The thermal decomposition of four iron carbonates (siderites) and their decomposition products in a vacuum ( 2·10− 5 Pa) was investigated for the first time using in-situ transmission 57Fe Mössbauer spectroscopy. These measurements were supported by X-ray diffraction, X-ray fluorescence, Raman spectroscopy, magnetic measurements, and transmission electron microscopy. Mössbauer spectra were collected from room temperature (RT) to 750 °C, and the sample was then cooled to RT. The initial samples contained siderite as the only Fe-mineral, and its content in the analyzed samples was greater than 80

Implantology is the field of industry in which titanium alloys play a crucial role. The most prevalent titanium alloy is Ti-6Al-4V, due to its high biocompatibility, corrosion and mechanical resistance. By using plasma electrolytic oxidation (PEO) it is possible to form a porous oxide layer, which provides a finer connection between the skeleton and an implant. Nonetheless, PEO coatings tends to lose their properties, such as wettability and bioactivity over time. The phenomenon that stands after that is called surface ageing process. To prevent it, surface-activating processes are used - such as plasma treatments. Owing to them, it is possible to maintain desire properties and further enhance the connection at the bone-implant interface. The main objective of that study is to quantitatively assess the influence of O2 and N2 plasma treatments on surface aging, wettability, morphology, and composition of PEO-coated Ti-6Al-4V alloy over 14 days. Plasma cleaning seems to erase carbon contaminants, so it has made the surfaces extra hydrophilic. Moreover, bioactivity has increased as the number of cells has risen. Wettability has marginally decreased over the time. Nevertheless, the process of ageing has been inhibited. The results suggest that plasma cleaning impacts positively on the surface properties, making the treatment worthy of further examinations. This work is unique in its assessment of the time-dependent degradation of PEO coatings after plasma treatment, as it provides an overview of their long-term performance.

Hybrid electrolytes combining ionic liquids with nanoscale fillers offer a transformative route toward safe, high-performance energy storage; however, the lack of understanding of their charge transport over a broad range of temperature and pressure conditions limits their application. Herein, we address this issue by examining the structural, conducting, viscoelastic and thermodynamic properties of a model quasi-solid electrolyte composed of an ammonium ionic liquid and charged polyhedral oligomeric silsesquioxane (POSS) nanoparticles over an extended temperature (173-393 K) and pressure (0.1-600 MPa) range. We demonstrate that the rigid POSS scaffold creates excess free volume, reduces compressibility and thermal expansion, and introduces reversible shear-thinning viscoelasticity while maintaining efficient ion conduction. Furthermore, our high-pressure experiments reveal that ion dynamics is mostly thermally activated in this nano-hybrid electrolyte and satisfies the density-scaling concept, enabling accurate prediction of ionic conductivity over 12 decades across a wide T-P landscape. This work establishes a fundamental and predictive framework for designing next-generation nano-hybrid electrolytes for operation in extreme environments.

The low aqueous solubility of crystalline enzalutamide (ENZ) and the limited physical stability of amorphous ENZ present significant formulation challenges. In this study, we explore binary co-amorphous systems of ENZ with octaacetyl maltose (acMAL), focusing on the system having eutectic concentration (ENZ + 75 wt % acMAL) as a potential strategy to enhance both stability and solubility. Based on differential scanning calorimetry (DSC) studies of crystalline materials, the eutectic point was identified, while analysis of DSC thermograms of co-amorphous systems revealed pronounced deviations in values of glass transition temperature (Tg) from Gordon-Taylor predictions, implicating the existence of strong specific intermolecular interactions. FTIR studies confirmed the presence of heteromolecular bonding within the mixtures. Broadband dielectric spectroscopy (BDS) showed that, although acMAL increases ENZ molecular mobility, the eutectic co-amorphous formulation significantly suppresses recrystallization under isothermal conditions (T = 413 K), delaying crystallization onset by over 30 h and limiting crystallinity to ≤2% after 55 h. The eutectic ENZ + acMAL composition exhibited sustained supersaturation in both aqueous and biorelevant media, demonstrating a balanced combination of efficient drug release and superior stabilization against recrystallization. These results confirm that eutectic formation followed by co-amorphization of ENZ with acMAL effectively addresses the dual challenges of limited physical stability and poor aqueous solubility. This approach provides a mechanistically rational and transferable strategy for improving the performance of poorly water-soluble APIs in pharmaceutical formulations.

