X-ray Diffraction Patterns Research Articles

Molten Salt Modulation of Potassium-Nitrogen-Carbon for the Breaking Kinetics Bottleneck of Photocatalytic Overall Water Splitting and Environmental Impact Reduction.

Sluggish interfacial water dissociation and the O2 evolution reaction (OER) kinetics are the main obstacles that limit the photocatalytic overall water-splitting performance. A molten salt modulation of potassium-nitrogen-carbon is herein demonstrated as the formation of highly crystalline potassium-doped poly(triazine imide) (KPTI). The in situ X-ray diffraction patterns and theoretical calculation show that the KCl melt can significantly reduce the free energy for the polycondensation of triazine building blocks owing to the formation of a kinetically stable KPTI. Benefiting from the presence of potassium-carbon-nitrogen moiety, the catalyst not only weakens the excitonic confinement to improve the separation efficiency of photogenerated charge carriers but also enhances the stability of carbon sites by suppressing the undesired C═O formation. Moreover, KPTI accelerates water dissociation by forming interfacial K·H2O clusters with an ordered structure, which supplies sufficient protons for the H2 evolution reaction and lowers the energy barrier to enhance the kinetics of OER. Therefore, a stable photocatalytic overall water-splitting performance can be achieved over KPTI with a stoichiometric generation of products (H2 and O2). Life cycle assessment shows that a carbon-neutral scenario can be achieved on KPTI production in the near term with an increase in green power in the electricity grid.

Microstructural, dielectric, electrical, electromagnetic, and magnetic property enhancements in GdIG /TrIG/ Mn0.2Co0.3Zn0.5Fe2O4 ferrites composites for electronic devices application

Gadolinium garnet ferrite (GdIG) and terbium garnet ferrite (TrIG), known for their favourable magnetic and dielectric characteristics, were combined with doped zinc spinel ferrite (GdIG)x-(TrIG)y/Mn0.2Co0.3Zn0.5Fe2O4(1-x-y) (at x=1 y=0, x=0 y=1, x=y=0.5, x=y=0.25, x=y=0) to achieve improved permittivity, permeability and magnetic properties with reduced magneto-dielectric losses. Our study details the synthesis process and the resulting enhancements in structural, magnetic, and dielectric properties of the prepared samples. Analysis of the X-ray diffraction (XRD) patterns confirmed the presence of a crystalline structure characterized by both cubic spinel and cubic garnet phases in the composites. The microstructures of the composites were analysed with field emission scanning electron microscopy (FESEM), revealing the variation in a grain size from 0.11 μm to 0.96 μm at x =y=0.5. A thorough link between the crystal structure and XRD spectra, transmission electron microscope (TEM), and selected area electron diffraction (SAED) patterns have all been investigated in order to enhance the characterisation of the samples. At 1KHz, the composites exhibit highest electrical resistivity values of 5.9×106 Ωm and 2.6×106 Ωm. With the incorporation of spinel ferrites in garnet ferrite composite (x=y=0.25) the highest value of dielectric constant (885.2) and low value of dielectric loss (0.07) at 100 KHz has been obtained. Permeability values, derived from permittivity data, showed an increase in real permeability values of from 1.4×1012 to 9.2×1017 for x=y=0.5 to x=y=0.25 composite. Vibrating sample magnetometer (VSM) further confirm that the composite x=y=0.25 has highest magnetic saturation (148.8 emu/g), coercivity (502 Oe) and microwave operating frequency (33.6 GHz). The observed high dielectric constant, low loss values, switching field distribution and good magnetic properties suggest the potential suitability of these samples for various electronic devices like: high frequency devices, antennas, switching devices and magnetic recording devices.

Biosynthesis and biological activities of magnesium hydroxide nanoparticles using Tinospora cordifolia leaf extract.

