Search Results (1,027)

We report here an in-depth study concerning the synthesis, NMR, and X-ray structure determination of two new polymorphs of 2-chloro-3′,4′-diacetoxy-acetophenone. A new, ecologically friendly method of synthesis in the solid phase, as well as a suitable method for protecting hydroxyl functionality, is presented. The ¹H- and ¹³C-NMR spectra as well as the single crystal X-ray diffraction studies proved unambiguously the structure of the compounds: the two polymorphs of 2-chloro-3′,4′-diacetoxy-acetophenone and 2-chloro-3′-hydroxy-4′-acetoxy-acetophenone. The polymorph I crystalizes in the monoclinic P21/c space group, while polymorph II crystalizes in the Sohnke P212121 space group of the orthorhombic system, with no interstitial solvate molecules. Significant differences were observed in the supramolecular interactions in the crystal structure of the two polymorphs. Polymorph I is characterized as a parallel packing of weakly interacting supramolecular layers oriented in the 1 1 0 plane. The crystal structure of polymorph II is much more complex: each molecule is interconnected through 12 (twelve) hydrogen bonds with 9 (nine) adjacent symmetry-related molecules. The monoacetoxy derivative 2-chloro-3′-hydroxy-4′-acetoxy-acetophenone 3 crystallizes in the monoclinic P2₁/c space group, with one molecule in the asymmetric unit. Full article

Geopolymers represent an innovative and environmentally sustainable alternative to traditional construction materials, offering significant potential for reducing anthropogenic CO₂ emissions. Among these, phosphoric acid-activated metakaolin-based systems have attracted increasing attention for their chemical and thermal resilience. In this study, we present a comprehensive structural and mechanical evaluation of metakaolin-based geopolymers synthesized across a wide range of Al/P molar ratios (0.8–4.0). Six formulations were systematically prepared and analyzed using X-ray powder diffraction (XRPD), small-angle X-ray scattering (SAXS), Fourier-transform infrared spectroscopy (FTIR), solid-state nuclear magnetic resonance (ssNMR), and complementary mechanical testing. The novelty of this work lies in the integrated mapping of composition–structure–property relationships across the broad Al/P spectrum under controlled synthesis, combined with the rare application of SAXS to reveal composition-dependent nanoscale domains (~18–50 nm). We identify a stoichiometric window at Al/P ≈ 1.5, where complete acid consumption leads to a structurally homogeneous AlVI–O–P network, yielding the highest compressive strength. In contrast, acid-rich systems exhibit divergent flexural and compressive behaviors, with enhanced flexural strength linked to hydrated silica domains arising from metakaolin dealumination, quantitatively tracked by ²⁹Si MAS NMR. XRPD further reveals the formation of uncommon Si–P crystalline phases (SiP₂O₇, Si₅P₆O₂₅) under low-temperature curing in acid-rich compositions. Together, these findings provide new insights into the nanoscale structuring, phase evolution, and stoichiometric control of silica–alumino–phosphate geopolymers, highlighting strategies for optimizing their performance in demanding thermal and chemical environments. Full article

Diaza-peptidomimetics are constrained compounds that mimic the biological efficacy of peptides while offering increased stability. We have previously reported the synthesis of bis-cyclic guanidine heterocyclic peptidomimetics as opioid ligands with mixed μ-, κ- and δ-opioid receptor interactions and their potential activity as novel analgesics. Using the same approach, we report here the synthesis of sulfonated and piperazine-tethered bis-cyclic guanidines and their in vitro screening results from radioligand competition binding assays at the μ- (MOR), δ- (DOR), and κ- (KOR) opioid receptors. Full article

