Crystalline Samples Research Articles

Sedimentation of large, soluble proteins up to 140kDa for 1H-detected MAS NMR and 13C DNP NMR - practical aspects.

Solution NMR is typically applied to biological systems with molecular weights < 40kDa whereas magic-angle-spinning (MAS) solid-state NMR traditionally targets very large, oligomeric proteins and complexes exceeding 500kDa in mass, including fibrils and crystalline protein preparations. Here, we propose that the gap between these size regimes can be filled by the approach presented that enables investigation of large, soluble and fully protonated proteins in the range of 40-140kDa. As a key step, ultracentrifugation produces a highly concentrated, gel-like state, resembling a dense phase in spontaneous liquid-liquid phase separation (LLPS). By means of three examples, a Sulfolobus acidocaldarius bifurcating electron transfer flavoprotein (SaETF), tryptophan synthases from Salmonella typhimurium (StTS) and their dimeric β-subunits from Pyrococcus furiosus (PfTrpB), we show that such samples yield well-resolved proton-detected 2D and 3D NMR spectra at 100kHz MAS without heterogeneous broadening, similar to diluted liquids. Herein, we provide practical guidance on centrifugation conditions and tools, sample behavior, and line widths expected. We demonstrate that the observed chemical shifts correspond to those obtained from µM/low mM solutions or crystalline samples, indicating structural integrity. Nitrogen line widths as low as 20-30Hz are observed. The presented approach is advantageous for proteins or nucleic acids that cannot be deuterated due to the expression system used, or where relevant protons cannot be re-incorporated after expression in deuterated medium, and it circumvents crystallization. Importantly, it allows the use of low-glycerol buffers in dynamic nuclear polarization (DNP) NMR of proteins as demonstrated with the cyanobacterial phytochrome Cph1.

Probing Self-Diffusion of Guest Molecules in a Covalent Organic Framework: Simulation and Experiment.

Covalent organic frameworks (COFs) are a class of porous materials whose sorption properties have so far been studied primarily by physisorption. Quantifying the self-diffusion of guest molecules inside their nanometer-sized pores allows for a better understanding of confinement effects or transport limitations and is thus essential for various applications ranging from molecular separation to catalysis. Using a combination of pulsed field gradient nuclear magnetic resonance measurements and molecular dynamics simulations, we have studied the self-diffusion of acetonitrile and chloroform in the 1D pore channels of two imine-linked COFs (PI-3-COF) with different levels of crystallinity and porosity. The higher crystallinity and porosity sample exhibited anisotropic diffusion for MeCN parallel to the pore direction, with a diffusion coefficient of Dpar = 6.1(3) × 10-10 m2 s-1 at 300 K, indicating 1D transport and a 7.4-fold reduction in self-diffusion compared to the bulk liquid. This finding aligns with molecular dynamics simulations predicting 5.4-fold reduction, assuming an offset-stacked COF layer arrangement. In the low-porosity sample, more frequent diffusion barriers result in isotropic, yet significantly reduced diffusivities (DB = 1.4(1) × 10-11 m2 s-1). Diffusion coefficients for chloroform at 300 K in the pores of the high- (Dpar = 1.1(2) × 10-10 m2 s-1) and low-porosity (DB = 4.5(1) × 10-12 m2 s-1) samples reproduce these trends. Our multimodal study thus highlights the significant influence of real structure effects such as stacking faults and grain boundaries on the long-range diffusivity of molecular guest species while suggesting efficient intracrystalline transport at short diffusion times.

Process development in Quality‐by‐Design paradigm for anti‐solvent aided crystallization: impact of crystallization parameters on particle morphology and dissolution behaviour of Dexlansoprazole active pharmaceutical ingredient

