Powder X-ray diffraction (PXRD) and X-ray absorption near-edge structure (XANES) spectroscopy are complementary techniques for probing cobalt-based (Co-based) Fischer-Tropsch synthesis (FTS) catalyst structures. PXRD reveals crystalline composition, while XANES provides information on coordination geometry and oxidation state. We developed a fast, automated measurement method, based on rapid selection of X-ray beam energy and a dedicated sample environment at beamline ID10 (ESRF), to combine in situ PXRD and XANES in a single experiment. This approach enables simultaneous monitoring of structural and electronic changes in Co-based FTS catalysts under in situ conditions up to 60 bar, offering a comprehensive view of catalyst dynamics.

Under-calcination thermal reactivation of hydrated cement pastes and construction and demolition waste: A comparison of different commercial products

The chiral ligand (R)-3-(1-carboxyethoxy)benzoic acid [(R)-H2cea], was synthesized by modifying an aromatic carboxylic acid with lactic acid. This ligand was used to react with Zn2+ and Cd2+ ions under hydrothermal conditions in the presence of N-containing heterocyclic auxiliary ligands [1,4-bis(2-methyl-1H-imidazol-1-yl)benzene (1,4-bmib) and 1,1'-(2,5-dimethyl-1,4-phenylene)bis(1H-imidazole) (2,5-dpb)], successfully constructing two chiral coordination polymers (CPs), namely, poly[[μ-1,4-bis(2-methyl-1H-imidazol-1-yl)benzene-κ2N:N'][μ-(R)-3-(1-carboxylatoethoxy)benzoato-κ2O:O']zinc(II)], [Zn(C10H8O5)(C14H14N4)]n or HCU40-R, and poly[[μ-1,4-bis(1H-imidazol-1-yl)-2,5-dimethylbenzene-κ2N:N'][μ-(R)-3-(1-carboxylatoethoxy)benzoato-κ4O,O':O'',O''']cadmium(II)], [Cd(C10H8O5)(C14H14N4)]n or HCU41-R. Both CPs crystallize in the chiral space group P21, and the central chirality from the (R)-cea2- anion is transferred and amplified into supramolecular helical chirality. In HCU40-R, the Zn2+ ions adopt a tetrahedral geometry, forming a one-dimensional right-handed helical chain that further extends into a two-dimensional helical layer. In HCU41-R, the Cd2+ ions exhibit an octahedral geometry, displaying a double-helical chain and a twofold interpenetrated two-dimensional layered structure. Powder X-ray diffraction and elemental analysis confirmed the phase purity of the samples. Thermogravimetric analysis revealed thermal stability up to 350 °C for HCU40-R and 300 °C for HCU41-R. Fluorescence measurements showed emission peaks at 451 nm for HCU40-R and 491 nm for HCU41-R. Furthermore, both compounds exhibited second-order nonlinear optical (NLO) effects, with second harmonic generation (SHG) intensities of 0.38 and 0.35 times that of KDP, respectively.

