tb3+ as well as TbIV. PL emission in blue, green, and red was observed under an excitation at 228 nm, that originated from the interconfigurational 4f8–4f75d1 transitions of Tb3+. Time-of-flight secondary ion mass spectroscopy, UV–vis diffuse reflectance, and PL revealed the presence of a Cr3+ impurity. The 0.5 mol% Tb3+ doped BaAl2O4 exhibited a strong TL band at 354, 437 and 598 K, which were attributed to the traps formed by Tb3+ doping and subsequent O2− charge compensation. A persistent luminescence mechanism was constructed for the Tb3+ doped BaAl2O4. After the energy was stored in thermally liberated Tb3+ in the Ba2+ substitution sites and charge compensation defects, the Tb3+ was the source of the continuous luminescence.

A Grafting Hydrogen-bonded Organic Framework for Benchmark Selectivity of C2H2/CO2 Separation under Ambient Conditions.

Reticular chemistry and pore engineering have garnered significant advancements in metal-organic frameworks and covalent organic frameworks, leveraging robust metal-coordination and covalent bonds. However, these achievements remain elusive in hydrogen-bonded organic frameworks, hindered by their inherent weakness in hydrogen bonding. Herein, we strategically manipulate the porosity of hydrogen-bonded frameworks through a grafting approach, culminating in the synthesis of two isomorphic HOFs, HOF-FJU-99 and HOF-FJU-100, with distinct pore environments. Remarkably, HOF-FJU-100, with its microporous architecture, not only showcases exceptional stability but also achieves unparalleled separation efficiency and ultrahigh selectivity for C2H2/CO2 mixtures (50/50, v/v) under ambient conditions. Its IAST selectivity value of 201 stands as a benchmark, towering over all previously reported HOFs. The pore of HOF-FJU-100 boasts an electrostatic potential highly favourable for C2H2 adsorption, as evidenced by single crystal X-ray diffraction analysis revealing multiple hydrogen bonding interactions between C2H2 molecules and the framework. In situ gas-carrier powder X-ray diffraction analysis underscores the adaptability of pore structure, dynamically adjusting its orientation in response to C2H2, thereby enabling a highly efficient and specific separation of C2H2/CO2 mixtures through specific adsorptive interactions.

Spin reorientation and the interplay of magnetic sublattices in Er2CuMnMn4O12.

Through a combination of magnetic susceptibility, specific heat, and neutron powder diffraction measurements we have revealed a sequence of four magnetic phase transitions in the columnar quadruple perovskite Er2CuMnMn4O12. A key feature of the quadruple perovskite structural framework is the complex interplay of multiple magnetic sublattices via frustrated exchange topologies and competing magnetic anisotropies. It is shown that in Er2CuMnMn4O12, this phenomenology gives rise to multiple spin-reorientation transitions driven by the competition of easy-axis single ion anisotropy and the Dzyaloshinskii-Moriya interaction; both within the manganese B-site sublattice. At low temperature, one Er sublattice orders due to a finite f-d exchange field aligned parallel to its Ising axis, while the other Er sublattice remains non-magnetic until a final, symmetry-breaking phase transition into the ground state. This non-trivial low-temperature interplay of transition metal and rare-earth sublattices, as well as an observed k = (0, 0, ½) periodicity in both manganese spin canting and Er ordering, raises future challenges to develop a complete understanding of the R2CuMnMn4O12 family.