The synthesis of magnesium hydroxide nanoparticles (Mg(OH)2 NPs) using plant extracts are known to be a practical, economical, and an environmentally friendly approach. In this work, Mg(OH)2 NPs were synthesized using aqueous leaf extract of Tinospora cordifolia, a medicinal plant commonly found in India. The synthesized Mg(OH)2 NPs were characterized using various spectroscopic techniques. The ultraviolet-visible (UV-Vis) absorption peak of the Mg(OH)2 NPs was detected at 289nm, Fourier transform infrared (FTIR) analysis confirmed the presence of various functional groups, and X-ray diffraction (XRD) patterns revealed the well-crystallized structure of the Mg(OH)2 NPs. High-resolution transmission electron microscopy (HR-TEM) and scanning electron microscopy (SEM) analyses depicted spherical morphology and an average particle size (PS) of 27.71nm. The energy-dispersive X-ray (EDX) analysis confirmed the presence of C, O, and Mg elements, and the X-ray photoelectron spectroscopy (XPS) survey spectrum confirmed the elements for the Su 1s peak at 280.2eV. The dynamic light scattering (DLS) analysis displayed an average PS of 54.3nm, and the Zeta potential (ZP) was of 9.89mV. The fabricated Mg(OH)2 NPs displayed notable antibacterial activity against S. epidermidis, E. coli, and S. aureus. In addition, these NPs exhibited strong antioxidant properties (> 75%) based on DPPH, ABTS, and hydrogen peroxide (H2O2) assays. Further, the same NPs exerted a potent anti-inflammatory activity (> 65%) based on COX-1 and COX-2 evaluations. The anti-Alzheimer' disease (AD) potential of Mg(OH)2 NPs was assessed through effective inhibition (> 70%) of acetylcholinesterase (AChE) and butyrylcholinesterase (BChE) activities. Molecular docking (MD) studies confirmed that caryophyllene has higher binding affinity with AChE (-5.3kcal/mol) and BuChE (-6.4kcal/mol) enzymes. This study emphasizes the green synthesis of Mg(OH)2 NPs using T. cordifolia as a plant source and highlights their potential for biomedical applications.

Influence of annealing on the physicochemical properties of 2L ferrihydrite synthesized by radiation-chemical method from iron (III) nitrate

In this study, ferrihydrite (Fhy) nanoparticles (NPles) synthesized by the radiation chemical method (RCM) from an iron nitrate alcohol solution were annealed in air at temperatures ranging from 100 to 1200 ºC. The effects of annealing temperature on the phase transformation and basic physicochemical properties of the annealed Fhy nanopowders (NPs) were investigated. Fhy NPles annealed at 400 ºC and above can be converted to hematite NPles. The X-ray diffraction (XRD) pattern of the RCM-synthesized product corresponded to two-line (2 L) Fhy NPles, with no additional peaks, confirming their chemical purity. Up to 200 ºC, no significant phase transformation of Fhy NPles was observed; at 300 ºC, Fhy transformed into maghemite, which further transformed into hematite at 400 ºC. TEM/HRTEM analysis showed the formation of mesoporous agglomerates consisting of amorphous-crystalline NPles approximately 2 nm in size in the Fhy S95 sample annealed at 95 ºC. Selected area electron diffraction (SAED) images indicated the presence of two crystalline phases in sample S95: FeO and zero-valence Fe. The specific surface area (SSA) of mesoporous Fhy NPles varied non-monotonically between 100 and 500 ºC, peaking at 53.2 m2/g at 300 ºC. X-ray photoelectron spectroscopy (XPS) analysis revealed a minor nitrogen impurity, likely from the initial iron nitrate precursor, and a significant amount of adsorbed carbon on the developed porous surface of Fhy NPles. The phase composition of annealed Fhy samples correlated with their photoluminescent (PL) spectra. In samples S400 and S500 containing hematite, a small ferromagnetic contribution emerged, disrupting the linear magnetization-field dependence observed in samples S0-S200. Thus, the properties of 2 L Fhy nanoparticles produced by the radiation chemical method can be modified through thermal annealing while maintaining their potential biomedical applications as nanocontainers for drug delivery and contrast agents.

Enhancement in ZnO-based self-powered photodetector by inserting Mn dopant

In this study, the effect of Mn doping on the photovoltaic properties of ZnO films deposited on a p-Si substrate via spray pyrolysis has been evaluated. The Mn concentration was varied at 0, 1, and 3 wt%. The spray was carried out at 400 °C for 10 min. As a result, the X-ray diffraction pattern shows that the crystallite size decreases linearly with increasing Mn doping, from 44 nm (0% Mn) to 31 nm (3% Mn). Scanning electron microscopy images show that the increase in Mn concentration causes the nanostructure size to be smaller, from 325 nm (0% Mn) to 112.3 nm (3% Mn). Interestingly, the best photosensitivity and response time are found in the doped sample (3% Mn) at a bias voltage of 0 V rather than 1 V and 5 V, indicating the photovoltaic effect. This result is important to develop future self-powered devices.