• The first Mo/phenanthroline polymeric hybrid applied for catalytic olefin epoxidation • Robust performance of the Mo/phenanthroline hybrid catalyst for limonene valorization • Limonene to limonene oxide with TOF of thousands per hour and high selectivity • Hybrid generates soluble active species that self-construct into the original hybrid • Structure of peroxo active species inferred from catalytic and spectroscopic evidence In this work, the first Mo/phenanthroline polymeric hybrid is reported for the chemical valorization of biobased olefins via selective catalytic epoxidation. Catalytic epoxidation is of strategic importance to the chemical industry, as it produces epoxides that serve as renewable key intermediates for many end-user products. A relevant example is limonene (Lim), a terpene abundantly found in biobased waste, which can be valorized to limonene oxide (LimO) for the manufacture of renewable chemicals and materials. Molybdenum coordination compounds are effective epoxidation catalysts due to their ability to coordinate with a wide range of ligands. Among them, the bidentate N,N′ -donor ligand 1,10-phenanthroline (phen) is attractive because of its strong affinity toward transition metals and its stable, versatile heterocyclic structure. A newly developed hybrid, namely [MoO 3 (phen)] ( 2 ), was synthesized from the mononuclear precursor [MoO 2 Cl 2 (phen)] ( 1 ) using water as the solvent. Its structure was investigated using a combination of techniques, including elemental and thermogravimetric analyses, ATR FT-IR and Raman vibrational spectroscopies, powder X-ray diffraction, and solid-state 13 C{ 1 H} magic-angle spinning (MAS) NMR spectroscopy. This hybrid promoted the catalytic epoxidation of Lim with tert -butyl hydroperoxide at 70°C, with a turnover frequency of 2000 mol mol Mo −1 h −1 and 100% selectivity toward LimO. This study combines the identification of the structure of the active species, the investigation of catalytic reaction conditions, and mechanistic studies supported by kinetic modeling. The results suggest the formation of monooxodiperoxomolybdenum active species and a mechanism involving hydroperoxide activation followed by oxo transfer to Lim, giving LimO.

Sustainable cementitious materials from bamboo leaf-derived hydrochar: Process optimization and mechanical performance

High-temperature polymorphs of hafnia (HfO2) are of significant interest in electronics and fuel-cell applications, and stabilization at ambient conditions can be achieved by aliovalent substitution and nanosize effects. Y3+ stabilization of hafnia (YSH) introduces local cation disorder around charge-compensating oxygen-ion vacancies, and here we establish both the average and local structure of YSH nanoparticles using synchrotron powder X-ray diffraction (PXRD) and pair distribution function (PDF) analysis. A range of phase-pure crystalline nanoparticles of Hf1-xYxO2-x/2 were prepared via continuous flow solvothermal synthesis and subsequent high-temperature annealing, and full stabilization of the cubic phase is achieved already at 13 at% Y3+. The average structure conforms to the cubic fluorite phase of HfO2, but local displacive disorder caused by electrostatic attraction of neighbouring oxygen ions and repulsion of neighbouring metal ions by the net-positive oxygen-ion vacancies is established. The well-known Zr3Y4O12 structure, which incorporates such relaxation motifs, provides a good proxy description of YSH. In situ X-ray total scattering experiments provide insight into the formation mechanism of the YSH nanoparticles and initial precipitation of an atomically mixed amorphous phase is followed by crystallization over several minutes. The crystallization rate increases with higher reaction temperature, whereas an increased doping level results in slower crystallization.

• The combined experimental–theoretical framework elucidate olanzapine and risperidone's solid-state behavior. • Dispersion-corrected DFT accurately reproduces experimental crystal structures. • Crystal lattice dynamics provide a solid-state basis for drug stability. • Low-frequency lattice modes govern thermal behavior of olanzapine and risperidone. • Hydrogen-bond topology controls lattice thermodynamics in both drugs. Olanzapine and risperidone are widely used antipsychotics whose solid-state properties are governed by crystal packing and low-energy lattice dynamics. Here, we combine powder X-ray diffraction (PXRD), differential scanning calorimetry (DSC), and infrared/Raman spectroscopy with dispersion-inclusive periodic density functional theory (DFT) and density-functional perturbation theory (DFPT) calculations to establish a consistent vibrational, phonon, and thermodynamic description of their crystalline forms. Bulk structure optimizations performed at LDA, GGA-PBE, and GGA+TS levels support the importance of van der Waals interactions for accurate molecular-crystal geometries, while simulated IR/Raman spectra enable mode assignments based on phonon eigenvectors across three spectral windows (0–900, 900–1800, and 2750–3250 cm −1 ). Phonon dispersion relations are computed along selected high-symmetry directions, with emphasis on the 0–100 cm −1 region to highlight lattice modes most relevant to thermal behavior. From the phonon spectrum, we derive temperature-dependent thermodynamic functions, including Debye temperature ΘD(T), constant-volume heat capacity CV(T), vibrational enthalpy Hvib(T), Helmholtz free energy Fvib(T), and the entropic contribution TSvib(T) over 0–1000 K. The results reveal systematic differences between olanzapine and risperidone consistent with distinct low-frequency mode distributions and vibrational phase space, providing a microscopic basis for comparative thermal trends. Risperidone exhibits a higher density of low-frequency lattice modes and, consequently, larger phonon-derived entropic and heat-capacity responses than olanzapine across the investigated temperature range. Overall, this study delivers an integrated experimental–theoretical framework that advances solid-form identification, packing-sensitive vibrational fingerprinting, and phonon-based thermodynamic interpretation in pharmaceutical molecular crystals.