Synthesis, characterization, DFT computational studies and biological activity of transition metal complexes derived from 4-(((6-nitrobenzo[d]thiazol-2-yl)imino)methyl)benzene-1,3-diol

A series of Co(II), Ni(II), Cu(II), Zn(II) complexes have been synthesized with a benzothiazole azo dye containing tridentate (NNO) donor ligand 4-(((6-nitrobenzo[d]thiazol-2-yl)imino)methyl)benzene-1,3-diol derived from 2-amino-6-nitrobenzothiazole and 2,4-dihydroxybenzaldehyde. The structures of the novel ligand and metal complexes were identified and confirmed via various spectroscopic techniques (FT-IR,1H NMR,13C NMR, UV-Vis, mass spectrometry), TGA-DTA, powder X-ray diffraction, and DFT calculations. The optimal structural parameters and chemical reactivity of the ligand and metal complexes have been investigated using Density Functional Theory calculations (DFT/B3LYP,6-31G** and LanL2DZ basis sets) to provide insight about their frontier molecular orbitals (FMO) and molecular electrostatic potential (MESP). In vitro DPPH radical scavenging techniques have been used to assess the antioxidant activity of the ligand and complexes, indicating good antioxidant activity. The Ni(II) complex was the most potent with the lowest IC50 values. The in vitro antibacterial activities have been explored by screening against bacteria (Bacillus subtilis) and bacteria (E. coli) exhibiting significant activity against the tested strains of bacteria with Zn(II) complex as most potent with the lowest MIC value against E. coli and B. subtilis) and highest zone of inhibition against E. coli and B. subtilis at 1000 μg/mL concentration). The antifungal activity of complexes against Aspergillus niger and Candida albicans indicate that the Co(II) complex is most active for C. albicans and Zn(II) complex for A. niger .

Synthesis, Structural Characterization, Optical Properties, and Biological Potency of Co(II), Cu(II), and Cd(II) Complexes With Heterocyclic Thiosemicarbazide Ligand: Insights From Molecular Docking Studies

ABSTRACTA novel heterocyclic thiosemicarbazide ligand, [(Z)‐N‐(2‐oxoindolin‐3‐ylidene)nicotinohydrazide] (H2L), and its Co(II), Cu(II), and Cd(II) metal chelates were synthesized and characterized using a variety of analytical methods, including elemental analysis, FT‐IR, UV–Visible spectroscopy, EI‐mass, fluorescence spectroscopy, X‐ray powder diffraction, and TGA. The structures and geometries of the complexes were determined using these methods as [Co2(H2L)2Cl2(H2O)4]·2H2O, [Cu(H2L)2Cl2(H2O)2]·2H2O, and [Cd(H2L)2Cl2(H2O)2], all having octahedral geometry. The particulate diameters for [Co2(H2L)2Cl2(H2O)4]·2H2O, [Cu(H2L)2Cl2(H2O)2]·2H2O, and [Cd(H2L)2Cl2(H2O)2] were 192.68, 68.48, and 192.74 nm, respectively using Debye–Scherrer equation and FWHM approach. The corresponding FWHM values were 0.0078, 0.0217, and 0.0075, whereas the crystal strain was calculated as (ε) = 0.0018, 0.0056, and 0.0054, and the dislocation density (δ) as 2.69 × 10−5, 2.13 × 10−4, 2.69 × 10−5 Å−2. Quantum chemical calculations for the ligand and its solid metal complexes were carried out utilizing DFT with the DMOL3 module. Furthermore, the optical sensing response of the free ligand H2L to Co(II), Cu(II), and Cd(II) ions was investigated, revealing that the presence of these metal ions enhanced the fluorescence spectra of the ligand. Additionally, the antibacterial effects of these compounds, as well as their cytotoxicity in human cancer cells, were investigated. Compared to its metal complexes, the ligand, H2L exhibits increased antibacterial activity against various bacteria. Tests on HepG‐2 and MCF‐7 cells were conducted to evaluate the compounds' anticancer efficacy against the standard, Doxorubicin. The ligand, H2L, demonstrated greater cytotoxicity against the HepG‐2 cell line than its metal complexes. Docking experiments were conducted to assess the interaction of the ligand and its complexes with HepG‐2 (PDB ID: 2OH4) and MCF‐7 (PDB ID: 3W2S) cells, using the XP glide technique and Schrödinger suite software.

