Lithium titanates are used in various applications, such as anode materials for lithium intercalation (Li4Ti5O12) or breeding materials in fusion reactors (Li2TiO3). Here, we report the formation of nano-crystalline lithium titanates by a mechanochemical approach and present a deeper insight into their structural characteristics by PXRD and solid-state NMR spectroscopy. The compounds were synthesized in a high energy planetary ball mill with varying milling parameters and different grinding tools. NaCl type Li2TiO3 (α-Li2TiO3) was formed by dry milling of lithium hydroxide with titania (rutile or anatase) and by a milling induced structure transformation of monoclinic β Li2TiO3 or spinel type Li4Ti5O12. Heating of mechanochemical prepared α Li2TiO3 induces a phase transformation to the monoclinic phase similar to hydrothermal reaction products, but a higher thermal stability was observed for the mechanochemical formed product. Microstructure and crystallographic structure were characterized by PXRD via Rietveld analysis. Detailed phase analysis shows the formation of the cubic phase from the various educts. A set of two lattice parameters for α Li2TiO3 was refined, depending on the presence of OH- during the milling process. An average crystallite size of less than 15 nm was observed for the mechanochemical generated products. The local Li environment detected by 6Li SPE MAS NMR revealed Li defects in the form of tetrahedral instead of octahedral site occupation. Subsequent adjustment of the structural model for Rietveld refinement leads to better fits, supporting this interpretation.

Taking into consideration the arising resistance towards the currently available antimycobacterial, there is still an unmet need for the development of new chemotherapeutic agents to combat the infectious agent. This study presents the X-ray single-crystal analysis to verify the structure of leading sulfonyl hydrazone 3b, which have proven their potent antimycobacterial activity against Mycobacterium tuberculosis H37Rv with MIC value of 0.0716 μM, respectively, low cytotoxicity and very high selectivity indexes (SI=2216) and fully characterized by NMR and HRMS methods. Furthermore, this study assessed the ex vivo antioxidant activity, acute and subacute toxicity, and in vitro inhibition capacity against enoyl-ACP reductase of hydrazones 3a and 3b, as 3a was identified as the second leading compound in our previous research. Compared to isoniazid, compounds 3a and 3b demonstrated lower acute toxicity for intraperitoneal administration, with LD50 values of 866 and 1224.7 mg/kg, respectively. Subacute toxicity tests, involving the repeated administration of a single dose of the test samples per day, revealed no significant deviations in hematological and biochemical parameters or pathomorphological tissues. The compounds exhibited potent antioxidant capabilities, reducing malondialdehyde (MDA) levels and increasing reduced glutathione (GSH). Enzyme inhibition assays of the sulfonyl hydrazones 3a and 3b with IC50 values of 18.2 µM and 10.7 µM, respectively and molecular docking studies revealed enoyl acyl carrier protein reductase (InhA) as the possible target enzyme of the compounds to show their antitubercular activities. In conclusion, the investigated sulfonyl hydrazones display promising antitubercular drug-like properties and warrant further investigation.

Abstract Octreotide is the first synthetic peptide hormone, consisted of eight amino acids, that mimics the activity of somatostatin, a natural hormone in the body. During the past decades, advanced instrumentation and crystallographic software established X-ray Powder Diffraction (XRPD) as a valuable tool for extracting structural information of biological macromolecules. The latter was demonstrated by the successful structural determination of octreotide at a remarkably high d-spacing resolution (1.87 Å) (PDB code: 6vc1). This study focuses on the response of octreotide to different humidity levels and temperatures, with a particular focus on the stability of the polycrystalline sample. XRPD measurements were accomplished employing an Anton Paar MHC-trans humidity-temperature chamber installed within a laboratory X’Pert Pro diffractometer (Malvern Panalytical). The chamber is employed to control and maintain precise humidity and temperature levels of samples during XRPD data collection. Pawley analysis of the collected data sets revealed that the octreotide polycrystalline sample is remarkably stable and no structural transitions were observed. The compound retains its orthorhombic symmetry (space group: P212121, a = 18.57744(4) Å, b = 30.17338(6) Å, c = 39.70590(9) Å, d~ 2.35 Å). However, a characteristic structural evolution in terms of lattice parameters and volume of the unit-cell is reported mainly upon controlled relative humidity variation. In addition, an improvement of signal-to-noise ratio in the XRPD data under a cycle of dehydration/rehydration is reported. These results underline the importance of considering the impact of environmental factors, as humidity and temperature, in the context of structure-based drug design, thereby contributing to the development of more effective and stable pharmaceutical products.

