Search Results (612)

Perovskite manganites (AMnO₃) and perovskite-like manganites (A’_1−xA_xMnO₃) are complex oxide materials that have attracted significant attention from the scientific community in recent years due to their structural flexibility, mixed-valence state, tunable electronic configuration, and multifunctional properties. This review systematically analyzes the synthesis methods, structural classification, and physicochemical characterization of perovskite manganites, as well as their magnetic, optical, electrical, dielectric, and catalytic properties. The influence of solid-state reactions, sol–gel, Pechini, hydrothermal, co-precipitation, microwave, and other mild chemical approaches on phase purity, morphology, particle size, and oxygen stoichiometry was examined. The structural diversity of perovskite and perovskite-like manganites, including simple ABO₃, double perovskites, multilayer, and low-dimensional systems, was characterized in relation to their functional properties. The review discussed the capabilities of methods for synthesizing and analyzing morphological properties, demonstrating the role of doping, cation substitution, oxygen vacancies, and Jahn–Teller distortions in controlling material properties. Prospects for the application of perovskite manganites in spintronics, magnetocaloric cooling, photocatalysis, gas-sensing devices, and energy conversion and storage systems were analyzed. This review highlights the structure–property–application relationship in perovskite manganites. Full article

M-type hexaferrites are widely used in magnetic applications, and tailoring their properties via aliovalent substitution requires a detailed understanding of charge compensation and cation distribution. In this work, Mg²⁺/M⁴⁺ (M = Zr, Hf) co-substituted BaFe₁₂O₁₉ was synthesized via Na₂CO₃ flux and comprehensively characterized by wavelength-dispersive X-ray spectroscopy, powder and single-crystal X-ray diffraction, Rietveld refinement, X-ray absorption near-edge structure, and magnetic measurements. Increasing substitution levels x, y in BaFe_12−x−yMg_xM_yO₁₉ result in increasing lattice parameters and decreasing the room-temperature magnetic parameters saturation magnetization, remanence, and coercivity, while remanence and coercivity increase at low temperatures. Secondary phases form for nominal substitution ≥ 1. Zr⁴⁺ and Hf⁴⁺ preferentially occupy the 4f₂ site, whereas Mg²⁺ is distributed over multiple sites, as indicated by polyhedral volume analysis. Wavelength-dispersive X-ray spectroscopy confirms homogeneous elemental distribution within individual crystals but reveals significant variation in substitution levels within batches. The maximum degree of substitution for the tetravalent metals was y ≈ 1.2–1.7, with lower Mg incorporation of x ≈ 0.9–1.1. Charge compensation was found to be partially achieved via vacancy formation, while minor Fe²⁺ contributions cannot be excluded. Full article

Background/Objectives: Tuberculosis remains a major public health challenge due to the persistence of Mycobacterium tuberculosis (Mtb) and the emergence of multidrug-resistant strains. In this study, Pep-H, an HNP-1-derived antimicrobial peptide with the sequence RRYGTCIYQGRLWAF-NH₂, was used as a compact scaffold to examine how single-residue substitutions at the Cys position affected its biological and functional profile. Methods: A focused single-position substitution panel was generated by replacing Cys with Trp, Ala, Arg, or Met while preserving peptide length and sequence context, and the analogs were computationally prioritized according to their predicted antitubercular potential and contrasting side-chain properties. The peptides were synthesized, purified, characterized by HPLC and mass spectrometry, and evaluated for activity against Mtb H37Rv, cytotoxicity, hemolysis, ethidium bromide accumulation, and DPPH radical scavenging. Results: Pep-H retained the most favorable profile, showing the highest antimycobacterial potency, low hemolysis, favorable selectivity indices, enhanced ethidium bromide accumulation, and the strongest antioxidant response. All Cys substitutions reduced antimycobacterial activity, indicating that none of the tested residues reproduced the integrated biological profile of Pep-H. Conclusions: The contrasting outcomes of the Arg- and Met-containing analogs suggest that increased cationicity or sulfur retention alone was insufficient, while supporting a multifactorial contribution of Cys side-chain chemistry and the local GTCIY environment. Full article