Lapping the surfaces of Si(111) crystals in a double-crystal monochromator significantly increases the intensity of high-energy X-ray beams. Systematic characterization using 100 keV X-rays shows that the total flux increases by factors of 7-11 relative to polished crystals. The resulting energy bandwidth (0.12-0.21%) remains substantially narrower than that of multilayer optics. These characteristics provide a useful compromise between spectral selectivity and beam intensity, enabling practical X-ray measurements that are difficult to achieve with either perfect-crystal monochromators or multilayer optics alone. Demonstrations of imaging, powder diffraction, and incoherent micro-focusing further highlight the practical utility of the resulting beams in applications where high photon statistics are prioritized. These results demonstrate that lapped Si crystals provide a robust and cost-effective approach to generating high-flux, moderate-bandwidth high-energy X-ray beams.

Oral bioavailability of fenofibrate from melt-extruded phospholipid-containing solid dispersions: A rat study.

Cadmium sulfur selenide and cadmium zinc sulfide pigments have been widely employed by artists of the twentieth century. A deep knowledge of these artworks, also in view of their conservation and/or restoration, relies on comprehensive and robust databases of reference materials of the pigments to easily detect their composition and their tendency and routes to deterioration. In this work, we initiate the construction of such a database by applying exclusively non-invasive techniques-X-ray Fluorescence (XRF) and Fiber Optics Reflectance Spectroscopy (FORS) in the Vis-SWIR range-to two sets of historical pigments: a group of pure commercial tube paints and a mixed palette representative of artistic practice. To strengthen the interpretative framework, mock-up samples were prepared using modern Cd-based pigments. These reference materials were first analysed using the same non-invasive protocols to ensure full data compatibility. In addition, they were further characterized through synchrotron-based techniques, namely High-Resolution X-ray Powder Diffraction (HR-XRPD) and X-ray Absorption Spectroscopy (XAS), providing additional structural and phase information not accessible through laboratory non-invasive methods alone. The integration of non-invasive and synchrotron-based data on the modern reference materials enables a more rigorous interpretation of the spectra collected on historical pigments. This combined approach enhances phase discrimination, compositional assessment, and the understanding of pigment variability, thereby increasing the reliability and internal consistency of the historical database. The resulting dataset establishes a solid foundation for future non-invasive studies of twentieth-century Cd-based pigments in complex stratigraphic and binding media contexts.

The synthetic discovery of new metal-telluride phases remains challenging due to the limitations of stabilizing increasingly complex compositions using conventional solid-state reactions. Described herein, a boron-tellurium mixture (BTM) reaction is demonstrated to provide an effective route to synthetically access ternary telluride phases within the alkali-triel-telluride (A-Tr-Te, A = alkali metal, Tr = Ga or In) compositional space. High quality single crystals and polycrystalline phases of the new NaIn3Te5 (1) and NaGa3Te5 (2) were prepared and structurally characterized by single crystal and powder X-ray diffraction techniques. These isostructural analogues crystallize in the noncentrosymmetric and chiral space group R32, exhibiting three-dimensionally condensed TrTe4 tetrahedra with a filled β-Mn-type network. Diffuse reflectance spectroscopy reveals that both are small bandgap semiconductors, with direct optical bandgaps of 1.18 eV and 0.79 eV for 1 and 2, respectively. Compound 1 exhibits a weak second-harmonic generation response under stimulation by a Ho:YAG laser at 2090 nm. Density functional theory calculations show that the valence band maximum is dominated by Te 5p states in both 1 and 2. Conversely, the conduction band states stem from mixed contributions of Tr and Te orbitals. These results provide the first experimental evaluation of the optical properties of the Na-Tr-Te (Tr = Ga, In) 1 : 3 : 5 telluride compounds, providing insights into the electronic structure and nonlinear optical properties of stuffed β-Mn-type telluride frameworks.