AbstractBACKGROUNDIn this work, a process development study for the crystallization step of dexlansoprazole API has been demonstrated under the Quality‐by‐Design (QbD) paradigm. Dexlansoprazole (crystalline) samples prepared under different crystallization conditions of reactor temperature and addition time of anti‐solvent were subjected to solid‐state characterization with variety of analytical techniques, including X‐ray powder diffraction (XRPD), differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), dynamic vapour sorption (DVS), scanning electron microscopy (SEM), particle size distribution (PSD) by laser diffraction and intrinsic dissolution rate (IDR).RESULTSThe crystalline samples were observed to have identical polymorphic phase integrity but differed in their physical characteristics. The particle size distribution and microscopy data collectively elucidated the particle growth kinetics and the extent of agglomeration could be correlated to crystallization conditions, namely reactor temperature and addition time of anti‐solvent. The intrinsic dissolution rate of samples was in good agreement with the morphological properties.CONCLUSIONAn empirical model has been proposed for intrinsic dissolution rate correlating with crystallization process parameters. In conclusion, it was possible to elucidate the impact of crystallization parameters on the solid‐state behaviour of dexlansoprazole for development of appropriate pharmaceutical dosage forms. © 2024 Society of Chemical Industry (SCI).

Sunlight-Driven Smart Windows with a Wide Temperature Range of Optical Switching Based on Chiral Nematic Liquid Crystals.

Photoresponsive liquid crystals are promising materials for sunlight-driven smart windows, which can automatically change their optical states in response to sunlight and control energy flow between the inside and outside of a building. Herein, liquid-crystalline systems are developed that show a transparent-scattering transition upon irradiation with sunlight in a wide temperature range. Push-pull azobenzenes with axial chirality have been newly developed as photochromic chiral dopants to allow changes in mesostructures of liquid crystals in response to sunlight. To realize optical switching, photochromic and photoinert chiral compounds with opposite handedness of helical twisting are doped in liquid crystals. This liquid crystalline sample with a compensated nematic phase is transparent in its initial state. Upon irradiation with sunlight, this sample transforms to a scattering state due to the formation of helical mesostructures along with photoisomerization of azobenzene moieties and the change in the helical twisting power. After the cease of irradiation, the sample reverts to the transparent state through thermal back isomerization of azobenzene moieties. This system significantly improves the operating temperature range of sunlight-driven smart windows based on liquid crystals: the transparent-scattering transition is observed at 4-42 °C. The present mechanism allows development of autonomous and wireless smart windows adaptable to various environments.

Defectivity of Al:ZnO thin films with different crystalline order probed by Positron Annihilation Spectroscopy

Three Positron Annihilation Spectroscopy (PAS) techniques have been employed to investigate the point defects of Al-doped Zinc Oxide (AZO) thin films grown by Radio Frequency (RF) magnetron sputtering with different substrates and deposition parameters. The films were grown with thickness varying from 100 to 300 nm, and their crystalline quality ranged from single crystalline epitaxial to partially amorphous. We found that the main defect in the crystalline samples is the 3VZn−VO four vacancy complex, with a concentration around 1018−1019 cm−3. In polycrystalline films larger vacancy clusters, within 10%−20% of the total concentration, were detected. These vacancy clusters are inferred to be most likely located at the grain boundaries. In partially amorphous films the concentration of these larger vacancy clusters, located either at grain boundaries or in the amorphous regions of the film, approached even the 40%, and also some sub-nano voids have been observed.

Regular relations of the composition, structure and properties of crystals of hydrogen-containing compounds

Research subject. Crystals of hydrogen-containing compounds belonging to the superprotonic family. Aim. To obtain knowledge about regular relations between composition, atomic structure, real structure and physical properties of materials, with the purpose of elucidating processes occurring in condensed state and forming the basis for modification of known or obtaining new compounds. Materials and methods. Experimental data were obtained using a set of complementary physical methods, including structural analysis using X-rays, synchrotron radiation and neutrons, optical microscopy, and atomic force microscopy. Results. Experimental data on the atomic structure, real structure, and physical properties of superprotonic crystals, including systems of hydrogen bonds and their changes, were obtained. Conclusions. The physical properties of superprotonic crystals are significantly affected by hydrogen bonding systems and their changes, primarily by the formation of dynamically disordered hydrogen bonds with energetically equivalent positions of hydrogen atoms. When carrying out diagnostics of crystalline samples, account should be taken of their real structure, including the structure of surface layers and the presence of crystallization water. These factors may affect the measured physical parameters, the boundaries of existence of phases, the formation of a multiphase state under variations in temperature.