Structural, magnetic and electrical properties of gadolinium doped cobalt ferrite nanoparticles: Role of Gd doping level

In this communication, effect of Gd doping for CoFe2–xGdxO4 (CFGO) nanoparticles has been investigated for structural, magnetic and electrical properties. X–ray diffraction (XRD) patterns reveal the presence of matrix like CFGO phase fraction with coexisting GdFeO3 (GFO) smaller crystallites and α–Fe2O3 (FO) phase fraction. Variation in crystallite size (D) for all three phases has been explored from the analysis on XRD patterns. Magnetic nature has been understood on the basis of lattice disorder, magnetic linkages between different ions of CFGO lattices that conduces magnetic characteristic of three different phases coexist within the CFGO nanoparticle lattices. Influence of frequency, temperature and Gd doping level on different electrical behaviors has been understood on the bases of various relaxation processes, charge conduction mechanism, correlated barrier hopping (CBH) mechanism, maximum barrier height, activation energy and structure–property correlations.

Phase diagram of ruthenium characterized In Situ by synchrotron X-ray diffraction and Ab Initio simulations

In this work, an in situ characterization of the high-pressure and high-temperature phase diagram of ruthenium was carried out. This experiment was performed using a combination of laser-heated diamond anvil cell (LH-DAC) and X-ray diffraction (XRD) techniques at the beamline ID27 of the European Synchrotron Radiation Facility (ESRF). XRD patterns were collected in the range of 15 GPa to 110 GPa and from ambient temperature up to 6600 K. While the hcp-fcc transition, predicted to occur at elevated temperatures was not observed, this study has produced the first experimental observation of a solid–liquid phase transition of Ru at HP conditions. A P-V-T equation of state valid up to 100 GPa and 3000 K is reported.

Enhanced Propylene/Propane Separation via Aniline-Decorated ZIF-8 Membrane: Lattice Rigidity Adjustment and Adsorption Site Introduction.

Metal-organic framework (MOF)-based membranes excel in molecular separation, attracting significant research interest. The crystallographic microstructure and selective adsorption capacity of MOFs closely correlate with their gas separation performance. Here, aniline was added to the ZIF-8 synthesis in varying concentrations. Aniline, encapsulated within ZIF-8 cavities, interacts strongly with the 2-methylimidazole linker, resulting in both a shift in crystallographic phase from I_43m to Cm in Rietveld refinement of X-ray diffraction (XRD) patterns and the selective adsorption behavior between propylene and propane. Consequently, an aniline decorative ZIF-8 (Anix-ZIF-8) membrane was prepared using a fast current-driven synthesis method, which exhibits good propylene/propane separation selectivity of up to 85. Calculation of the interaction energy between aniline and the various crystallographic phases of ZIF-8 using density functional theory (DFT) further verifies that aniline not only promotes the formation of crystallographic Cm phase, but also enhances the adsorption selectivity of propylene over propane.Aniline modification effectively tunes the crystallographic microstructure of ZIF-8, thereby, improving molecular sieving capabilities.

Synthesis and characterisation of visible light-responsive Fe-doped BiOCl NPs and their application for the remediation of textile dye by LED irradiation