Certain fish display silvery or blue colour, not through pigments, but through specialized guanine crystals that exist within iridophore cells in their skin. Within these cells, guanine (C5H5N5O) crystals are precisely arranged in stratified layers that reflect incident light, resulting in structural colour. This phenomenon has garnered growing scientific attention due to its potential applications in advanced materials. However, the minute size of guanine crystals significantly hinders their structural characterization. Guanine crystals exist in multiple polymorphic forms. Previous powder X-ray diffraction (PXRD) studies have revealed that fish-derived guanine primarily adopts the anhydrous α- and/or β-polymorphs. More recently, MicroED analyses have identified the β-polymorph in salmon. Nonetheless, the crystal forms in other fish species remain insufficiently characterized. Due to their nanoscale dimensions and sensitivity to electron irradiation, reliable structural determination requires data collection from a large number of crystals. Here we established a semi-automated MicroED data collection and processing system. Initial validation was performed using synthetic guanine crystallized under acidic and basic conditions. Subsequently, guanine crystals were analyzed from three fish species: Pacific saury, Pacific cutlassfish and blue damselfish. Our findings revealed the presence of both α- and β-polymorphs in all three species, corroborating previous PXRD reports and demonstrating the efficacy of our system for the structural investigation of submicrometer-scale biogenic crystals.

We report the synthesis and characterization of a series: UOS, UOSe and β-US2, the first examples of uranium-chalcogen-containing nanomaterials using colloidal synthetic techniques. The challenge to these syntheses is the oxophilicity of uranium, as uranium dioxide is difficult to avoid and the only actinide nanomaterial reported previously. All reagents, the metal, chalcogen source and solvent, were investigated to understand phase formation in solution. We found a post-synthetic modification, commonly known as digestive ripening, that led to size control of the β-US2 nanoparticles. The phases were confirmed using powder x-ray diffraction and Rietveld analysis, as well as microscopy ( transmission electron microscopy), and magnetic susceptibility measurements. The oxychalcogenide nanomaterials are antiferromagnetic, in contrast to previously reported UO2 nanoparticles. As found in bulk β-US2, the nanoparticles are paramagnetic, with a moment consistent with localized f electrons.

High-quality single crystals of the formula K2[M(H2O)6][Zr2F12] (M = Fe, Co), Rb2[M(H2O)6][Zr2F12] (M = Fe, Co, Ni, Cu, Zn), Cs2[M(H2O)6][Zr2F12] (M = Fe, Co, Ni), and Cs2Zr3Mn3F20 were obtained through a mild hydrothermal synthesis. The new materials crystallize in the monoclinic space group P21/n. The crystal structures and chemical compositions were determined using single crystal and powder X-ray diffraction. The thermal and optical properties of these materials are reported. UV-vis diffuse reflectance data identifies d-d electronic transitions of the Co-, Ni-, and Cu-containing compounds. Each hydrated compound (except the Fe containing compounds) exhibits similar thermal decomposition, fully dehydrating by 200 °C based on thermogravimetric analysis measurements. Magnetic measurements indicate that the new compositions are paramagnetic down to 2 K.