The new pincer-type NHCs obtained by synthesizing Ag(I)-NHC complexes with various tails containing hydroxyl or acetate derivatives: Structural properties and in vitro antibacterial activities

This article discusses the synthesis, chemistry, and uses of transition metal complexes containing functionalized N-Heterocyclic carbenes (NHCs). NHCs were obtained by coupling functional group compounds containing ethyl acetate, propyl acetate, and ethanol to the 5,6-dimethylbenzimidazole compound. Thermogravimetric analysis (TGA), FT-IR, and solution (1H and 13C) NMR spectroscopy were used to characterize the elements in these compounds, and Rietveld analysis using X-ray powder diffraction (XPD) and ICP (Inductively Coupled Plasma) data was used to determine their structures. Major uses include catalyst modification and immobilization using a functional group to immobilize catalysts on a 5,6-dimethylbenzimidazole derivative support. The effects of the drug ampicillin were compared with the antimicrobial activities of 3a-c and 4a-c determined by the minimum inhibitory concentration (MIC; μg/ml). The MIC value of the compound bis(1,3-bis(3-ethoxy-3-oxopropyl)-5,6-dimethyl-1H-3λ4-benzo[d]imidazol-2-ylidene)silver(I)hexafluorophosphate (4b) was measured as 0.25 ± 2.05 μg/mL. This value indicates that this complex has strong antibacterial abilities.

Features of the Structure and Thermal Properties of LnBWO6 (La = Ln, La0.999Nd0.001, La0.99Gd0.01) Synthesized by the Sol-Gel Method

Borate tungstates LnBWO6 (Ln = La, La0.999Nd0.001, La0.99Gd0.01) were synthesized by the Pechini method with subsequent annealing of intermediates. They were analyzed by X-ray diffraction (XRD) and DSC methods. Crystallographic parameters of synthesized LnBWO6 were refined by powder X-ray diffraction in two systems: monoclinic, space group P21, and orthorhombic, space group P222. The presence of reversible first-order phase transitions in synthesized LnBWO6 was detected using the DSC method, and the temperatures and enthalpies of phase transformations were determined. It has been shown that Nd3+ and Gd3+ dopants lowers the L- → H- phase transition temperature of LaBWO6. According to experimental electron paramagnetic resonance (EPR) data gadolinium has two independent positions in the La0.99Gd0.01BWO6 structure.

UiO-67 MOF-Encapsulated NHC-Based Single-Site Copper Catalyst and Its Application in Regioselective Borylation of Terminal Alkynes.

N-Heterocyclic carbenes (NHCs) act as versatile ligand backbones due to their strong σ-donation and π-acceptance properties. However, the encapsulation of NHC-coinage metal complexes in a metal-organic framework (MOF) to utilize them in organic catalysis is rare. In this work, an NHC-coordinated CuBr (NHC = Bn2Im; 1,3-dibenzyl-imidazol-2-ylidene) complex was encapsulated in UiO-67 MOF ((Bn2Im)2CuBr@UiO-67) and further utilized toward the regioselective protoboration of terminal alkynes. (Bn2Im)2CuBr@UiO-67 was found to show superior catalytic performance in aiding the protoboration of terminal alkynes, with a very high turnover frequency (TOF) of 14333.3 h-1, much higher than those of many other reported copper-based heterogeneous catalysts. Our catalyst also retained excellent catalytic efficiency for up to five cycles for the above-mentioned process. The newly synthesized (Bn2Im)2CuBr@UiO-67 and the recovered catalyst post-catalysis were characterized using various analytical techniques, including powder X-ray diffraction (PXRD), IR spectroscopy, field-emission scanning electron microscopy (FESEM), high-resolution transmission electron microscopy (HRTEM), and X-ray photoelectron spectroscopy (XPS).