Colour tuning in Sm3+ activated and Sm3+/Eu3+ co-activated SrBi4Ti4O15 phosphors for w-LED applications

SrBi4Ti4O15 (SBT) phosphors activated by Sm3+ and co-activated by Eu3+ have been synthesized in the current research using a straightforward solid-state reaction technique. X-ray Diffraction (XRD) confirms the sample's crystallinity. Scanning electron microscopy (SEM), energy dispersive x-ray spectroscopy (EDX), and elemental mapping have been used to analyse the morphology and elemental composition of the synthesized phosphor. Fourier-transform infrared spectroscopy (FT-IR) analysis has confirmed the vibrational characteristics of the as prepared phosphor. Photoluminescence studies show increase in luminescence intensity in case of Sm3+/Eu3+ co-activated phosphors as compared with singly doped Eu3+ and Sm3+ activated SBTO phosphors. Colour tunability was also observed from reddish-orange to pure red region when Sm3+ activated phosphors were co-activated with Eu3+ ions. These outcomes demonstrate that SrBi4Ti4O15 phosphors activated or co-activated with Sm3+ and Eu3+ can be deployed in w-LEDs and other display devices applications.

Formation of Binary Compounds of Impurity Atoms of Sulfur and Zinc in Silicon

The paper presents the information on thermodynamic conditions and describes process stages required in order to form binary zinc-and-sulfur (ZnS) elementary cells in single-crystalline silicon while doping it with impurity atoms of group II and VI elements, i.e., zinc and sulfur, respectively. The thermodynamic conditions that ensure shaping of such elementary cells in silicon have been established. It has also been revealed that before binary compound (consisting of zinc and sulfur atoms) nanoclusters, those chemical elements may have been present in the silicon matrix in the form of separately located atoms or various naturаl compounds. It is supposed that it might be possible to engineer previously-unknown silicon-based materials with unique fundamental properties by applying the technique of assembling elementary cells and binary compounds of the ZnS type with pre-set concentrations. Using a scanning tunneling microscope, it was possible to determine the elemental composition of binary compounds that were formed in the matrix and on the surface of a silicon sample. An analysis of the results of the above experiments showed that binary compounds of the ZnS type are possibly formed in the Si crystalline sample characterized by new electrophysical parameters.

Producing Conventional and Transient Amino(mercapto)methyl Radicals by Addition of Muonium to a Crystalline Thioformamide (Mes*NHCH=S).

Muonium (Mu=μ+e-) is composed of a muon of light isotope of proton (μ+) and electron (e-) and can be used as a light surrogate for a hydrogen atom. In this paper, we investigated addition of muonium to a newly synthesized Mes*-substituted thioformamide (Mes*NHCH=S, Mes*=2,4,6-tBu3C6H2). Transverse-field muon spin rotation (TF-μSR) of a solution sample of the thioformamide confirmed addition of muonium to the sulfur atom leading to the corresponding C-centered radical [Mes*NHC(H)⋅-SMu]. Density functional theory (DFT) calculations assigned a conventional amino(mercapto)methyl radical, in which both nitrogen and carbon were slightly pyramidalized, and the calculated muon hyperfine coupling constant (hfcc) including the muon isotope effect was compatible with the experimentally determined parameter. However, the muon level-crossing resonance (μLCR) spectrum of an anisotropic crystalline sample indicated two paramagnetic species, and the major product showed the considerably larger muon hfcc compared with the conventional structure of the amino(mercapto)methyl radical. The unusual transient muoniated thioformamide with the larger muon hfcc that showed rapid relaxation could be only explained by a transient structure including planarization of the nitrogen and carbon atoms in Mes*NHC(H)⋅-SMu.

Isochemical crystallization in condensed borate LaMgB5O10 glass-ceramics doped with optical probe Eu3.