ABSTRACT In the present research work, Fe-doped bismuth oxychloride (Fe-doped BiOCl) photocatalyst is synthesised through the precipitation technique, and the mineralisation of textile dye is investigated in the presence of light-emitting diode (LEDs) irradiation (400–700 nm). The prepared photocatalysts were characterised through various spectroscopic techniques for the detailed morphological, elemental and surface properties. The UV–vis absorbance maxima of Fe-doped BiOCl by UV-Vis was near 358 nm, while the band gap was 4.8 eV which is comparatively higher than the average value. Fourier transform infrared spectra showed typical bands of Fe doped BiOCl at 506 cm−1, 1601, 2337 and at 3565.0 cm−1. From the X-ray diffraction (XRD) pattern, the crystalline nature of the Fe-doped nanocomposite was confirmed whose calculated crystallite size was 41.12 nm. The major and sharp two theta peaks of XRD were at 11.95°, 24.07°, 25.81°, 32.46°, 33.39°, 36.47°. The microscopic technique showed that the size of the nanocomposite was 200–400 nm which was in the form of small nanosheets. The energy dispersive X-ray spectroscopy (EDS) showed peaks for Bi, O, Cl and Fe 36.91%, 26.48%, 36.37% and 0.24%, respectively, indicating the formation of the nanocomposite. The BET surface area of the Fe-doped BiOCl photocatalyst was 10.224 m2/g, while the pore volume was 0.065 cc/g. Further, the potential of the developed photocatalytic nanocomposite was evaluated for the photocatalytic degradation of the ethyl violet dye from the aqueous solutions. Various optimisation parameters have been discussed, and it has been found that 89% of the dye was degraded in 125 min with a 5.11 × 10−4 s−1 rate constant. The photocatalyst had shown excellent reusability and stability during the degradation of ethyl violet. The photocatalytic activity of Fe-doped BiOCl was compared with other photocatalysts and current literature and exhibited enhanced efficiency.

Effect of gamma and ultraviolet irradiation on the optical properties of copper oxide nanostructured thin films by chemical spray pyrolysis

Nanostructured copper oxide thin films were grown by the chemical spray pyrolysis (CSP) technique. Utilizing a homemade spray pyrolysis method, thin films are created. This work investigates the role of gamma ray and ultraviolet ray irradiation on the optical properties of copper oxide thin films(CuO) prepared. In this framework, used different substrate temperatures 300 °C, 350 °C, and 400 °C for the layers were grown on glass for the prepared CuO thin films. UV–visible spectrometer, field emission scanning electron microscopy (FE-SEM) and X-ray diffraction patterns(XRD) measurements were all used to characterize the samples. The UV–visible spectroscopy showed a decrease in the absorbance and the optical band gap of CuO thin films with the increase in the higher substrate temperatures before irradiation. Additionally, surface plasmon resonance peaks (λSPR) were observed at 329 nm. FE-SEM images revealed spherical-like shapes with an average diameter range of 48 nm,56 nm and 62 nm for 300 °C, 350 °C, and 400 °C, respectively. An analysis of X-rays revealed that CuO thin films contained the crystallographic planes of a monoclinic and an orthorhombic crystal system. Also, when samples were exposed to gamma and UVC radiation, the absorbance intensity of CuO thin films increased, but the optical band gap decreased.

Synthesis, characterization and effective UV photo-sensing properties of Ga3+ doped NiO nanoparticles

In this work, resistive type photodetectors were fabricated using Gd3+ ions doped NiO nanoparticles to improve the detection of ultraviolet (UV) light. The occurrence of the simple cubic phase in NiO systems has been shown by X-ray diffraction patterns. The crystalline size of the NiO nanoparticles doped with different concentrations of Gd3+ at levels of pure, 1 %, 2 %, and 3 % were 6 nm, 8 nm, 9 nm, and 12 nm, respectively. The presence of dopants in the material was established by the Raman spectrum analysis. Transmission electron microscopy (TEM) pictures were used to validate the morphological properties of Gd3+ doped NiO nanoparticles nanoparticles at different degrees of dopant concentration (0 %, 1 %, 2 % and 3 %). The introduction and concentration of dopants alter the shape of NiO material. Based on the findings of UV–visible absorption spectroscopic studies, it can be concluded that the addition of Gd3+ ions to the system improved the absorption characteristics. The measured bandgap values for various degrees of Gd3+ doping, namely 0 %, 1 %, 2 %, and 3 %, are 3.51 eV, 3.45 eV, 3.36 eV, and 3.23 eV, respectively. According to the measured photoluminescence spectrum, Gd3+ ions may efficiently trap and maintain excited electrons within an energy level between the ground and excited states. This process greatly extends the lifespan of excitons from immediate recombination. The use of Gd3+-doped NiO sensors in UV photodetection resulted in a significant increase in conductivity and photocurrent. The photodetector fabricated using a 3 % concentration of Gd3+ doped NiO, has a responsivity of 24 × 10−2 AW−1, a detectivity of 14 × 109 Jones, and an external quantum efficiency (EQE) of 62 %.