Vibrational, optical, electronic and electrocatalytic properties of SrCuSi4O10 ceramic

This research reports the synthesis of powdered SrCuSi4O10 ceramic powder, obtained through a solid-state chemical reaction methodology. The sample was characterized using X-ray powder diffraction (XRPD), Raman and Fourier transform infrared (FT-IR) spectroscopy, scanning electron microscopy (SEM), reflectance (R), electron paramagnetic resonance spectrum (EPR), lattice dynamic calculations, electronic and electrocatalytic properties analyses. The X-ray analysis showed that crystalline structure of SrCuSi4O10 compound belongs to a tetragonal system with the P4/ncc space group, containing four formulas per unit cell (Z = 4). The SEM micrographs present a morphology of layered microplates with some irregularity in size and shapes. UV–vis diffuse reflectance spectra show three intense reflection regions. Regarding the vibrational properties, the theoretical calculation was performed using a rigid ion model in order to assign the experimental Raman and IR modes. Additionally, electronic properties calculations were carried out using Density Functional Theory (DFT). Finally, the hydrogen evolution reaction (HER) performance of the SrCuSi4O10 electrocatalyst was evaluated.

In-Depth Characterization of Natural Clays from Southeast Albania

Clays have been exploited in the manufacture of diverse products from ceramics to paints, pharmaceuticals, plastics, cosmetics, and more. Thus, they can be used in many industrial applications, showing good adsorbent ability thanks to their lamellar structure, high cation exchange capacity, pore size distribution, and large surface area. For this reason, considerable attention has been paid to their in-depth characterization, for further integration in sectors such as biomedicine, construction, remediation, aerospace, and nanotechnology. For this aim, two samples of natural clays, ALO1 and PRE4, from the southeast part of Albania, were subject to a multi-methodological characterization, with the aim of addressing the use of such geomaterials in possible sensing applications. X-ray fluorescence analysis, morphological characterization of the samples, and energy-dispersive system spectroscopy pointed to an extreme mineralogical variety, with kaolinite in AL01 and montmorillonite in PRE4 as the most abundant phases. This fact was further confirmed by powder X-ray diffraction, showing a quartz content of 20%, a kaolinite content of 64%, and a muscovite content of 16% for ALO1; meanwhile, for PRE4, we found a content of quartz of 45%, a content of montmorillonite of 34.9%, and a content of clinochlore of 20%. Infrared spectroscopy and thermal analyses confirmed the presence of hydroxyl groups in both samples, suggesting a higher content in ALO1. Measurement of N2 adsorption isotherms on the clay samples yields specific surface areas of 87 m2/g for PRE4 and 32 m2/g for ALO1, pore volumes of 0.721 cm3/g for PRE4 and 0.637 cm3/g for ALO1, and similar pore sizes in the range of 6–12 nm. Electrochemical analysis highlighted a good conductivity of ALO1 and PRE4 when used for the modification of commercial carbon-based screen-printed electrodes. In detail, higher currents were registered by differential pulse voltammetry for the electrodes modified with the clays with respect to bare electrodes, as well as good repeatability of the measurements. In addition, a comparative study with nanomaterials, known for their good conductivity, was achieved, using carbon black and gold nanoparticles as a reference, showing that the conductivity of the clays was lower than but not so different from those of the reference materials.

Structure and Magnetic Properties of the n = 3 Ruddlesden-Popper Oxyfluoride La0.5Sr3.5Fe3O7.5F2.6.