Oral infections caused by antibiotic-resistant bacteria represent an emerging biomedical hazard and growing challenge for modern dentistry. To address this issue, Ag- and Cu-ZnO nanocomposites (NCs) were synthesized using ZnO carrier to combat the oral pathogens Streptococcus mutans and Streptococcus sobrinus. A comprehensive analysis of chemically synthesized metal oxide nanocomposites (MONCs) was performed, combining physicochemical characterization (TEM, XRD, ζ-potential, DLS, pH, and PFO/PSO kinetic models) with biological toxicity assessment (MIC, ATR-FTIR, SEM, and FAMEs) to better understand their antimicrobial mechanisms. The results confirmed that the synthesized nanoproducts fulfill the criteria for nanomaterials (NMs) (particle size < 100 nm). Among them, Ag-ZnO exhibited the highest antibacterial activity against both strains (MIC = 50 mg L-1). Kinetic modeling revealed faster and more efficient Ag ion release from Ag-ZnO NCs compared to Cu from Cu-ZnO NCs. Molecular analyses indicated strong MONC-bacterial interactions at the cell surface, leading to changes in protein secondary structures, alterations in lipid composition, and disruption of Gram-positive bacterial membranes. Additionally, Ag-ZnO inhibited chain and cluster formation in both bacterial species, while Cu-ZnO affected only S. sobrinus. Overall, Ag- and Cu-ZnO NCs show strong potential as antimicrobial agents against oral pathogens.

A thermally programmable mesoporous silica nanoreactor was developed that integrates copper adsorption, stabilization, and confinement-driven phase transformation within a single ordered host. It is based on SBA-15 mesoporous silica functionalized with propyl-phosphonate groups, which act as immobile high-affinity coordination sites for Cu2+ during aqueous adsorption. In parallel, mobile Cu(acac)2 complexes diffuse through the hydrophobic mesopore channels and serve as uniformly distributed molecular copper precursors. This dual-functional architecture combines strong interfacial binding with preserved molecular mobility, enabling efficient copper capture while allowing copper species to reorganize and react within the confined pore environment. Structural analyses demonstrate that copper incorporation and thermal treatment induce controlled mesoscopic reorganization without disrupting the long-range hexagonal order of SBA-15. Small-angle diffraction reveals a moderate shift of the (100) reflection consistent with lattice contraction caused by pore filling and framework densification. At the same time, transmission electron microscopy confirms preservation of the ordered cylindrical mesopore structure. Wide-angle diffraction and Raman spectroscopy exclude the presence of bulk crystalline Cu(acac)2, confirming high dispersion and confinement of copper species within the pores. Upon thermal activation, confined copper precursors decompose and undergo diffusion-driven restructuring, forming spatially confined copper phosphate and copper hydrophosphate nanophases. Statement of environmental implications From the perspective of environmental protection and resource efficiency, the proposed SBA-15-based system can operate in two complementary modes: in the first, a reusable-adsorbent scenario, Cu2+ ions can be removed by controlled acid washing prior to thermal treatment, consistent with regeneration strategies for Cu-loaded functionalized SBA-15 materials; in the second, the spent material can be subjected to calcination as a post-use valorization step transforming immobilized copper into confined copper phosphate or hydrophosphate-type nanophases within the mesoporous matrix. Hence, thermal treatment should be considered a waste-to-material conversion pathway rather than a true adsorbent regeneration process. As a result, the system enables effective immobilization of Cu2+ ions, thereby reducing their mobility and environmental risk while simultaneously providing a route for stabilization and potential recovery of captured metal species, in line with circular economy principles that integrate water remediation with resource valorization and reduced dependence on primary copper extraction. Practical implementation, however, will require further validation, including adsorption–desorption cycling, performance in multi-ion and real wastewater systems, leaching stability studies, and techno-economic and scalability assessments.