The structural evolution and phase composition of multi-block thermoplastic polyurethanes, with different nature of the soft segments based on poly(butylene adipate) (PBA), were analyzed during in-situ thermal treatments. A combination of synchrotron small- and wide-angle X-ray scattering, differential scanning calorimetry, thermogravimetric analysis, and FTIR spectroscopy was used to determine the influence of macrodiol nature and crystallization conditions on the polymorphic behavior of PBA. Using a new synthesis scheme, a relatively high degree of crystallinity for urethane blocks was achieved, which depends on the diisocyanate type in the structure of the soft segment. The hard segment domains impose geometrical constraints on PBA, thereby altering its crystallization process compared to the neat oligomer. Thus, crystallization after annealing at a low temperature (80 °C) is fast, predominantly yielding a metastable β-phase. When heated to 180 °C, which is higher than the hard-segment melting temperature, a phase-separated structure is observed. Subsequent crystallization is slower, favoring the formation of the stable α-PBA modification. The phase separation can be observed even after the hard block melting. A notably slow crystallization from an isotropic melt was documented after the disruption of phase separation at 230 °C.

2-(Adamantan-1-yl)-2H-isoindole-1-carbonitrile (1) has been identified as a neurobiological fluorescent ligand that may be used to develop receptor and enzyme binding affinity assays. Compound 1 was synthesised using an optimised microwave irradiation reaction and crystallised from ethanol. Crystallization occurred in the orthorhombic space group P212121 with unit cell parameters: a = 6.4487(12) Å, b = 13.648(3) Å, c = 16.571(3) Å, V = 1458(5) Å3, Z = 4. Density functional theory (DFT) (B3LYP/6-311++G (d,p)) calculations of 1 were carried out. Results showed that the optimised geometry is similar to the crystal structure parameters with a root-mean-squared deviation of 0.143 Å. Frontier molecular orbital energies and net atomic charges are discussed with a focus on potential biological interactions. Docking experiments within the active site of the neuronal nitric oxide synthase (nNOS) protein crystal structure were carried out and analysed. Important binding interactions between the DFT optimised structure and amino acids within the nNOS active site were identified that explain the strong NOS binding affinity reported. Fluorescent properties of 1 were studied using aprotic solvents of different polarities. Compound 1 showed the highest fluorescence intensity in polar solvents with excitation and emission values of 336 nm and 380 nm, respectively.

A metastable β-Ti alloy, Ti–10V–3Fe–3Al (wt.%), was subjected to thermos-mechanical processing including the compression test at 725°C, which is below the β transus temperature (780°C), and at strain rate of 10-3s-1. The presence of phases was determined using transmission electron microscopy and X-ray diffraction. Although the dynamic recovery took place together with slip, both deformation-induced α˝ martensite and ω were detected as other operating mechanisms for the first time in metastable-β Ti alloys deformed in α+β region. The volume fraction of stress-induced α˝ was higher than that of the same alloy deformed at room temperature due to higher strain applied. Stress-induced twinning was not operational, which could be related to the priority of slip mechanism at high temperature resulted from thermally-assisted nucleation and lateral migration of kink-pairs.