As landfill mining becomes more widely applied, growing attention is being paid to the waste-to-energy conversion of landfill waste. Co-disposal of landfill waste with municipal solid waste represents one of the primary strategies for achieving energy recovery of landfill waste. In this paper, the emission characteristics of pollutants were systematically analyzed during the co-disposal of landfill waste and municipal solid waste in a full-scale municipal solid waste incineration. The study investigated the formation patterns of toxic PCDD/Fs and gaseous pollutants under different co-disposal ratios of landfill waste (0%, 15%, 25%, 35%, and 45%). In total, 136 PCDD/Fs were analyzed to investigate the influence of co-disposal ratios on PCDD/F formation in both flue gas and fly ash. The influence of varying co-disposal ratios on the phase and elemental composition of fly ash was also investigated. Co-disposal led to a significant reduction in the toxic PCDD/F concentration at the boiler outlet, mainly attributed to the higher sulfur content of LW compared to MSW. With increasing co-disposal ratios, the annual emission amounts of toxic PCDD/Fs in fly ash significantly increased. The ∑PCDD/∑PCDF ratio in both flue gas of boiler outlet and fly ash also increased, indicating an enhancement of the precursor formation pathway, while the de novo synthesis pathway was relatively suppressed. The fly ash exhibited a high proportion of highly chlorinated dioxins (degree of chlorination: 7.19–7.23), likely due to their low saturated vapor pressure. According to the Hagenmaier congener distribution, high co-disposal ratios (25–45%) suppressed the chlorination of DD/DF in fly ash but promoted the formation of gas-phase PCDFs. Different co-disposal ratios significantly influenced both the emission concentrations and removal efficiencies of air pollutants, including NOx, SO₂, and HCl. Although co-disposal did not alter the crystalline phase composition of fly ash, it led to an increased content of heavy metals such as Cu, Hg, and Pb. Full article

Skutterudite (CoSb₃)-based thermoelectric materials are regarded as one of the most promising candidates for mid-temperature commercial thermoelectric applications, thanks to their excellent electrical performance and alloy-based attributes. By utilizing techniques such as doping, microstructure design, and high-temperature solid-state reactions, synthesis of Brass_x/Co₄Sb_11.5Te_0.5 (x = 0.1, 0.3, 0.5, 0.7, representing wt%) in composite form can be rapidly achieved. XRD analysis indicates that the prepared Brass_x/Co₄Sb_11.5Te_0.5 samples primarily exhibit the CoSb₃ crystal structure, with the formation of minor impurity phases such as Cu₁₃Te₇ and ZnTe. SEM and EDS analyses reveal that the sample is composed of nanoscale equiaxed grains, some of which are micrometer in size, with a large number of microporous structures distributed uniformly, forming abundant grain boundaries. By co-doping with brass and tellurium (Te), the carrier concentration can be effectively regulated, thereby enhancing the power factor of CoSb₃-based thermoelectric materials. Meanwhile, the introduction of nanostructures, grain boundaries, and defects optimizes the microstructure of the samples, leading to a reduction in the lattice thermal conductivity of the CoSb₃-based thermoelectric materials. At a testing temperature of 781 K, Brass_0.1/Co₄Sb_11.5Te_0.5 achieved a maximum power factor of 1.86 mW·m⁻¹·K⁻², a minimum lattice thermal conductivity of 1.02 W/(mK), and a maximum thermoelectric figure of merit ZT of 0.81. Full article

In this work, (NaBi)_0.5−x(LiSm)_xBi₂Nb₂O₉ (NBN-xLS, x = 0.00–0.06) ceramics were fabricated by co-doping of LiSm into Na_0.5Bi_2.5Nb₂O₉. The traditional solid-phase technique was employed for the entire synthesis process. The impact of LiSm doping on the crystal structure, dielectric, ferroelectric, and piezoelectric properties, as well as the underlying conduction mechanisms in the NBN-xLS ceramics, was analyzed systematically. The XRD patterns and the Rietveld refinement revealed that lattice distortion reduced with an increase in the LiSm doping amount. The decrease in lattice distortion significantly contributed to its improved ferroelectric and piezoelectric characteristics. The results showed that the NBN-xLS ceramics were primarily p-type materials due to their bulk-limited conduction, with oxygen holes and vacancies acting as the conducting species, and the appearance of weak ion conduction at high temperatures. The NBN-0.04LS ceramic, in particular, displayed the highest performance, with P_r, T_c, and d₃₃ values of 9.05 μC/cm², 777 °C, and 25.2 pC/N, respectively. Additionally, the ceramic displayed remarkable thermal stability, with its d₃₃ retaining 95.0% of its original value after annealing at 760 °C. These results demonstrate that LiSm co-doped Na_0.5Bi_2.5Nb₂O₉ ceramics have potential for use in high-temperature sensors. Full article