Electrochemical processes on titanium and its alloys play a crucial role in the biomaterials industry. Such methods, as a plasma electrolytic oxidation (PEO) are commonly used in the process of producing a porous surface, which provides a better interaction at the bone-implant interface. Nevertheless, PEO surfaces tend to lose their hydrophilicity and bioactivity after certain amount of time. It is a phenomenon called surface ageing. By using surface-activating processes like plasma treatment, it is possible to prevent it and increase the association between the endoskeleton and implant. The main objective of that study is to quantitatively evaluate how O2 and N2 plasma treatments influence surface ageing, wettability, morphology, and composition of PEO-coated titanium over 14 days. The O2/N2 plasma cleaning seem to detach carbon contaminants, which made the surfaces extra hydrophilic. That modification of the coatings also made the surfaces more bioactive by enhancing the cell adhesion and proliferation. Wettability has slightly diminished with time. Nonetheless, the process of ageing has decelerated. Obtained results suggest that plasma cleaning affects positively on the surface properties, what makes the treatment worthy of further investigations. That study is one of a few, which examine the timedependent degradation of PEO coatings after plasma treatment, providing an overview of their long-term performance.

Rising triple-negative breast cancer (TNBC) cases and Candida infection risks during chemotherapy demand novel therapies, with metal-oxide nanocomposites emerging as a promising solution. In this study, we synthesized Ag-ZnO and Cu-ZnO nanocomposites as established quantitative links between their physicochemical properties, ion release behaviour, and biological activity, evaluating antifungal effects against Candida albicans (ATCC 90028) and Saccharomyces cerevisiae (ATCC 9763), and their anticancer potential against MDA-MB-231 cells (ATCC HTB-26). The results revealed Ag (similar to 13-19 nm) and Cu (similar to 4-8 nm) nanoparticles dispersed in a ZnO matrix, with XPS confirming mixed Ag-0/Ag(I)/Ag(III) and Cu(I)/Cu(II) speciation. Ag-ZnO NC exhibited strong antifungal activity (MIC = 25 mg L-1) against both fungi, while Cu-ZnO NC was only effective (MIC = 100 mg L-1) against S. cerevisiae. Aqueous release of Ag+ was similar to 2.6-fold higher than Cu2+. Ag-ZnO NC induced marked ROS generation (similar to 6-fold higher than S. cerevisiae) and dehydrogenase inhibition (6.6- and similar to 20-fold, respectively). ATR-FTIR linked species-specific susceptibility to cell-wall architecture. SEM confirmed membrane destabilization and perforation. In MDA-MB-231, necrotic fractions reached similar to 9% and >40% for Ag-ZnO and Cu-ZnO, respectively. Both metal oxide nanocomposites (MONCs) act through ion release, revealing a selectivity window, especially for Ag-ZnO. Further studies on non-cancerous cells, ion-release kinetics, uptake and in vivo validation are essential to establish a therapeutic index.

The structural and physical properties of microencapsulated iron sucrose and their changes upon dissolution in saline were tested. For the undissolved sample, calcium alginate microcapsules with irregular shapes were registered via scanning electron microscopy, inside which core–shell nanoparticles were identified by transmission electron microscopy micrographs. Magnetic studies (DC and AC) performed on the undissolved sample revealed the presence of a low temperature blocking process ( ≈ 10 K), and confirmed its superparamagnetic state between 70– 250 K. X-ray photoelectron spectroscopy and Raman studies showed a varied composition of the undissolved sample in which organic compounds and SiO2 are the major phases, while the iron phase was recognized as iron oxyhydroxide (FeOOH) (most probably the α polymorph). The dissolution procedure had significant influence on structural and physical properties of the investigated compound, such as lowering of the blocking temperature with the dissolution time. Electron paramagnetic resonance (EPR) studies performed on the completely dissolved sample revealed that some of the Fe3+ ions became paramagnetic, while the rest remained exchange coupled into clusters. The nonintentional manganese contamination was determined using EPR in the completely dissolved sample.

Condensed matter physics has long struggled to obtain a comprehensive picture of the liquid-glass transition. Consequently, over the years, universal manifestations of glassy and supercooled dynamics have been established, including a correlation between the static dielectric constant (Δε) and relaxation stretching (βKWW), as well as βKWW and Kirkwood correlation factor (gK), or deviation degree from Arrhenius behavior of structural relaxation times quantified by dynamic fragility (mP). Herein, we report a simple, highly polar liquid that breaks all of these rules established for glass-forming liquids. We show that the fluorine-assisted self-assembly, confirmed by temperature-dependent Raman and XRD measurements, brings peculiarities in relaxation dynamics, that is, extremely low dielectric strength, Debye-like shape of dielectric permittivity spectra, gK much below unity, and enormous acceleration of structural relaxation times and viscosity at T = Tg + 20 K. All these peculiarities reveal a strong effect of molecular self-assembly on the dynamics of glass-forming systems.