The isochemical glass-ceramics doped with Eu3+ were prepared by the heat treatment of lanthanum magnesium borate glass. The crystalline phase was chemically identical to a glass matrix and consisted of condensed borate LaMgB5O10. The isochemical crystallization process begins with the formation of rings by BO4 groups. The emergence of ordered crystalline phase gives rise to intense charge transfer absorption of Eu3+, allowing the efficient luminescence under UV. The analysis of Judd-Ofelt parameters and comparison to purely crystalline samples obtained by solid-state synthesis reveal a switch of parameter relations from Ω2 > Ω4 for glass to Ω2 < Ω4 for crystals but also a maximum value of Ω6 for glass-ceramic sample, which indicates enhanced structural rigidity and results in superior luminescence output. The quantum yield measurements confirmed higher luminescence efficiency for glass-ceramics compared to both pure glass and pure crystalline samples.

Iterative Bragg peak removal on X-ray absorption spectra with automatic intensity correction.

This study introduces a novel iterative Bragg peak removal with automatic intensity correction (IBR-AIC) methodology for X-ray absorption spectroscopy (XAS), specifically addressing the challenge of Bragg peak interference in the analysis of crystalline materials. The approach integrates experimental adjustments and sophisticated post-processing, including an iterative algorithm for robust calculation of the scaling factor of the absorption coefficients and efficient elimination of the Bragg peaks, a common obstacle in accurately interpreting XAS data, particularly in crystalline samples. The method was thoroughly evaluated on dilute catalysts and thin films, with fluorescence mode and large-angle rotation. The results underscore the technique's effectiveness, adaptability and substantial potential in improving the precision of XAS data analysis. While demonstrating significant promise, the method does have limitations related to signal-to-noise ratio sensitivity and the necessity for meticulous angle selection during experimentation. Overall, IBR-AIC represents a significant advancement in XAS, offering a pragmatic solution to Bragg peak contamination challenges, thereby expanding the applications of XAS in understanding complex materials under diverse experimental conditions.

Processing and cytocompatibility of Cu-doped and undoped fluoride-containing bioactive glasses

Sintered or additive-manufactured bioactive glass (BG) scaffolds are highly interesting for bone replacement applications. However, crystallization often limits the high-temperature processability of bioactive glasses (BGs). Thus, the BG composition must combine high bioactivity and processability. In this study, three BGs with nominal molar (%) compositions 54.6SiO2-1.7P2O3-22.1CaO-6.0Na2O-7.9K2O-7.7MgO (13–93), 44.8SiO2-2.5P2O3-36.5CaO-6.6Na2O-6.6K2O-3.0CaF2 (F3) and 44.8SiO2-2.5P2O3-35.5CaO-6.6Na2O-6.6K2O-3.0CaF2-1.0CuO (F3–Cu) were investigated. The dissolution and ion release kinetics were investigated on milled glass powder and crystallized particles (500–600 μm). All glasses showed the precipitation of hydroxyapatite (HAp) crystals after 7 days of immersion in simulated body fluid. No significant differences in ion release from glass and crystalline samples were detected. The influence of surface roughness on cytocompatibility and growth of pre-osteoblast cells (MC3T3-E1) was investigated on sintered and polished BG pellets. Results showed that sintered BG pellets were cytocompatible, and cells were seen to be well attached and spread on the surface after 5 days of incubation. The results showed an inverse relation of cell viability with the surface roughness of pellets, and cells were seen to attach and spread along the direction of scratches.

Supramolecular assembly, structure, magnetic property, and proton conductivity of a nickel(II) hydrogen-bonded organosulfonate framework

A three-dimensional nickel(II) hydrogen-bonded organic framework (NiHOF), formulated as [Ni(H2O)2(EtOH)2(MeCN)2][nds] (NiHOF-HGNU-2, H2nds = 1,5-Naphthalenedisulfonic acid, HGNU = Huanggang Normal University), was synthesized and magnetically and electrically characterized. Single-crystal X-ray diffraction (SC-XRD) analysis revealed that extensive hydrogen bonding interactions formed between the [Ni(H2O)(EtOH)(MeCN)]2+cations and organodisulfonate anions nds2−, leading to a highly hydrogen-bonded network. Variable-temperature SC-XRD and thermogravimetric analysis both reveal the crystalline sample of NiHOF-HGNU-2 can be thermally stable up to 400 K. Magnetic investigations reveal the uniaxial magnetic anisotropy (D = -9.87 cm−1) of the distorted octahedral Ni2+ ions of NiHOF-HGNU-2 without slow magnetic relaxation. Alternating current impedance spectroscopy indicate NiHOF-HGNU-2 exhibits temperature- and humidity-dependent proton conduction behavior with the highest measured conductivity reaching 1.15 × 10−4 S cm−1 at 85 °C and 98 % relative humidity, suggesting a supramolecular proton conductor of the NiHOF-HGNU-2. The forgoing results not only provide a new Ni-based proton conductor but also an organodisulfonate strategy for building supramolecular proton-conducting materials.