This study investigates potassium-L zeolite (K-L) as an adsorbent for the removal of thallium (Tl⁺) from aqueous solutions, focusing on the relationship between cation exchange and framework structural response. X-ray powder diffraction (XRPD), thermal analysis, and Rietveld refinements were employed to monitor structural modifications upon Tl⁺ uptake, combined with batch adsorption experiments to evaluate the removal performance. At low Tl⁺ uptake, only minor structural perturbations occur, mainly involving slight shifts in extra-framework cation positions and limited rearrangement of channel water molecules. At higher Tl⁺ concentrations, a measurable anisotropic expansion of the zeolite framework is observed, consistent with partial substitution of K⁺ by Tl⁺ and progressive modification of the hydration environment within the pores. Moreover, the crystallographic distribution of Tl⁺ differs from that of the original K⁺ cations, suggesting a specific site preference during the uptake process. Batch experiments reveal rapid uptake kinetics, with equilibrium reached within minutes, and high removal efficiency up to 99.5%. The adsorption behaviour is well described by the Langmuir model, with a maximum adsorption capacity of 631 mg g⁻¹. These findings highlight the coupling between ion exchange and structural flexibility in K-L zeolite and support its potential application for efficient thallium removal from contaminated water. Full article

Ferrocenium-catalyzed transformations provide a practical and sustainable approach to propargylic substitution reactions. Herein, we investigate the ring-opening of cyclopropyl-substituted propargylic alcohols with alcohol nucleophiles, catalyzed by ferrocenium tetrafluoroborate ([FeCp₂][BF₄]) to afford synthetically valuable enyne ethers. Mechanistic studies using GC and NMR spectroscopy reveal that the reaction proceeds via initial formation of a ring-closed propargylic ether intermediate, which subsequently undergoes ring opening to the enyne ether. Experimental evidence supports a carbocationic pathway in which the ferrocenium cation promotes ionization to a stabilized cyclopropyl ether intermediate, followed by intramolecular, ferrocenium-assisted cyclopropyl ring opening to the enyne product. Reaction rates and product distributions are strongly influenced by temperature and solvent polarity, with polar solvents and elevated temperatures favoring ring opening. At room temperature, the ring-closed substitution product predominates, whereas efficient formation of enynes occurs at 65 °C. The reaction progresses faster in a polar solvent, indicating an ionic mechanism. Studies employing substrates containing substituted cyclopropyl rings demonstrated pronounced regioselectivity during nucleophilic ring opening with alcohols, with preferential cleavage of the bond between the two substituted carbon atoms. This selectivity is consistent with partial positive-charge stabilization in the transition state. The corresponding enyne ether products were isolated in 98–31% isolated yields, in most cases as a single regio- and E/Z stereoisomer (5 h at 45 °C, 5 mol% [FeCp₂][BF₄] catalyst load, six equivalents alcohol nucleophile). The ferrocenium-catalyzed cyclopropyl ring opening establishes a convenient method for accessing enyne motifs, which are important structural units in organic synthesis and medicinal chemistry. Full article

Ring-opening polymerization (ROP) of β-lactones yields biodegradable and bioresorbable polyesters exhibiting potential utility in medicine and environmental protection. β-butyrolactone (BL) is especially interesting, as it yields polymers analogous to natural poly(3-hydroxybutyrates) produced by bacteria, fungi, and enzymes in nature. The biopolymer produced by these microorganisms is isotactic. While it can be synthesized biotechnologically through the bacterial fermentation of substrates, such as sucrose, corn, and sugar, laboratory production typically involves the ring-opening polymerization of BL. However, the latter process is mainly atactic, syndiotactic, or partly isotactic, and other β-substituted β-lactones are less well-known. Ring-opening polymerization is an excellent pathway for the production of poly(β-lactones). This critical review presents the different conditions required to synthesize poly(β-lactones) and a broad overview of the different kinds of ROPs, i.e., anionic, cationic, coordinative, supramolecular-based, and enzymatic processes. A great variety of initiators/catalysts have been studied, covering both metal-based and metal-free systems (organo- and biocatalysts). In this review, several mechanisms of β-lactone polymerization are presented and discussed, especially with regard to the processes’ initiation steps. Full article