Borates exhibit exceptional structural diversity, yet high-pressure/high-temperature (HP/HT) synthesis has predominantly focused on increasingly extreme conditions, leaving moderate pressure-temperature regimes largely unexplored. Here, we demonstrate that this limitation is primarily kinetic rather than thermodynamic. By integrating sol-gel-derived, chemically homogeneous precursors with HP/HT treatment, we establish a precursor-controlled strategy that enables systematic access to a chemically fertile moderate-pressure regime (≤3 GPa, ≤ 800 °C). This approach allows the synthesis of known high-pressure borates (β-SmB3O6, β-SnB4O7, δ-BiB3O6) under substantially milder conditions and extends the β-REB5O9 (RE = Pr, Nd) series. Moreover, it leads to the discovery of two new families of hydrated borates, β-REB6O9(OH)3 (RE = La-Nd) and RE6B36O59(OH)8 (RE = Nd, Sm, Eu), whose structures are resolved by 3D electron diffraction and powder XRD. Both families adopt polar P63 symmetry and feature large 12- and 16-membered ring channel topologies within fully tetrahedral borate frameworks, an outcome that contrasts with the expected densification under compression. Temperature-dependent phase evolution further reveals that moderate HP/HT conditions can stabilize partially dehydrated, metastable frameworks inaccessible at ambient pressure. These results demonstrate that precursor-controlled kinetics can redefine accessible phase space in HP/HT synthesis, establishing moderate-pressure regimes as productive platforms for discovering structurally complex borates and beyond.

The optimum process for andrographolide nanocrystal-loaded liposomes was optimized using Box-Behnken design, and its in vitro and in vivo evaluation was subsequently studied. Scanning electron microscopy, transmission electron microscopy, X-ray powder diffraction, and differential scanning calorimetry were used to study the physical and chemical properties. Short-term stability was assessed by measuring changes in particle size and PDI. The in vitro release behavior of andrographolide nanocrystals, andrographolide liposomes, and andrographolide nanocrystal- loaded liposomes in pure water and PBS buffer was studied by the dialysis bag method. The pharmacokinetic properties of andrographolide formulations in vivo were explored when using male Sprague-Dawley rats. Encapsulation within liposomes, regardless of the initial drug form, effectively sustained the drug, with Slow release of 80 % in PBS (p<0.05). Andrographolide nanocrystal-loaded liposomes had good short-term stability. Additionally, the pharmacokinetic behavior showed that, excluding the higher Cmax of andrographolide liposomes and andrographolide nanocrystal-loaded liposomes, the pharmacokinetic parameters were similar (p<0.05). These hardly improve the pharmacokinetic behaviors by the intravenous route, and the potential mechanisms for the widely reported higher therapeutic efficacy of these technologies may be enhanced target efficacy or cellular uptake. This study conducted in vitro and in vivo performance tests on liposomes loaded with nanocrystals, and explored the performance of this preparation from various perspectives. This nanocrystal-loaded liposomes display great potential for the therapeutic mechanisms of nanoformulations, and helps researchers to better design and understand the therapeutic mechanisms of nanoformulations.

Low-characteristic-signal propellants are critical for aviation and missile technology, but existing flame retardants suffer from poor water stability and undesirable combustion interference. A bimetallic MOF strategy is proposed to enhance water stability by immobilizing K+ through coordination interactions, while synergistically integrating flame retardancy with catalytic performance. Two bimetallic MOFs, [Me2NH2][KPb2(TATAB)2]·DMF (MOF 1) and [Me2NH2]2[KNi2(TATAB)2(H2O)6]2·3DMF (MOF 2) (H3TATAB = 4,4,4-(1,3,5-triazine-2,4,6-triyl)tris(azanediyl)tribenzoic acid), were successfully synthesized and structurally characterized by single-crystal X-ray diffraction (SC-XRD). The composition and valence states of the bimetallic MOFs were determined by elemental analysis (EA) and X-ray photoelectron spectroscopy (XPS). Their excellent water stability, thermal stability, and nitrocellulose (NC) compatibility were confirmed by powder X-ray diffraction (PXRD), scanning electron microscopy (SEM), thermal analysis (DTA), and other characterization methods. Through a combustion observation device, the burning characteristics of each formulation were recorded, revealing the flame-retardant and catalytic mechanisms of the MOFs. Compared with KNO3 or K-TATAB controls, the formulation containing MOF 1/2 produced narrower, shorter, and darker flames, with shortened ignition delay and combustion duration. Pb/Ni-TATABs further shortened combustion duration, confirming the catalytic activity of Pb2+/Ni2+. Thus, the distinctive architecture of these bimetallic MOFs offers superior multifunctional additives, integrating water stability, flame retardancy, and catalytic performance.