The CaO-SiO₂-P₂O₅ system is one of the main systems studied aiming for the synthesis of new bioactive materials for bone regeneration. The interest in materials containing calcium-phosphate-silicate phases is determined by their biocompatibility, biodegradability, bioactivity, and osseointegration. The object of the present study is the synthesis by the sol-gel method of biocompatible glass-ceramics in the Ca₂SiO₄-Ca₃(PO₄)₂ subsystem with the composition 6Ca₂SiO₄·Ca₃(PO₄)₂ = Ca₁₅(PO₄)₂(SiO₄)₆. The phase-structural evolution of the samples was monitored using X-ray diffraction analysis (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), energy-dispersive spectroscopy (EDS), and surface area analysis. A powder (20–30 µm) glass-ceramic material containing fine crystalline aggregates of dicalcium silicate and plates of silicon-substituted hydroxyapatite was obtained after heat treatment at 700 °C. After heat treatment at 1200 °C, Ca₁₅(PO₄)₂(SiO₄)₆, silicocarnotite Ca₅(PO₄)₂(SiO₄), and pseudowollastonite CaSiO₃ were identified by XRD, and the particle size varied between 20 and 70 µm. The compact glass-ceramic obtained at 1400 °C contained Ca₂SiO₄-Ca₃(PO₄)₂ solid solutions with an α-Ca₂SiO₄ structure as a main crystalline phase. SEM showed the specific morphology of the crystalline phases and illustrated the trend of increasing particle size depending on the synthesis temperature. Effects of the glass-ceramic materials on cell viability of HL-60-derived osteoclast-like cells and on the expression of apoptotic and osteoclast-driven marker suggested that all materials at low concentrations, above 1 µg mL⁻¹, are biocompatible, and S-1400 might have a potential application as a scaffold material for bone regeneration. Full article

Antimicrobial peptides (AMPs) are the promising candidates for the development of next-generation antimicrobials for agriculture and medicine; however, their large-scale production is costly. The γ-core motif peptides, functionally significant fragments of AMPs responsible for the antimicrobial activity, provide a more economical and feasible approach for the commercial development of novel antimicrobials. In the present work, we undertook a comprehensive study of antimicrobial properties of several γ-core peptides derived from defensins and snakins of Filipendula ulmaria, a medicinal plant known for its valuable pharmacological properties. The γ-core peptides were produced by solid-phase synthesis and purified by RP-HPLC. Their physicochemical properties underlying biological activity were predicted. All the peptides ranging in size from 14 to 18 amino acid residues were positively charged. All peptides except one were predicted to be α-helical and antimicrobial. The synthetic peptides were in vitro tested against a wide panel of plant and human fungal and bacterial pathogens. A short overview of the pathogens used in antimicrobial assays with a special emphasis on their economic, social, and medicinal impacts is provided. As a result of our work, we identified the peptides with pronounced activity in low-micromolar range against particular pathogens that can serve as prototypes for the development of novel biopesticides and antimicrobials for medicine. We also revealed synergism of action between particular γ-core peptide pairs and demonstrated that interference with membrane permeabilization contributes to the peptides’ mode of action. The results obtained broaden our understanding of plant AMPs, the key players in plant immunity, and provide novel highly efficient peptides with high potential in practical applications. Full article

During the annealing, recrystallization processes in ceramics can occur, manifested in the formation of new grains, grain-boundary migration, and grain coarsening. It was expected that recrystallization in mechanically deformed zones, which contain residual stresses and high defect densities, will proceed in a different way compared to the surrounding, relaxed material. Characterizing these spatial variations in defect evolution, phase transformations, and microstructural recovery is essential for predicting performance and avoiding critical structural changes when designing zirconia-based ceramics for high-temperature, load-bearing applications. To study these effects, we used partially stabilized Ce-doped ZrO₂ ceramics, fabricated by solid-state synthesis. Phase composition, structural features, and morphology of these ceramics were studied using Raman spectroscopy, XRD and SEM before and after annealing in the mechanically stressed and relaxed regions. In mechanically deformed regions a more pronounced phase transformation from monoclinic to tetragonal was observed compared to relaxed zones. This result indicates that strain can facilitate tetragonal phase formation in zirconia ceramics when the material is subjected to elevated temperatures. Mechanical stresses should be taken into account when fabricating ceramic components, as they can induce phase transformation during heat treatments and change the properties of ceramics significantly. Full article