Plasma electrolytic oxidation (PEO) enables efficient metal surface modification via spark-driven incorporation of bath additives. Due to some fundamental limitations of the PEO process and the specific nature of carbonates, the latter have been relatively overlooked as valuable bath components. Concurrently, carbonate-based PEO coatings show promise for applications in photocatalysis, adsorption, corrosion protection, and biomedicine. This study introduces an unconventional strategy to facilitate carbonate inclusion into the PEO layer, using a bath formulation with calcium carbonate (CC) and hydroxyapatite (HA) particles as a model system. The PEO bath was the product of physicochemical interactions between a Na2HPO4 electrolyte and CC nanoparticles synthesized via a carbonation route. Meanwhile, these interactions were traced and attributed to competing dissolution-precipitation and chemisorption phenomena. PEO was conducted on titanium in near-DC mode, applying a limiting voltage of 450 V. The resulting coating displayed typical PEO features, was rich in Ca and P, moderately porous, and approximately 25 mu m thick. Raman spectroscopy detected CC, HA, carbonate HA, anatase, and amorphous TiO2, evenly distributed across the surface. In addition, the mechanism of coating growth under these conditions was described and discussed. This work provides practical evidence of the feasibility of carbonate incorporation via PEO, presents a confirmed approach to integrating CC particles into PEO coatings, and lays groundwork for their specialized applications.

Raman imaging and K-means cluster analysis of individual mineral grains supplemented by scanning electron microscopy, electron probe microanalysis, and X-ray powder diffraction were applied to study fine-grained, multi-component products of the pyrrhotite three-stage oxidative alteration in migmatitic gneiss. During the first stage, related to the kaolinization of feldspars in gneisses, pyrrhotite was replaced by marcasite via intermediate amorphous iron sulfide. Increased oxygen fugacity caused the localized crystallization of either maghemite or ferric (oxyhydr)oxides. Even higher oxygen fugacity and an increase in solution pH during the second stage of alteration resulted in the partial replacement of marcasite by pyrite, followed by the replacement of both sulfides by Fe oxides (hematite, maghemite, magnetite) and ferric (oxyhydr)oxides (goethite, feroxyhyte). The final stage of sulfide oxidative alteration resulted in the predominance of sulfates of the alunite–jarosite series over ferric oxyhydroxides and relicts of Fe sulfides. Quartz–calcite–pyrite hydrothermal veins were affected by the most recent weathering, which resulted in the crystallization of the dominant alunite–jarosite-series minerals (alunite, jarosite, Al-jarosite) and ferric (oxyhydr)oxides (goethite, lepidocrocite).

Objectives: This study highlighted the key role played by high-pressure (HP) dielectric spectroscopic measurements of amorphous CBD to probe the molecular dynamics in order to examine the physical stability of the drug. The pharmacological properties of CBD assure that this can be a promising drug for the pharmaceutical industry. Hence, it is important to check the physical stability under elevated temperature and pressure conditions to understand the behavior of the drug under manufacturing conditions. Methods: This research investigated the molecular dynamics at various temperatures and pressures. We utilized the HP dielectric studies which are considered as an advanced and sensitive tool to determine both the molecular dynamics and the phase transformations. Results: This paper discusses the physical stability by analyzing the behavior of structural relaxation and crystallization tendencies of the amorphous drug under ambient and elevated pressure conditions. This study verified that amorphous CBD is highly physically stable at storage and elevated temperature conditions under ambient pressure. Conclusions: Accordingly, we examined the physical stability under elevated pressures at storage temperature, and we observed that the compression induced the crystallization of amorphous CBD. The breaking of weak hydrogen bonds present in the CBD might be the reason for this destabilization at elevated pressures. The least physical stability at high-pressure conditions was also confirmed by the broadening of the α-relaxation peak at high pressures.