Rational control of polymorph selection, particularly for metastable phases typically accessible only under extreme conditions, remains a pressing challenge. Here, we demonstrate a simple polyanion-substitution strategy to stabilize PrCrO4 (PrCr1-xPxO4 (x = 0.075-1.00) and high-pressure PrVO4 (PrP1-xVxO4 (x = 0.00-0.40)) in the monazite (S.G. P21/n) structure under ambient conditions. In addition to powder X-ray diffraction, the structure was confirmed by using high-resolution transmission electron microscopy and Raman spectral measurements. A medium-entropy system, PrCr1/3P1/3V1/3O4, was fabricated to investigate the phase stability drivers. Optical investigations of PrCr1-xPxO4 (x = 0.075-1.00) highlighted the role of distorted C1 tetrahedral symmetry in Cr5+ d-d transitions, yielding a color comparable to that of the standard inorganic green pigment Cr2O3 at a lower chromium content. The metastability of Cr5+ enables a low-temperature reversible oxygen-storage capability in PrCr0.50P0.50O4. The Cr5+/Cr4+ redox interplay underpinned the oxygen sorption and desorption. The chemical pressure in these systems was confirmed and quantified approximately using the available hydrostatic pressure coefficients and Raman mode hardening, with certain assumptions made. Furthermore, the successful transformation of zircon-CeVO4 to a monazite structure when 50 mol % of VO43- was substituted with PO43- demonstrates the applicability of this strategy for realizing metastable polymorphs in [Pr/Ce](V, Cr, P)O4 systems under ambient conditions.

Novel polyherbal-mediated ZnFe₂O₄ nanoparticles: Synthesis, characterization, antimicrobial, and anti-inflammatory evaluation against respiratory pathogens.

Systematically exploring the multidimensional parameter space of metal-organic framework (MOF) crystallization remains challenging due to limited adoption of high-throughput (HT), automated experimental workflows. MOF development is dominated by manual synthesis and characterization methods and a trial-and-error approach, and the integration of HT MOF synthesis with HT characterization and analysis is uncommon. Here, we present a practical HT MOF discovery workflow that combines automated solvothermal synthesis with three scalable characterization methods. First, we characterize bulk structure using HT powder X-ray diffraction (PXRD) and rapid matching of PXRD data to reported MOF crystal structures. We also employ a custom machine-learning based computer vision (CV) model to identify MOF formation rates from images of sample vials. Finally, we develop a HT X-ray fluorescence (XRF) method to quantify elemental ratios in bimetallic MOF samples. As a case study, we investigate the crystallization of rare earth (RE) MOFs, systematically probing the effects of reaction conditions such as metal identity, linker structure, temperature, and acid concentration. We then leverage these insights to demonstrate a proof-of-concept selective crystallization from a mixed RE solution. Using our HT workflow, we performed 1488 unique MOF crystallization reactions and characterized the resulting samples through the collection of >800 PXRD patterns, CV analysis of >13 000 images, and elemental analysis measurements of 144 bimetallic crystallization reactions. We identified 5 previously unreported rare earth MOFs (NU-2501-NU-2505) and characterized their structures with single-crystal X-ray diffraction (SCXRD) and microcrystal electron diffraction (MicroED). Our HT approach enabled us to construct phase diagrams mapping out the crystallization preferences and formation kinetics for 18 distinct RE-MOF products. By unifying automated MOF synthesis with multimodal characterization, we demonstrate the efficient exploration of a complex synthetic landscape, generating insights into MOF structure, crystallization kinetics, and composition.