We report herein the development of a polyclonal antibody against ochratoxin A (OTA) using a specially designed synthetic OTA derivative as the immunizing hapten. This OTA derivative contains a tetrapeptide linker (glycyl-glycyl-glycyl-lysine, GGGK), through which it can be linked to a carrier protein and form an immunogenic conjugate. The OTA derivative (OTA-glycyl-glycyl-glycyl-lysine, OTA-GGGK) has been synthesized on a commercially available resin via the well-established Fmoc-based solid-phase peptide synthesis (Fmoc-SPPS) strategy; overall, this approach has allowed us to avoid tedious liquid-phase synthesis protocols, which are often characterized by multiple steps, several intermediate products and low overall yield. Subsequently, OTA-GGGK was conjugated to bovine thyroglobulin through glutaraldehyde, and the conjugate was used in an immunization protocol. The antiserum obtained was evaluated with a simple-format ELISA in terms of its titer and capability of recognizing the natural free hapten; the anti-OTA antibody, as a whole IgG fragment, was successfully applied to three different immunoanalytical systems for determining OTA in various food materials and wine samples, i.e., a multi-mycotoxin microarray bio-platform, an optical immunosensor, and a biotin–streptavidin ELISA, which has proved the analytical effectiveness and versatility of the anti-OTA antibody developed. The same approach may be followed for developing antibodies against other low-molecular-weight toxins and hazardous substances. Full article

Background: With the increasing shift in drug design away from classical drug targets towards the modulation of protein-protein interactions, synthetic peptides are gaining increasing relevance. The synthesis and purification of peptides via solid-phase peptide synthesis (SPPS) strongly rely on trifluoroacetic acid (TFA) as a cleavage agent and ion-pairing reagent, respectively, resulting in peptides being obtained as TFA salts. Although TFA has excellent properties for peptide production, numerous studies highlight the negative impact of using peptides from TFA⁻ salts in biological assays. Methods: Investigated peptides were synthesized via SPPS and the TFA⁻ counterion was exchanged for Cl⁻ via freeze-drying in different concentrations of HCl. Detection and quantification of residual TFA⁻ were carried out via FT-IR, ¹⁹F-NMR, and HPLC using an evaporative light-scattering detector (ELSD). A liposomal fluorescence assay was used to test for the influence of the counterion on the peptides’ passive membrane permeability. Results: All TFA⁻ detection methods were successfully validated according to ICH guidelines. TFA⁻ removal with 10 mM HCl was determined to be the optimal condition. No impact on peptide purity was observed at all HCl concentrations. Influences on permeability coefficients depending on peptide sequence and salt form were found. Conclusions: This study presents a systematic investigation of the removal of TFA⁻ counterions from synthetic peptides and their replacement with Cl⁻ counterions. Detected counterion contents were used to understand the impact of sequence differences, especially positive charges, on the amount and potential localization of counterions. Our findings emphasize the importance of counterion quantification and specification in assays with synthetic peptides. Full article

Background/Objectives: Pancreatic ductal adenocarcinoma (PDAC) remains one of the deadliest solid tumors, with a five-year overall survival rate below 10%. While the introduction of multi-agent chemotherapy regimens has improved outcomes marginally, most patients with advanced disease continue to have limited therapeutic options. Molecular profiling has uncovered actionable genomic alterations in select subgroups of PDAC, yet the clinical impact of targeted therapies remains modest. This review aims to provide a clinically oriented synthesis of emerging molecular targets in PDAC, their therapeutic relevance, and practical considerations for biomarker testing, including current FDA and EMA indications. Methods: A narrative review was conducted using data from PubMed, Embase, Scopus, and international guidelines (NCCN, ESMO, ASCO). The selection focused on evidence published between 2020 and 2025, highlighting molecularly defined PDAC subsets and the current status of targeted therapies. Results: Actionable genomic alterations in PDAC include KRAS G12C mutations, BRCA1/2 and PALB2-associated homologous recombination deficiency, MSI-H/dMMR status, and rare gene fusions involving NTRK, RET, and NRG1. While only a minority of patients are eligible for targeted treatments, early-phase trials and real-world data have shown promising results in these subgroups. Testing molecular profiling is increasingly standard in advanced PDAC. Conclusions: Despite the rarity of targetable mutations, systematic molecular profiling is critical in advanced PDAC to guide off-label therapy or clinical trial enrollment. A practical framework for identifying and acting on molecular targets is essential to bridge the gap between precision oncology and clinical management. Full article