Crystal and thermodynamic properties of [formula omitted], (X = Al, Ga)

The crystal and thermodynamic properties of Tb2Ni2X (X = Al, Ga) are reported through measurements of X-ray diffraction (XRD), magnetic susceptibility, χ(T), magnetization, M(μ0H) and heat capacity, Cp(T). XRD pattern analysis confirms the orthorhombic W2CoB2-type structure with the space group of Immm. χ(T) at high temperature for both compounds follows the Curie – Weiss relationship giving an effective magnetic moment close to that expected for the trivalent Tb ion. The low-temperature χ(Cp) data indicate that both compounds order antiferromagnetically at TN = 41 K (40.4 K) and 41.5 K (41.4 K) for Al and Ga compounds, respectively. Cp(T) data of the nonmagnetic counterparts Y2Ni2X (X = Al, Ga) are well described by the Debye model giving a Debye temperature, θD = 236.9(4) K and 225.3(2) K for Al and Ga compounds, respectively. The low-temperature part of the 4f-magnetic contribution to the total heat capacity, C4f(T) can be described by the antiferromagnetic spin-wave dispersion, giving an energy gap Δsw = 47(3) K and 26(2) K for Al and Ga compounds, respectively. The 4f – magnetic entropy S4f(T) for both compounds reaches the value of 2Rln(2) close to their respective TN values.

Exploring the impact of CuCl2 modification on structural variations and dielectric constant in bismuth borate tellurite glasses

Copper chloride doped boro-tellurite-based glass series with compositions 60TeO2-(25-x) Bi2O3–15B2O3-xCuCl2 (x = 0, 5, 10, 15, and 20) were synthesized using the traditional melt-quench procedure. The X-ray diffraction patterns of the examined glasses reveal their amorphous nature. The effect of CuCl2 addition on the glass network/structural units was studied using vibrational (FTIR/Raman) spectroscopy, and CuCl2 inclusion in the glass matrix resulted in a transformation from compact TeO4 to TeO3 structural units This shows that copper chloride acts as a modifier in the examined glass series, resulting in the creation of non-bridging oxygen (NBOs), meaning that the loosening of the glass network is further supported by a decrease in the glass transition temperature as CuCl2 content increases. UV–Vis DRS spectra of examined glasses reveal an absorption band corresponding to the typical transition of Cu2+ ions from 2B1g → 2B2g, situated in deformed octahedral sites in absorption spectra. As Cu+ concentration rises, the indirect optical band gap values drop from 2.94 eV to 1.75 eV. The metallization criterion values lie between 0.383 and 0.300 suggesting that these glasses are potential candidates for nonlinear optical applications. With an increase in Cu+ concentration, the values of molar refractive index (Rm) and molar electronic polarizability αm increases from 22.412 to 26.205 and 8.894 to 10.398 respectively, which correlate with increasing dielectric constant (ε′) values as the Cu+ amount increases. Further dielectric studies reveal non-Debye-type relaxation behaviour.

Deep learning for symmetry classification using sparse 3D electron density data for inorganic compounds

We report a novel deep learning (DL) method for classifying inorganic compounds using 3D electron density data. We transform Density Functional Theory (DFT)-derived CHGCAR files from the Materials Project (MP) and experimental data from the Inorganic Crystal Structure Database (ICSD) into point clouds and sparse tensors, optimized for use in DL models such as PointNet and Sparse 3D CNN. This approach effectively overcomes the limitations of handling the dense 3D data, a common challenge in DL. Contrasting with traditional 1D or 2D X-ray diffraction (XRD) patterns that necessitate complex reciprocal space analysis, our method utilizes 3D density data for direct interpretation in real lattice space. This shift significantly enhances classification accuracy, outperforming traditional XRD-driven DL methods. We achieve accuracies of 97.28%, 90.77%, and 90.10% for crystal system, extinction group, and space group classifications, respectively. Our 3D electron density-based DL approach not only showcases improved accuracy but also contributes a more intuitive and effective framework for materials discovery.

The Staged Photocatalytic Reactor in the Removal of Acetaminophen: Aspects of Adsorption and Photocatalysis.