The study of coherent vortices remains an urgent field of singular optics of vortex beams. In this paper, coherent properties of partially coherent vortex Bessel—Gaussian optical beams propagating through a uniform medium (free space) or a turbulent atmosphere are examined theoretically. The consideration is based on analytical solution of the equation for the transverse second-order mutual coherence function of the field of a partially coherent optical radiation in a turbulent atmosphere. For the partially coherent Bessel—Gaussian beam, the second-order mutual coherence function of the source field is taken as a Gaussian Shell-model. In this approximation, we analyze the behavior of the coherence degree and the integral coherence scale of these beams as a function of the propagation pathlength, propagation conditions, and beam parameters, such as the radius of the Gauss factor of the beam, parameter of the Bessel factor of the beam, topological charge, and correlation width of the source field of partially coherent radiation. In addition, the integral coherence scale of the partially coherent vortex Bessel—Gaussian beam is compared with that of the partially coherent Gaussian beam. It is found that as a partially coherent vortex Bessel—Gaussian beam propagates through a turbulent atmosphere, there appear not two (as might be expected: one due to atmospheric turbulence and another due to partial coherence of the source field), but only one ring dislocation of the coherence degree (due to the simultaneous effect of both these factors on the optical radiation). In addition, it is shown that the dislocation of the coherence degree that affects significantly the beam coherence level is formed only for beams, for which the coherence width of the source field is larger than the diameter of the first Fresnel zone.

With the decline in fossil fuels, hydrogen-based alternatives provide a reliable and clean source for sustainable energy generation. In these endeavors, photochemical splitting for hydrogen production through tandem cells has been the source of much theoretical and experimental research in science. Much focus has been placed on interfacial band gap engineering as one of the most promising routes in the generation of hydrogen.This present work explores sputtering of n-silicon to form the active electrode in a n-Si | n-TiO₂ tandem cell and investigates the effect of variations in sputtering and post sputtering treatment parameters (rapid thermal annealing and long cycle annealing) for successful deposition of crystalline Silicon. The samples were successfully characterized via Raman Spectroscopy, X-ray Diffraction and Optical Transmission Spectroscopy to ascertain prevalent crystalline order and optical band gap, under different sputtering and post-sputtering conditions. Relevant conclusions were drawn to ascertain the best possible deposition parameters of n-Si for photocatalytic water splitting.

Background/Objectives: Pentacyclic Triterpenoids are increasingly studied as anti-cancer agents with many advantages comparative to synthetic chemotherapeutics. The aim of this study was to prepare liposomal and nanostructured lipid formulations including a standardized extract of silver birch (Betula pendula) outer bark (TTs) and to evaluate their potential as anti-cancer agents in vitro, using Melanoma B16-F10 and Walker carcinoma cells. Methods: Appropriate solvents were selected for an efficient TTs extraction, and original recipes were used to obtain Pegylated liposomes and nanolipid complexes with entrapped TTs, comparative to pure standards (betulinic acid and doxorubicin) in similar conditions. The composition, morphology and sizes of all nanoformulations were checked by High Performance Liquid Chromatography/Mass spectrometry, Transmission Electronic Microscopy and Diffraction Light Scattering. The entrapment efficiency and their impact on cell viability, cell cycle arrest and apoptosis by Flow Cytometry was also measured on both cancer cell lines. Conclusions: The standardized TTs showed good stability, synergistic effects of main components and superior comparative to pure betulinic acid. According to experimental data, TTs showed good entrapment in liposomal and NLC nanoformulations, both delivery systems including natural, biodegradable ingredients and enhanced bioavailability. The apoptosis and necrosis effects were more pronounced for TTs liposomal formulations in both types of cancer cells, with lower cytotoxicity comparative to Doxorubicin, and can be correlated with their increased bioavailability.