A Six-Year Hydration Evaluation of Cs-Bearing Materials at Room Temperature and 55% Relative Humidity Simulating Radioactive Waste with Different Crystallinities.

Radioactive wastes often contain amorphous and crystalline phases, and vapor hydration can affect their durability. In this study, Cs-clinoptilolite was heated (at 1100 °C and for 2-36 h) to prepare the samples that were composed mainly of an amorphous phase (AmP) and CsAlSi5O12 (≥94%) with minor CsAlSi2O6. Six samples with an AmP/CsAlSi5O12 ratio from 26.5 to 0.1 were kept at 21 °C and 55% relative humidity, and their hydration was measured via thermogravimetry (TG) over a period of almost six years. The hydration that resulted was directly related to the AmP quantity. The increase in water content followed a logarithmic trend over time. It reached 1.95% in the AmP-richest material, while it attained only 0.07% in the most crystalline sample. The hydrolysis of the AmP led to an increase over time in the tightly bound water. Samples with an AmP of ≤19% demonstrated slightly higher durability due to the lower Cs content in the AmP.

Numerical simulation of proton backscattering spectra in GEANT4 toolkit

Rutherford backscattering spectroscopy (RBS) is a widely used technique for the atomic-scale analysis of sample composition, lattice displacement and impurity profiling. RBS is based on the elastic scattering of incident charged particles by target nuclei and the subsequent detection of scattered particles. The interpretation of RBS spectra, however, poses challenges due to overlapping peaks, corresponding to scattering from different atomic species, and uncertainties from energy loss, scattering geometry and detector response. To address this, an open source simulation model based on the versatile GEANT4 simulation toolkit has been developed. The flexibility of the open source enables users to tailor the model to its specific requirements, such as the use of specific particle stopping powers, cross-sections, and physics processes. This work presents the results of the comparison between the experimental and simulated backscattering spectra in crystalline silicon, silicon carbide and silicon dioxide samples by 1–2.5 MeV energy protons, obtained in random orientation conditions. The results demonstrate the capability of the model to accurately simulate backscattering spectra in both amorphous materials and single crystals. The overall agreement between the simulated and experimental results is highly promising for future development and use in the interpretation and simulation of RBS spectra.

Unveiling the correlation between the structure and property of the amorphous state of hydrated nickel sulfate (NiSO4·6H2O) induced by acoustic shock waves – An X-ray diffraction, thermal calorimetric and dielectric spectroscopic approach

In the present work, we report the phase transition from crystalline to amorphous (topological disorder) of NiSO4·6H2O (NSH) for which impedance spectroscopic and differential scanning calorimetric (DSC) techniques have been utilized to understand the changes in a better way thereby the electrical and thermal properties could be identified. According to the observed dielectric properties, the crystalline NSH has a low dielectric constant and low electrical conductivity whereas both of these values are high for the obtained amorphous state. DSC thermograms provide crystal clear details for the cause of the witnessed changes wherein the melting point region changes for both the crystalline and the amorphous samples. The values of magnetization for crystalline and amorphous samples are found to be 0.7339 and 2.070 emu/g, respectively. Because of the effective switchability between crystalline and amorphous states, the NSH crystal is suggested for the applications of sensors and dielectric switches.