Protein phosphatase PPM1A plays a critical role in cellular signaling by dephosphorylating key regulatory proteins. According to experimental data, the enzyme requires either Mn²⁺ or Mg²⁺ bound in the active center(s), hence its catalytic activity strongly depends on the chelated metal ions. In this study, the metal ion selectivity of PPM1A is investigated using DFT calculations on active site constructs of bi- and trinuclear metal centers and protein ligands from the first and second metal coordination shells. Binuclear Mn-Mn and trinuclear Mn-Mn-Mn sites show poor resistance to substitution by biogenic Fe²⁺ and Zn²⁺, with Gibbs energies of the Mn²⁺ → Fe²⁺/Zn²⁺ exchange being consistently negative in both the gas phase and condensed media. In contrast, Mg-Mg and Mg-Mg-Mg centers are substantially more robust, with a thermodynamically unfavorable Mg²⁺ → Fe²⁺/Zn²⁺ substitution—except in the case of the Mg-Mg-Zn complex. The primary factors governing this metal competition in the modeled structures are the nature of the competing cation and the solvation properties of its aqua complexes, while solvent exposure of the binding site and the number of metal cations in the catalytic center exert a comparatively minor effect. Overall, these findings demonstrate that Mg²⁺-loaded active sites offer considerably greater protection against biogenic metal displacement than their Mn²⁺ counterparts, thus shedding light on the metalloprotein stability and enzyme fidelity of PPM1A. Full article

The study investigates Co²⁺/M⁴⁺ (Sn, Zr, Hf)-substituted M-type barium ferrites to understand phase formation, structural evolution and magnetic behavior. Ferrites with the general composition BaFe_12−x−yCo_xM_yO₁₉ were synthesized via sodium carbonate flux and analyzed using powder and single-crystal X-ray diffraction, wavelength dispersive X-ray spectroscopy, X-ray absorption spectroscopy and magnetic measurements. Structural analysis showed increasing lattice parameters with increasing degree of substitution, confirming incorporation of the substituting tetravalent metals. Differing maximum substitution levels were determined for the different systems, with wavelength dispersive X-ray spectroscopy providing the most reliable compositional data. A slight excess of the tetravalent metals Sn⁴⁺, Zr⁴⁺ and Hf⁴⁺ relative to Co²⁺ was frequently observed. X-ray absorption spectroscopy and wavelength dispersive X-ray spectroscopy analyses indicated negligible Fe²⁺ formation and no clear trends for formation of vacancies. Site occupancy analysis assigned tetravalent cations primarily to the Fe(4) site (4f₂), with evidence that cobalt partially occupies the Fe(3) site (4f₁). Magnetic measurements revealed decreasing saturation magnetization, remanence and coercivity at room temperature with increasing substitution level, while low-temperature measurements showed enhanced remanence and coercivity. Full article

This study investigates the modulation of coercivity and magnetodielectric coupling in heat-treated, nickel-substituted lanthanum ferrite. LaFe_0.7Ni_0.3O₃ samples were synthesized by high-energy ball milling and sintered at temperatures between 1073 and 1473 K. Chemical composition, crystalline structural evolution, surface morphology, magnetic, dielectric, and electrical properties, as well as magnetodielectric coupling, were analyzed. The XPS spectra revealed the presence of adsorbed oxygen, associated with the high oxygen affinity of the material. This behavior is interpreted as a charge-compensation mechanism, related both to the formation of oxygen vacancies and to the partial oxidation of Fe³⁺ to Fe⁴⁺. XRD and Rietveld refinement confirmed a single-phase orthorhombic Pnma structure, and structural simulations revealed progressive octahedral distortions with increasing temperature, affecting the octahedral tilting and electronic bandwidth. Magnetic characterization revealed that thermal processing modifies the magnetic behavior, inducing weak ferromagnetism and a significant increase in coercivity, correlating with progressive densification, greater domain stability, and reduced microstrain. Impedance measurements revealed magnetodielectric coupling, the Maxwell–Wagner interfacial polarization mechanism, and reduced dielectric losses. These findings demonstrate that the coercivity and magnetodielectric response in cationic nickel-substituted lanthanum ferrite can be tuned through thermal processing. A semi-empirical magnetocrystalline anisotropy model is proposed to explain the coercivity evolution and associated multiferroic behaviors, thus contributing to the study of functional ferrites as sustainable alternatives to rare-earth magnetic materials with potential in sensors and memory devices. Full article