Ruddlesden-Popper (RP) compounds of the general formula (AX)(ABX3)n with their unique sequence of perovskite-like (ABX3) and rock-salt-like units (AX) promise applications in diverse fields such as catalysis and superconductivity. Fluorination of RP oxides often leads to dramatic changes in the material properties, caused by differences in the atomic and electronic structure. While current research focuses on fluorination of n = 1 type RP oxides (A2BO4), n = 3 RP oxyfluorides have remained elusive. We present the synthesis of the first iron-based n = 3 RP oxyfluoride, La0.5Sr3.5Fe3O7.5F2.6, which was obtained from an oxide precursor by topochemical fluorination with poly(vinylidene fluoride). Joint Rietveld refinements of neutron and powder X-ray diffraction data were used to determine the crystal structure. Best results were obtained in the space group Pbca (No. 61) with a = 5.5374(1) Å, b = 5.5441(1) Å, and c = 29.2541(2) Å. The effect of the aliovalent incorporation of fluoride ions is particularly evident with respect to changes in structure and magnetic properties. The magnetic behavior was studied using field- and temperature-dependent magnetization measurements, Mößbauer spectroscopy, and neutron diffraction. Additional magnetic Bragg reflections observed in the room-temperature neutron data were successfully refined in the space group Pbca (61.1.497 in Opechowski-Guccione notation), indicating a G-type antiferromagnetic ordering with a surprisingly high Néel temperature above 300 K. This strong increase of TN by several hundred Kelvin compared to the parent oxide is particularly remarkable.

Kinetic origin of hysteresis and the strongly enhanced reversible barocaloric effect by regulating the atomic coordination environment

Hysteresis is an inherent property of first-order transition materials that poses challenges for solid-state refrigeration applications. Extensive research has been conducted, but the intrinsic origins of hysteresis remain poorly understood. Here, we report a study of the kinetic origin of hysteresis and the enhanced barocaloric effect (BCE) in MnCoGe-based alloys with ~2% nonmagnetic In atoms. First-principles calculations demonstrate that substituting In atoms at Ge sites rather than Co sites results in a lower energy barrier, indicating a narrower hysteresis for the former. Combining neutron powder diffraction (NPD) with magnetic and calorimetric measurements completely verified the theoretical prediction. Electron local function (ELF) calculations further reveal the atomic coordination origin of regulated hysteresis due to weaker Co–Ge bonds when In atoms replace Ge, which is opposite to Co sites. Moreover, we experimentally investigate the BCE and find that although MnCo(Ge0.98In0.02) has a lower barocaloric entropy change ΔSP than does Mn(Co0.98In0.02)Ge, the reversible ΔSrev of the former is advantageous owing to a smaller hysteresis. The maximum ΔSrev of MnCo(Ge0.98In0.02) is 1.7 times greater than that of Mn(Co0.98In0.02)Ge. These results reveal the atomic-scale mechanism regulating hysteresis and provide insights into tailoring the functional properties of novel caloric refrigeration materials.

Fabrication of Nd-Ho Cosubstituted Co0.5Ni0.5Fe2O4 Nanospinel Ferrites and Exploration of Their Microstructure, Magnetic, and Electromagnetic Characteristics.

The composition and hyperfine structures of Nd3+-Ho3+ ions cosubstituted CoNi nanospinel ferrites (Co0.5Ni0.5NdxHoxFe2-2xO4 (x ≤ 0.05) NSFs) as well as their magnetic and electrodynamic behavior have been presented. The compound Nd-Ho → CoNiFe2O4 (x ≤ 0.05) NSFs were produced using the sol-gel method. XRD powder patterns indicated phase- and substituent-induced modifications of crystallites. The SEM analysis indicated the homogeneous distribution of grains with Nd-Ho cosubstitution. It was found that the values of x had an impact on the hyperfine magnetic field of the A and B sites. The cation distribution was determined by using Mössbauer spectroscopy. The M-H loops' investigations showed that the current NSFs behave ferrimagnetically at both room and low temperatures. An almost continuous rise in the strength of the coercive field was noticed with a rise in Ho-Nd content. The value of calculated squareness ratio values was above 0.5 at both temperatures, entailing that the studied NSFs' structure is made of single magnetic domains. The electromagnetic characteristics of the samples can be explained by the main contribution to electromagnetic absorption being the electric energy losses. Electromagnetic absorbed materials can be applied to provide electromagnetic compatibility and develop functional electromagnetic shields.