High temperature Ni-superalloys are limited by reliance on critical elements and complex processing steps. High entropy alloys (HEAs) have demonstrated stable single/dual phase microstructures with strong ordering tendencies. A dual phase (FCC+BCC) Al0.5Co0.5CrFeNi1.5Ti0.25 alloy (developed using CALPHAD) was tested for room and high temperature compression behavior. The microstructure mainly comprises of coarse ordered FCC(L12) surrounding decomposed lamellae of ordered FCC(L12) and BCC(L21) phases, which coarsened upon annealing at high temperature (1100 °C) into a bi-continuous structure of disordered FCC+BCC(B2). Additionally, cold rollability of the cast alloy increased from <5% to ~40% after annealing, with a corresponding softening observed in room temperature compression mainly due to disordering of FCC and BCC phases. Peak flow stresses of 793.45MPa, 535.12MPa, and 324.40MPa were achieved at 800oC, 900oC, and 1000oC respectively for the high temperature annealed alloy.

In this work, we have studied microstructure and unusual ferromagnetic behavior in cobalt (Co)-implanted epitaxial tin dioxide (SnO2) films. The study was aimed to provide a comprehensive understanding of the interplay between cobalt implant distribution, crystal defects, such as oxygen vacancies, and magnetic properties in Co-implanted SnO2 films, which has potential applications in spintronics and memristor devices. The scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), vibrating sample magnetometry (VSM), differential thermo-magnetic analysis (DTMA), and ferromagnetic resonance (FMR) were employed for investigations of SnO2 films implanted with 40 keV Co+ ions at room or the elevated temperatures of substrate. The experimental data showed that the Co ion implantation with high fluence of 1.0 1017 ions/cm2 induces significant changes in the microstructure of SnO2 films, leading to the appearance of ferromagnetism with the Curie temperature significantly above room temperature. Strong influence of implantation temperature and subsequent high-temperature annealing in air or in vacuum on magnetic properties of Co-implanted SnO2 films were established. Moreover, the chemical effect of ethanol on FMR spectra were observed. The obtained results are discussed within the model of two magnetic layers with different concentration and valence states of the implanted cobalt and with high content of oxygen vacancies.

We extensively studied serigraphic screen-printed commercial silver flake inks loaded with silicon inclusions in order to achieve pinning at the grain boundaries. Based on grain size measurements using electron backscattered diffraction (EBSD), commercial silver ink with silicon microparticle content of 5 wt.% shows a significant grain growth retardation compared to the pristine silver ink, which stabilizes electrical conductivity up to 700 ◦C via Zener pinning mechanism. The modified silicon-loaded silver ink experiences a two times increase in grain size when heated up to 700 ◦C, compared to a seven times increase for the pristine silver ink. In turn, this enables operation temperatures significantly higher than the conventional operational window of microparticle-based silver inks, which are usually limited to 400 ◦C. Using isothermal exposures of 10 minutes up to 4 hours this phenomenon is observed at temperatures ranging from 250 ◦C to 900 ◦C. The electrical conductivity stability, grain size evolution and oxide contents were studied up to 4 hours. The activation energy of silver ink with silicon inclusions is 54% lower than for the pristine silver ink due to pining effect, which retards grain growth via the Zener mechanism. Most importantly, the electrical resistivity becomes stable up to 700 ◦C, which is more than twice the operation limit for off-the-shelf screen-printable silver flake inks. Hence, we demonstrate that adding controlled amounts of silicon particles to silver inks towards grain structure engineering can open new vistas of possibilities for screen-printed metallic inks.

We report on the application of time-resolved inline digital holography to study the nonlinear optical properties of quantum dots deposited onto the sample glass. Fresnel diffraction patterns of the probe pulse due to noncollinear degenerate phase modulation induced by the femtosecond pump pulse were extracted from the set of inline digital holograms and analyzed. Absolute values of the nonlinear refractive index of both sample glass substrate and the deposited layer of quantum dots were evaluated using the proposed technique. To characterize the inhomogeneous distribution of samples’ nonlinear optical properties we proposed to plot an optical nonlinearity map calculated as a local standard deviation of diffraction patterns intensity induced by noncollinear degenerate phase modulation.