The potential for the use of antimicrobial peptides (AMPs) as anticancer agents has garnered much interest because of their selective cytotoxicity to tumor cells and ability to evade multidrug resistance mechanisms. AMPs are shorter cationic amphiphilic molecules, part of our innate immune system, with direct membrane-disruptive activity and immunomodulatory effects. Anticancer peptides (ACPs) can be derived from natural biophysical sources or synthetically engineered, taking advantage of the unique biophysical properties of cancer cell membranes to exert their anti-tumor activities rapidly and often without significant effects on normal tissues. Advances in peptide engineering, such as D-amino acid substitution, cyclization, and PEGylation, combined with nanocarrier systems, have provided opportunities to improve peptide stability, bioavailability, and delivery to targeted sites. Studies in preclinical and clinical models show promise, indicating that AMPs and ACPs can induce immunogenic cell death, modify tumor microenvironments, and be used in combination with more conventional therapies. While the promise of AMPs and ACPs as relatively novel cancer therapeutics is substantial, challenges such as proteolytic degradation, dose-dependent toxicity, costs for production, and regulatory hurdles are notable. This review organizes the current literature on classification, mechanism(s) of action, delivery strategies, preclinical and clinical data, and provides areas for future work to improve and help speed their clinical translation as new cancer therapies. Full article

CeO₂ is a representative oxygen-storage oxide because its fluorite lattice can reversibly release and reincorporate oxygen through the Ce⁴⁺/Ce³⁺ redox couple and the associated formation and annihilation of oxygen vacancies. Although doped CeO₂ has been studied extensively, the literature has often treated oxygen-storage enhancement mainly in terms of dopant identity and composition, whereas the more fundamental issue is how a given doping strategy constructs a specific defect state within the fluorite host. Here, oxygen-storage enhancement is discussed from the standpoint of defect-state engineering. The discussion focuses on three routes, as follows: rare-earth single doping, cation–anion co-doping, and route-dependent dopant incorporation. Rare-earth single doping correlates aliovalent substitution with lattice expansion, vacancy generation, and finite oxygen-storage-capacity (OSC) optima. Cation–anion co-doping further shows that simultaneous perturbation of the cationic and anionic sublattices can amplify the defect response, while also demonstrating that vacancy concentration alone does not fully account for OSC enhancement. Route-dependent doping adds an additional dimension by showing that the same dopant can produce different lattice responses, defect populations, and oxygen-release behaviors when introduced through different pathways. On this basis, the review argues that OSC in doped CeO₂ is more meaningfully rationalized through a coupled descriptor set involving lattice accommodation, Ce³⁺/Ce⁴⁺ redistribution, oxygen-vacancy abundance, and dopant incorporation pathway. Taken together, these observations shift the design logic of oxygen-storage ceria from empirical dopant screening toward deliberate defect-state construction. Full article

The article presents the synthesis and characterization of double halide perovskites (DHPs) with the nominal composition Cs₂Ag_0.2Na_0.4In_0.6M_0.4Cl₆ (M = Si, Ti, Zr), including photoluminescence (PL), photoluminescence excitation (PLE) spectra measured over a range of temperatures and kinetics of luminescence. The materials were synthesized via a hydrothermal method. The phase purity and elemental composition of the synthesized perovskites were confirmed by X-ray diffraction (XRD), Rietveld refinement, scanning electron microscopy (SEM) equipped with energy-dispersive X-ray spectroscopy (EDS) and elemental analysis, which demonstrated that the samples showed a close match to the target stoichiometry. The PL spectra exhibit a systematic shift toward the lower-energy region with substitution from Si to Zr, correlating with the progressive increase in the ionic radii of the substituting cations. All samples display broad, asymmetric emission bands, characteristic of self-trapped excitonic (STE) states. Temperature-dependent PL measurements reveal a gradual decrease in emission intensity with increasing temperature for all samples. The maximum emission intensity is observed in the range of ~160–200 K, corresponding to optimal conditions for radiative recombination, whereas the lowest intensity is recorded at ~80–100 K, where thermal activation of radiative centers is minimal. An increase in temperature is accompanied by a red shift in the PL bands across all compositions. In the Ti-doped DHP, a pronounced blue shift at low temperatures is observed, which can be attributed to the involvement of Ti³⁺-related electronic states. An analysis of the activation energy of thermal luminescence quenching and the results of time-resolved spectroscopy revealed the activation of thermal processes in the titanium-containing sample and their rapid decay, whereas replacing titanium with silicon leads to more stable luminescence in the crystal under study. Thus, the enhanced luminescence characteristics of double halide perovskites doped with Ti, Si, and Zr highlight their potential for advanced photonic and optoelectronic applications. Full article