The efficiency of a staged photocatalytic reactor prototype was evaluated on a semi-pilot scale with the removal of acetaminophen, for which anatase particles were synthesized by Sol-Gel and impregnated on rectangular plates of clay. X-ray diffraction and Energy Dispersive X-ray Fluorescence patterns show that the final composite is made up of Al2O3 (14 %), SiO2 (41 %), CaO (3 %) TiO2 (34 %), and Fe2O3 (7 %). The impregnation method favors the dispersion of Anatase on the surface of the adsorbent. TiO2-Anatase/Clay, classified as a macro-porous solid with H3-type hysteresis loops by N2 physisorption. Adsorption processes are improved when using TiO2-Anatase/Clay compared to using TiO2-Anatase. The external mass transfer has a greater influence on the removal rate. The dimensionless parameters of the Biot number indicate there are no limitations due to the diffusive effect on the interior of the particle. The evaluation of the kinetic data under the Langmuir-Hinshelwood equation shows a decrease in efficiency as the initial concentration increases. The acetaminophen molecule shows destabilization in the structure of the aromatic ring with a visible decrease in the signals of this functional group evaluated by High-Performance Liquid Chromatography and Raman Spectroscopy.

Towards end-to-end structure determination from x-ray diffraction data using deep learning

Powder crystallography is the experimental science of determining the structure of molecules provided in crystalline-powder form, by analyzing their x-ray diffraction (XRD) patterns. Since many materials are readily available as crystalline powder, powder crystallography is of growing usefulness to many fields. However, powder crystallography does not have an analytically known solution, and therefore the structural inference typically involves a laborious process of iterative design, structural refinement, and domain knowledge of skilled experts. A key obstacle to fully automating the inference process computationally has been formulating the problem in an end-to-end quantitative form that is suitable for machine learning, while capturing the ambiguities around molecule orientation, symmetries, and reconstruction resolution. Here we present an ML approach for structure determination from powder diffraction data. It works by estimating the electron density in a unit cell using a variational coordinate-based deep neural network. We demonstrate the approach on computed powder x-ray diffraction (PXRD), along with partial chemical composition information, as input. When evaluated on theoretically simulated data for the cubic and trigonal crystal systems, the system achieves up to 93.4% average similarity (as measured by structural similarity index) with the ground truth on unseen materials, both with known and partially-known chemical composition information, showing great promise for successful structure solution even from degraded and incomplete input data. The approach does not presuppose a crystalline structure and the approach are readily extended to other situations such as nanomaterials and textured samples, paving the way to reconstruction of yet unresolved nanostructures.

The role of phase transformation (tetragonal – spinel) on the structural and mechanical properties of Ni doped CuFe2O4

Nano-ferrites of Cu1–xNixFe2O4 (x = 0 to 1 with step 0.2) system was synthesized utilizing the flash auto combustion process annealed at 600oC for 3 h. The structural characterization for synthesized samples was carried out using x-ray Diffraction (XRD), Fourier transition infrared spectroscopy (FTIR) and transmission electron microscopy (TEM). The hardness of the prepared material was measured using micro-indentation creep technology. XRD pattern verified the creation of a single-phase cubic spinel structure. The undesired CuO phase forms around \\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\:2\ heta\\:={50}^{^\\circ\\:}\\:$$\\end{document}for pure Copper ferrite and decreases with increasing Ni content. The average crystalline size decreases from 27.92 nm to 13.28 nm by doping process from x = 0.2 to x = 1 which retards the growth of crystalline size. FTIR spectra are distinguished by the presence of two prominent absorption bands, ν2 for the octahedral site and ν1 for the tetrahedral site, in the range of approximately 593 and 471 cm− 1, respectively. FTIR analysis verified the formation of the ferrite system’s spinel structure. The TEM images show a nanocrystalline nature with some agglomeration and the crystallites are spherical in shape which their sizes are agrees well with that obtained from XRD measurements. The hardness decreases as the dwell time increases. The hardness and yield strength (Y) values were significantly improved due to the decrease in the crystallite size after Ni doping. The stress exponent (n) value increases by increasing Ni content which means that the mechanical properties improved due to increment of resistance.