Because this issue journal is dedicated to Gelatin here we present a few applications of gelatin in the field of optics. It is understood that optics is the science that studies the production, propagation, interaction and detection of light. Regarding the detection there are some materials sensitive to light (photosensitive) that are used like photomultipliers, CCD’s, crystals, two dimension (2D) materials and more. Among the 2D materials the most popular through several centuries has been gelatin based photographic emulsion that records spatial distributions of light. More recently (1970) films made of Gelatin with Dichromate (DCG) and dyes have been used. We describe some characteristics and applications of these two photosensitive materials. Also we describe examples where gelatin is used as Relative Humidity (RH) sensor and in the fabrication of optical elements based on gelatin. This article is intended to researchers outside the optics community.

The structure and physicochemical properties of polyvinyl alcohol (PVA) and PVA/glycerol films have been investigated by Fourier-transform infrared spectroscopy (FT-IR), X-ray Diffraction (XRD), thermogravimetry/differential thermal analysis (TG/DTA), and advanced scanning probe microscopy (SPM). In the pure PVA films, SPM allowed us to observe ribbon-shaped domains with a different frictional and elastic contrast, which apparently originated from a correlated growth or assembly of PVA crystalline nuclei located within individual PVA clusters. The incorporation of 1.0 wt.% glycerol led to modification in shape of those domains from ribbon-like in pure PVA to rounded in PVA/glycerol 1.0 wt.% films; changes in the relative intensities of the XRD peaks and a decrease of the amorphous halo in the XRD pattern were also detected, while the DTA peak corresponding to the melting point remained at almost the same temperature. For higher glycerol content, FT-IR revealed additional glycerol-characteristic peaks presumably related to the formation of glycerol aggregates, and XRD, FT-IR, and DTA all indicated a reduction in crystallinity. For more than 2.0 wt.% glycerol, the plasticization of the films complicated the acquisition of SPM images without tip-induced surface modification. Our study contributes to the understanding of crystallinity in PVA and how it is altered by a plasticizer such as glycerol.

This study investigates the phase and elemental distribution in a suspension plasma-sprayed (SPS) Li4Ti5O12 (LTO) thin-film anode for solid-state lithium batteries, deposited on an SS-304 substrate. Advanced synchrotron-based μXRD and μXRF techniques were employed for micro-scale characterization, revealing distinct phase regions influenced by thermal exposure during the SPS process. The dominant Li4Ti5O12 phase was retained across most of the film, with localized transformations to secondary phases Li2Ti3O7, Li2TiO3, and TiO2 near the substrate interface, primarily due to prolonged high-temperature exposure and subsequent lithium loss. These findings underscore the importance of controlling SPS parameters to minimize lithium loss and optimize phase stability and interfacial integrity in solid-state battery components.

Many studies of hypervelocity impact craters have described the characteristics of quartz grains shock-metamorphosed at high pressures of > 10 GPa. In contrast, few studies have investigated shock metamorphism at lower shock pressures. In this study, we test the hypothesis that low-pressure shock metamorphism occurs in near-surface nuclear airbursts and that this process shares essential characteristics with crater-forming impact events. To investigate low-grade shock microstructures, we compared quartz grains from Meteor Crater, a 1.2-km-wide impact crater, to those from near-surface nuclear airbursts at the Alamogordo Bombing Range, New Mexico in 1945 and Kazakhstan in 1949/1953. This investigation utilized a comprehensive analytical suite of high-resolution techniques, including transmission electron microscopy (TEM) and electron backscatter diffraction (EBSD). Meteor Crater and the nuclear test sites all exhibit quartz grains with closely-spaced, sub-micron-wide fractures that appear to have formed at low shock pressures. Significantly, these micro-fractures are closely associated with Dauphiné twins and are filled with amorphous silica (glass), widely considered a classic indicator of shock metamorphism. Thus, this study confirms that glass-filled shock fractures in quartz form during near-surface nuclear airbursts, as well as crater-forming impact events, and by extension, it suggests that they may form in any near-surface cosmic airbursts in which the shockwave is coupled to Earth’s surface. The robust characterization of such events is crucial because of their potential catastrophic effects on the Earth’s environmental and biotic systems.