The safe immobilization of high-level waste (as actinide) remains a critical bottleneck in the disposal of high-level radioactive waste worldwide. Moreover, the higher specific surface area and surface energy of nano-scale powders enable the production of ceramic materials featuring denser crystal structures and superior strength, hardness, and toughness. Therefore, in this study, Gd³⁺ was used as a surrogate for actinides, and Nb⁵⁺ was introduced as a high-valence charge-compensating cation. Nano-scale powders of CaCO₃, ZrO₂, Gd₂O₃, TiO₂, and Nb₂O₅ were employed to prepare a series of defect-fluorite-derived ceramics, CaZr_1-xGd_xTi_2-xNb_xO₇ (x = 0.1–1.0), via a high-temperature solid-state reaction method, aiming to investigate the atomic substitution mechanisms, phase evolution, and chemical stability under high-valence charge compensation. Laboratory X-ray diffraction (XRD), synchrotron X-ray diffraction (SXRD), and backscattered scanning electron microscopy with energy-dispersive X-ray spectroscopy (BSEM-EDX) confirmed a phase evolution sequence from zirconolite-2M to zirconolite-4M and finally to pyrochlore. This behavior is consistent with that reported for other Ln³⁺-Nb⁵⁺ co-doped zirconolite systems. Rietveld refinement of the SXRD data further revealed, for the first time, the site-occupancy mechanism of Gd and Nb in zirconolite-4M. In both zirconolite-2M and zirconolite-4M, Gd preferentially occupies the Ca sites, whereas Nb substitutes at the Ti sites. In the pyrochlore structure, Ca, Zr, and Gd occupy the 16d sites, while Ti and Nb occupy the 16c sites. Static leaching tests following the MCC-1 protocol showed that pyrochlore exhibits the highest leaching resistance, whereas zirconolite-2M shows the lowest. After 28 days, the highest Gd leaching rate was 1.92(1) × 10⁻⁵ g m⁻² d⁻¹. These results provide new insights into actinide immobilization behavior and compositional design in zirconolite-based waste forms. Full article

This study was performed to elucidate the mechanism underpinning the nodal swelling induced by equinatoxin II (EqtII), a cation-selective pore-forming toxin derived from the sea anemone Actinia equina. Experiments were conducted using frog myelinated nerve fibers as a model system. Application of EqtII led to an approximately two-fold increase in the nodal volume of myelinated axons, but only when extracellular Ca²⁺ was present. Replacing extracellular Cl⁻ with isethionate had no measurable effect on this response, whereas substitution of NaCl with either sucrose or LiCl, an established Na⁺/Ca²⁺ exchanger (NCX) inhibitor, abolished the swelling. The persistence of the effect in the presence of tetrodotoxin indicates that voltage-gated Na⁺ channels are not involved in the underlying mechanism. Our data suggest that Ca²⁺ influx through EqtII-induced membrane pores raises intracellular Ca²⁺ levels, thereby stimulating the NCX in its forward-operating mode. This process promotes Ca²⁺ extrusion in exchange for Na⁺ entry. The resulting accumulation of intracellular Na⁺ increases osmotic pressure within the axon, leading to water influx and nodal swelling. Full article

The growing demand for sustainable and economically efficient road maintenance solutions has driven the development of materials that reduce the use of natural aggregates and promote waste valorization. In this context, this study evaluates the use of reclaimed asphalt pavement (RAP) and greywacke aggregates derived from Panasqueira mining by-products as partial or total substitutes for granite aggregates in cold asphalt mixtures intended for rapid pothole repair. Reference mixtures and recycled mixtures were produced with controlled proportions of RAP and greywacke, using cationic bituminous emulsion and hydrated lime, as well as an additional mixture composed only of RAP with a fluxing cold binder. Three commercial mixtures, identified as CCM1, CCM2, and CCM3, were also evaluated. Performance was analyzed through Cantabro particle loss, Marshall stability and flow, indirect tensile stiffness modulus, and water sensitivity (ITSR). The results show that greywacke provides a robust granular skeleton, while RAP content and binder type influence stiffness, cohesion, and moisture resistance. Overall, the combination of RAP and greywacke proved to be technically viable and, in several cases, superior to the commercial mixtures studied. Full article