Formation of magnetic nanoclusters in Fe implanted amorphous and crystalline SiO2

Conversion electron Mössbauer Spectroscopy (CEMS) studies have been conducted on Fe implanted amorphous and crystalline SiO2 which were annealed in air up to a temperature of 1000oC. For both samples, dramatic changes set in after the 1000oC anneal and the CEM spectra are dominated by strong ferromagnetic sextets. In the amorphous sample, the sextet is characterized by magnetic hyperfine fields of 33T, 31T and 29 T, consistent with the formation α-Fe nanoclusters. In the crystalline sample the ferromagnetic sextet has spectral parameters of δ = 0.38(3) mm/s and Bhf = 52.3T, consistent with formation of α-Fe2O3 clusters, reflecting the precipitation of the implanted Fe into such clusters. The line ratios of lines 1, 2 and 3 (and 6, 5 and 4) of the sextet are 3:4:1, reflecting alignment of the magnetic moment of the precipitates normal to the c-axis of the sample surface.

Hydantoin-D,L-valine: Synthesis, characterization, and non-covalent interaction analysis from crystallographic studies, DFTB calculations, and Hirshfeld surface analysis

The title compound, hydantoin-D,L-daline or (RS)-5-isopropyl-imidazolidine-2,4‑dione, a new amino acid hydantoin derivative with formula C6H10N2O2 has been synthesized and structurally characterized by FT-IR, NMR, and X-ray diffraction techniques. Spectroscopy results are consistent with the skeleton structure. The powder X-ray diffraction data confirms the phase purity of the crystalline sample. Single-crystal X-ray diffraction analysis indicated that the title compound crystallizes in the monoclinic space group P21/c (N°14), Z = 4, and unit cell parameters a = 5.493(3) Å, b = 23.53(2) Å, c = 6.254(3) Å, β= 115.09(4)°, V = 732.1(9) Å3. The molecular structure and crystal packing are stabilized by intermolecular N–H···O, C–H···O, and C–H···π hydrogen bonds forming an infinite two-dimensional network with chains described by the graph-set notation C(5), and centrosymmetric rings with graphs R22(8) and R44(16). The non-covalent interactions were analyzed employing DFTB calculations, which reproduce the main features of the stereochemistry and geometries exhibited by X-ray diffraction. Additionally, these intermolecular interactions were analyzed using Hirshfeld surfaces analysis and 2D fingerprint plots.

High-performance Ni-free sustainable cathode Na0.67Mg0.05Fe0.1Mn0.85O2 for sodium-ion batteries.

Having in mind the remarkable economic and environmental issues involved in the presence of nickel and cobalt metals in electrode compositions, new Na0.67Mg0.05Fe0.1NixMn0.85-xO2 (x=0.0, 0.05, 0.1, 0.15) with a P2 type layered structure, are synthesized to be essayed as positive electrodes in sodium-ion batteries. The sol-gel route here proposed favors the obtention of highly pure and crystalline samples with a homogeneous distribution of the constituting elements. Both galvanostatic and voltammetric tests reveal a superior electrochemical behavior for the Ni-free sample, which delivers 94 mA h g-1 at 5C. This excellent performance is associated with a good kinetic response in terms of low charge and discharge hysteresis, high Na+ diffusivity, and low cell resistance. Ex-situ measurements evidenced the combined contribution of both the reversible electrolyte insertion and the formation of peroxo species. These advantageous properties allow this electrode to reach a remarkable behavior when is cycled either to low temperatures or high rates.

Investigations on physical properties of (Sm, Ni) co-doped LaFeO3 perovskite

Nano crystalline samples of LaFeO3 (LFO) and La0.9Sm0.1Fe0.9Ni0.1O3 have been successfully synthesized through the sol-gel process. X-ray diffraction patterns confirm the orthorhombic phase of standard LaFeO3. FTIR spectroscopy shows the existence of two active vibrational modes around 410 and 550 cm−1. Specific heat capacity (Cp) displays exothermic and endothermic peaks, related to evaporation of water vapor and phase transitions respectively. The Cp is seen to rise in the doped sample, which ensures its increased thermal stability. Magnetic studies reveal the increase in magnetization and the transition from antiferromagnetic to ferromagnetic state in doped sample. Magnetoelectric study confirmed the multiferroic nature of LFO.