Many studies of hypervelocity impact craters have described the characteristics of quartz grains shock-metamorphosed at high pressures of >10 GPa, but in contrast, few studies have investigated shock metamorphism at lower shock pressures. In this study, we test the hypothesis that low-pressure shock metamorphism occurs in near-surface nuclear airbursts and that this process shares important characteristics with impact-cratering events. To investigate low-grade shock microstructures, we compared quartz grains from Meteor Crater, a 1.2-km-wide impact crater, to those from near-surface nuclear airbursts at the Alamogordo Bombing Range, New Mexico in 1945 and Kazakhstan in 1949/1953. This investigation utilized a comprehensive analytical suite of high-resolution techniques, including transmission electron microscopy (TEM) and electron backscatter diffraction (EBSD). Meteor Crater and the nuclear test sites all exhibit metamorphosed quartz grains with closely-spaced, sub-micron-wide fractures that appear to have formed at low shock pressures. Importantly, these micro-fractures are closely associated with Dauphiné twins and are filled with amorphous silica (glass), widely considered to be a classic indicator of shock metamorphism. Thus, this study confirms that glass-filled shock fractures in quartz form during near-surface nuclear airbursts, as well as crater-forming impact events, and by extension, it suggests they also may form in near-surface cosmic airbursts.

Camptothecin (CPT) is a potent anticancer drug, and its putative oral administration is envisioned although difficult due to physiological barriers that must be overcome. A comprehensive biophysical analysis of CPT interaction with biointerface models can be used to predict some pharmacokinetic issues after oral administration of this or other drugs. To that end, different models were used to mimic the phospholipid composition of normal, cancer, and blood-brain barrier endothelial cell membranes. The logD values obtained indicate that the drug is well distributed across membranes. CPT-membrane interaction studies also confirm the drug’s location at the membrane cooperative and interfacial regions. The drug can also permeate membranes at more ordered phases by altering phospholipid packing. The similar logD values obtained in membrane models mimicking cancer or normal cells imply that CPT has limited selectivity to its target. Furthermore, CPT binds strongly to serum albumin, leaving only 8.05% of free drug available to be distributed to the tissues. The strong interaction with plasma proteins, allied to the large distribution (VDSS=5.75 ± 0.932 L·Kg-1) and tendency to bioaccumulate in off-target tissues, were predicted to be pharmacokinetic issues of CPT, implying the need to develop drug delivery systems to improve its biodistribution.

Vanadium(IV) chalcogenide materials are of increasing interest for use in catalysis and energy conversion-related applications. Since no ternary compounds are yet known in the V–Se–Te system, we studied ternary VwSeyTe2–y (w = 1.10, 1.13; y = 0.42, 0.72) phases crystallizing in space group P3m1 (no. 164). Two single-crystal specimens with differing compositions of a solid solution were obtained using the ceramic method. All products were characterized by either single-crystal or powder X-ray diffraction. The lattice parameters increase with rising tellurium content in accordance to the larger ionic radius of the tellurium anion compared to selenium. The chemical compositions were confirmed by energy dispersive X-ray spectroscopy. Further, magnetic measurements revealed mostly antiferromagnetic properties. Simultaneous differential scanning calorimetry/thermogravimetric analyses in nitrogen atmosphere showed endothermic decomposition accompanied by the formation of VN. The results of this work can serve as a basis for the synthesis of new phases in the V–Se–Te and related vanadium chalcogenide systems.