In this work, we report a novel mechanochemical synthesis method for the synthesis of quinoxaline derivatives—a spiral gas–solid two-phase flow approach, which enables the efficient preparation of quinoxaline compounds. Compared to conventional synthetic methods, this approach eliminates the need for heating or solvents while significantly reducing reaction time. The structures of the synthesized compounds were characterized using nuclear magnetic resonance (NMR), Fourier-transform infrared spectroscopy (FT-IR), ultraviolet-visible (UV–Vis) absorption spectroscopy, powder X-ray diffraction (XRD), differential scanning calorimetry (DSC), and high-performance liquid chromatography (HPLC). Using the synthesis of 2,3-diphenylquinoxaline (1) as a model reaction, the synthetic process was investigated with UV–Vis spectroscopy. The results demonstrate that when the total feed amount was 2 g with a carrier gas pressure of 0.8 MPa, the reaction completed within 2 min, achieving a yield of 93%. Furthermore, kinetic analysis of the reaction mechanism was performed by monitoring the UV–Vis spectra of the products at different time intervals. The results indicate that the synthesis of 1 follows the A4 kinetic model, which describes a two-dimensional diffusion-controlled product growth process following decelerated nucleation. Full article

In this study, high-energy milled (HEM) samples of natural phosphorites from Estonian deposits were investigated. The activation was performed via planetary mill with Cr-Ni grinders with a diameter of 20 mm. This method is an ecological alternative, since it eliminates the disadvantages of conventional acid methods, namely the release of gaseous and solid technogenic products. The aim of the study is to determine the changes in the structure to follow the solid-state transitions and the isomorphic substitutions in the anionic sub-lattice in the structure of the main mineral apatite in the samples from Estonia, under the influence of HEM activation. It is also interesting to investigate the influence of HEM on structural-phase transformations on the structure of impurity minerals-free calcite/dolomite, pyrite, quartz, as well as to assess their influence on the thermal behavior of the main mineral apatite. The effect of HEM is monitored by using a complex of analytical methods, such as chemical analysis, powder X-ray diffraction (PXRD), wavelength-dispersive X-ray fluorescence (WD-XRF) analysis, and Fourier-transformed infrared (FTIR) analysis. The obtained results prove the correlation in the behavior of the studied samples with regard to their quartz content and bonded or non-bonded carbonate ions. After HEM activation of the raw samples, the following is established: (i) anionic isomorphism with formation of A and A-B type carbonate-apatites and hydroxyl-fluorapatite; (ii) solid-phase synthesis of calcium orthophosphate-CaHPO₄ (monetite) and dicalcium diphosphate-β-Ca₂P₂O₇; (iii) enhanced chemical reactivity by approximately three times by increasing the solubility via HEM activation. The dry milling method used is a suitable approach for solving technological projects to improve the composition and structure of soils, increasing soil fertility by introducing soluble forms of calcium phosphates. It provides a variety of application purposes depending on the composition, impurities, and processing as a soil improver, natural mineral fertilizer, or activator. Full article

The mechanism for the upscale deposition of energy into the atmosphere from molecules and photons up to organized wind systems is examined. This analysis rests on the statistical multifractal analysis of airborne observations. The results show that the persistence of molecular velocity after collision in breaking the continuous translational symmetry of an equilibrated gas is causative. The symmetry breaking may be caused by excited photofragments with the associated persistence of molecular velocity after collision, interaction with condensed phase surfaces (solid or liquid), or, in a scaling environment, an adjacent scale having a different velocity and temperature. The relationship of these factors for the solution to the Navier–Stokes equation in an atmospheric context is considered. The scale invariant version of Gibbs free energy, carried by the most energetic molecules, enables the acceleration of organized flow (winds) from the smallest planetary scales by virtue of the nonlinearity of the mechanism, subject to dissipation by the more numerous average molecules maintaining an operational temperature via infrared radiation to the cold sink of space. The fastest moving molecules also affect the transfer of infrared radiation because their higher kinetic energy and the associated more-energetic collisions contribute more to the far wings of the spectral lines, where the collisional displacement from the central energy level gap is greatest and the lines are less self-absorbed. The relationship of events at these scales to macroscopic variables such as the thermal wind equation and its components will be considered in the Discussion section. An attempt is made to synthesize the mechanisms by which winds are generated and sustained, on all scales, by appealing to published works since 2003. This synthesis produces a view of the general circulation that includes thermodynamics and the defining role of turbulence in driving it. Full article