Single-crystal growth, crystal structure, and molecular dynamics of organic–inorganic [NH3(CH2)2NH3]CuBr4

As part of obtaining excellent properties that can be used as lead-free hybrid solar cells, the crystal growth, crystal structure, phase transition temperature, and thermal properties for [NH3(CH2)2NH3]CuBr4 were discussed. The crystal structure at 300 K was determined to be monoclinic by single-crystal X-ray diffraction (XRD) analysis. The phase transition temperatures were determined to be 447 and 473 K, and the results were consistent with the powder XRD patterns. Thermogravimetric analysis revealed thermal stability up to ~ 460 K. The continuous changes in the 1H and 13C chemical shifts and 14N static resonance frequency with increasing temperature are related to variations in the local environment and coordination geometry. The significant differences in activation energies obtained from the 1H and 13C spin–lattice relaxation times (t1ρ) at low and high temperatures were discussed. The activation energy results suggested that the energy barrier at low temperatures was related to the reorientation of the NH3 and CH2 groups around the three-fold symmetry axis, and the energy barrier at high temperatures was related to the reorientation of the [NH3(CH2)2NH3] cation. These physical properties will be provide important insights or potential applications of this crystal.Please check and confirm that the corresponding author and their respective corresponding affiliation have been correctly identified and amend if necessary.OK !

Probing the structural evolution of cobalt hydroxide in electrochemical water splitting.

Transition-metal hydroxides are a category of earth-abundant and stable electrocatalysts for energy storage and conversion devices involving sluggish oxygen evolution reaction (OER). Understanding dynamic evolution at the solid/liquid interface of transition-metal hydroxides is crucial for the rational design of high-performance OER electrocatalysts. This study implemented in situ electrochemical atomic force microscopy (EC-AFM) to directly image the dynamic structural evolution of α-Co(OH)2 platelets during the electrochemical OER. Reconstruction of α-Co(OH)2, accompanied by ion insertion from the electrolyte, results in a volume expansion, which can be well confirmed from the X-ray diffraction patterns. Our findings are important for the fundamental understanding of transition-metal hydroxide oxygen-evolution catalysts, illustrating the dynamic nature of Co-based nanostructures under electrochemical conditions.

Polyoxometalate inhibition of SOX2-mediated tamoxifen resistance in breast cancer

BackgroundIncreased cancer stem cell (CSC) content and SOX2 overexpression are common features in the development of resistance to therapy in hormone-dependent breast cancer, which remains an important clinical challenge. SOX2 has potential as biomarker of resistance to treatment and as therapeutic target, but targeting transcription factors is also challenging. Here, we examine the potential inhibitory effect of different polyoxometalate (POM) derivatives on SOX2 transcription factor in tamoxifen-resistant breast cancer cells.MethodsVarious POM derivatives were synthesised and characterised by infrared spectra, powder X-ray diffraction pattern and nuclear magnetic resonance spectroscopy. Estrogen receptor (ER) positive breast cancer cells, and their counterparts, which have developed resistance to the hormone therapy tamoxifen, were treated with POMs and their consequences assessed by gel retardation and chromatin immunoprecipitation to determine SOX2 binding to DNA. Effects on proliferation, migration, invasion and tumorigenicity were monitored and quantified using microscopy, clone formation, transwell, wound healing assays, flow cytometry and in vivo chick chorioallantoic membrane (CAM) models. Generation of lentiviral stable gene silencing and gene knock-out using CRISPR-Cas9 genome editing were applied to validate the inhibitory effects of the selected POM. Cancer stem cell subpopulations were quantified by mammosphere formation assays, ALDEFLUOR activity and CD44/CD24 stainings. Flow cytometry and western blotting were used to measure reactive oxygen species (ROS) and apoptosis.ResultsPOMs blocked in vitro binding activity of endogenous SOX2. [P2W18O62]6− (PW) Wells-Dawson-type anion was the most effective at inhibiting proliferation in various cell line models of tamoxifen resistance. 10 µM PW also reduced cancer cell migration and invasion, as well as SNAI2 expression levels. Treatment of tamoxifen-resistant cells with PW impaired tumour formation by reducing CSC content, in a SOX2-dependent manner, which led to stem cell depletion in vivo. Mechanistically, PW induced formation of reactive oxygen species (ROS) and inhibited Bcl-2, leading to the death of tamoxifen-resistant cells. PW-treated tamoxifen-resistant cells showed restored sensitivity to tamoxifen.ConclusionsTogether, these observations highlight the potential use of PW as a SOX2 inhibitor and the therapeutic relevance of targeting SOX2 to treat tamoxifen-resistant breast cancer.