A Cippus from Turris Libisonis: Evidence for the Use of Local Materials in Roman Painting on Stone in Northern Sardinia

The ancient Roman town of Turris Libisonis was located on the northern coast of Sardinia and was known in the past as an important naval port. Located in the Gulf of Asinara, it was a Roman colony from the 1st century BCE and became one of the richest towns on the island. Among the archaeological finds in the area, the cippus exhibited in the Antiquarium Turritano is of great interest for its well-preserved traces of polychromy. The artefact dates back to the early Imperial Age and could have had a funerary or votive function. The artefact was first examined using a portable and non-invasive protocol involving multi-band imaging (MBI), portable X-ray fluorescence (p-XRF), portable FT-IR in external reflectance mode (ER FT-IR) and Raman spectroscopy. After this initial examination, a few microfragments were collected and investigated by optical microscopy (OM), X-ray powder diffraction (XRPD), Fourier-transform infrared spectroscopy in ATR mode (ATR FT-IR) and micro-ATR mode (μATR FT-IR) and Scanning Electron Microscopy/Energy Dispersive Spectroscopy (SEM-EDS) to improve our knowledge and characterize the materials and to determine their provenience. The results contribute to a better understanding of the provenance of materials and shed light on pigments on stone and their use outside the Italian peninsula and, in particular, Roman Sardinia.

An analysis of the synthesis, crystal structure, optical, spectroscopic, mechanical, self-focusing, and third-order nonlinear optical properties of Kojic acid single crystals

A single, excellent crystal of Kojic acid (KA) was developed utilising the traditional approach of gradual evaporation in a solution-growing procedure. A variety of characterisation techniques were utilised to evaluate the characteristics of the crystals generated. Single crystal x-ray diffraction (SXRD) was utilised to identify the crystal structure. The crystalline arrangement of the KA crystal was confirmed using a powder x-ray diffraction (PXRD) analysis. Experiments with UV–vis spectrometers revealed that the KA crystal has a lower wavelength at which it blocks UV light but has outstanding light transmission throughout the visible spectrum. The KA single crystal has an energy band gap (Eg) of 2.5 eV. The Z-scan method was used to examine the third order susceptibility, nonlinear refraction, and nonlinear absorption coefficient of the synthesised KA crystal. The dielectric characteristics and AC conductivity were examined, with a particular emphasis on their connection to resistance at room temperature. The presence of appreciable levels of kojic acid was confirmed by energy-dispersive spectrometry. The crystal’s thermal behaviour was investigated using differential thermal analysis (DTA) and thermogravimetric (TG) methods. The nucleation parameters and controlled nucleation rate were calculated using normal theoretical research methods.

Spectral characteristics and luminescence applications of Eu3+-activated fluorosilicate Na2MgGd2[SiO3]4F2

This work reports the luminescence spectra and application of novel Eu3+-doped Na2MgGd2[SiO3]4F2 phosphor. The X-ray powder diffraction confirmed the pure phase formation of the samples with the monoclinic space group P21/c (No:14). The phosphors demonstrated efficient red emission at 613 nm from the electric dipole transitions 5D0→7F2. The optimal doping concentration was found to be approximately 25 mol%. Na2MgGd2[SiO3]4F2:0.25Eu3+ exhibits a high quantum efficiency (QE) of 57 % with excellent thermal stability and pure chromaticity. Red- and the white light-emitting diode devices were packaged using InGaN chips and Na2MgGd2[SiO3]4F2:0.25Eu3+. The fabricated WLED has CIE coordinates of (x = 0.33, y = 0.34), which are very close to the white point in the National Television System Committee (x = 0.33, y = 0.33). The color rendering index (CRI, Ra) and correlated color temperature (CCT) of the WLED are 91 and 4400 K, respectively. The results show that as a red luminescent phosphor, it is a potential candidate for the preparation of near-UV/blue InGaN-based WLEDs.

Insight into the Cationic Charge Distribution in U1-y-zPuyAmzO2±x Mixed Oxides.

Uranium-plutonium mixed oxides, containing few mol % of Am, are currently studied as fuel for Sodium Fast Reactors. The study of the O/M ratio of these fuels is of main interest, as its variation can induce issues for reactor safety. For this purpose, four U1-y-zPuyAmzO2±x samples (0.235 ≤ y ≤ 0.39 and 0.005 ≤ z ≤ 0.02) were studied using electron probe microanalysis (EPMA), X-ray powder diffraction (XRD), and X-ray absorption spectroscopy (XAS) experiments. EPMA analyses revealed a homogeneous matrix phase with few U- and Pu-rich agglomerates. A matrix phase of fluorite structure (face-centered cubic), as well as a small contribution of a UO2 phase of the same structure, was evidenced for all of the samples by XRD. The O/M ratios of the (U,Pu)O2±x matrix were calculated based on the obtained lattice parameters. XANES experiments highlighted the simultaneous presence of U5+ and Pu3+/Am3+ for all of the samples, indicating a charge compensation mechanism even for stoichiometric samples. Based on the EPMA and XRD results, it was evidenced that this coexistence of U4+, U5+, Pu3+, Pu4+, and Am3+ was not originating from the U- and Pu-rich agglomerates. It was found to be rather a peculiarity of the U1-y-zPuyAmzO2±x matrix phase, discussed with the help of thermodynamic calculations performed on the U-Pu-Am-O system.

Enhanced lead adsorption by eco-hydroxyapatite derived from marble sludge: Optimization and kinetic study

In this study, eco-hydroxyapatite (e-HAP) was synthesized from marble sludge via a hydrothermal process for utilization as an adsorbent in the removal of Pb2+ ions from wastewater. X-ray powder diffraction (XRD) and thermal field emission scanning electron microscope (FE-SEM) revealed that increasing the Ca/P molar ratio (CPMR) and hydrothermal temperature (HT) increased crystallinity and that the influence of HT was more apparent. An increase in crystallinity, crystal length, and peak intensity was observed following an increase in the CPMR. Adsorption studies show that when the HT was 393 K, the CPMR was 0.67, the initial Pb2+ ion concentration was 100 mg/L, the equilibrium time was 20 min, and the adsorbent dosage was 0.6 g/L. The resulting removal efficiency (99.99 %) and maximum adsorption capacity (166.65 mg/g) are both very high. Adsorption kinetics are well described using a pseudo-second-order kinetic model. This paper presents a facile and economically sustainable approach to the synthesis of e-HAP from marble sludge for use in removing of Pb2+ from wastewater.

Structure Elucidation of Pharmaceutically Relevant Compounds Within Pyrene-Based Frameworks.

Single-crystal X-ray diffraction (SCXRD) is the preferred and most accurate technique for determining molecular structures. However, it can present challenges when dealing with specific small molecules and active pharmaceutical ingredients (APIs), as many do not form quality crystals without coformers or can be unstable. In this study, we introduce tetrakis(guanidinium) pyrenetetrasulfonate (G4PYR), a robust guanidinium-organosulfonate (GS) framework that efficiently encapsulates small molecules and APIs rich in functional groups. The hydrogen bonding frameworks formed by G4PYR display well-ordered structures with predictable pyrene-pyrene distances, making them ideally suited for targeting arene-based APIs with pendant groups. Successful encapsulation of various guests, including benzaldehyde, benzamide, and arenes containing multiple hydrogen bond donors and acceptors like uracil and thymine, was achieved. Furthermore, we successfully encapsulated important pharmaceutical and biologically relevant compounds, such as lidocaine, ropinirole, adenosine, thymidine, and others. Notably, we present a workflow for investigating host-guest complex formation using powder X-ray diffraction and high throughput experimentation.