Electrolytes are fundamental materials that have been used in various electrochemical devices, including fuel cells and batteries. Herein, we report a new class of quasi-solid electrolytes based on ionic liquids (ILs) and multiply charged polyhedral oligomeric silsesquioxane (POSS) nanoparticles that overcome the traditional conductivity-mechanical stability trade-off in solid electrolytes. By precisely controlling the stoichiometric interaction between octa-charged POSS nanoparticles and selected ILs, we achieve unique combinations of properties: room-temperature ionic conductivity σdcRT up to 4 mS/cm, matching or exceeding the parent ILs; reversible shear-thinning behavior enabling easy processing; and exceptional long-term stability against phase separation. Systematic characterization reveals that the 30 wt % POSS loading enhances interfacial charge transfer near the NPs or creates an optimal percolating network where cation-nanoparticle interactions favor fast anion transport. At the same time, the charged POSS framework provides mechanical stability to the quasi-solid electrolyte.

A calcium-silicate xenolith (no. 11) from the ignimbrite of the Upper Chegem Caldera in Kabardino-Balkaria, Russia, has revealed a diverse mineral assemblage with As- and B-bearing phases from the apatite supergroup such as the svabite and johnbaumite-hydroxylellestadite series, in addition to cahnite and datolite. Three distinct zones of variable arsenic content have been investigated. Notably, the outermost altered zone adjacent to the ignimbrite hosts the highest concentration of arsenic and arsenate minerals. A detailed structural analysis using Raman spectroscopy was carried out to investigate the distribution of boron and arsenic in tetrahedral coordination. This has provided the basis for describing a solid-solution system between hydroxylellestadite, svabite and johnbaumite and can be used as a novel technique for identifying apatite-supergroup minerals. One aim of the analysis was to elucidate the origin of various elements and content levels, particularly in relation to the distance from the xenolith-ignimbrite contact. The presence of boron and arsenic, probably derived from ignimbrites, highlights the important role of volcanic rocks as potential contributors of these elements in mineral formation processes.

The implantology field is rapidly developing, which requires researchers to search for new personalized solutions. With the improvement of scanning methods in medicine, there is a connection to the science of 3D printed materials. While the surface treatment of conventionally made implants is widely researched, this study focuses on analyzing the surface of a 3D printed titanium alloy. The samples were subjected to plasma electrolytic oxidation (PEO) and subjected to scanning electron microscopy (SEM), energy dispersive X-ray microscopy (EDX), wettability, X-ray photoelectron spectroscopy (XPS), cross section, Raman, and biological trials analysis. Oxide coatings composed of titanium oxide, zirconium oxide, and niobium oxide were formed on the surfaces of the treated materials. These coatings were enriched with calcium, phosphate, and amine groups. The surfaces differed in wettability, which did not affect their bioactivity. The results suggest that while the conditions of the PEO are slightly different for both groups of samples, they present with similar surfaces, which makes the 3Dprinted alloy a promising material for implant use.

In this work a novel method for synthesis of 1,8-dihydroxynaphthalene melanin was presented, as well as the physicochemical properties, molecular structure, and characteristics of the pigment. The proposed synthesis protocol is simple and cost-effective with no enzymes or catalysts needed. The final product is not adsorbed on any surface, since the pigment is the result of autooxidation of 1,8-dihydroxynaphthalene. Performed analyses revealed that the solubility, optical and paramagnetic properties are typical for melanins, and in the EPR spectra an unusual hyperfine structure was observed. The molecular structure of the pigment consists of three different layers forming polar and non-polar surfaces. Additionally, the presence of ether bonds presence was revealed. The developed method creates new opportunities for melanin research and eliminates the need to extract melanins from biological samples, which often lead to structural changes in isolated melanins, which undermines the reliability of analyses of the properties and structure of these polymers. On the other hand, the ubiquity of melanins in living organisms and the diversity of their biological functions have let to the growing interest of researchers in this group of pigments. The analyses carried out show that the obtained synthetic DHN polymer can be considered as a model DHN-melanin in mycological studies and material research.

Currently there are no widely recognized standards for assessing the environmental risk of nanopesticides. Therefore, whether they are safer than conventional pesticide products remains open to discussion. We used non-target soil microorganisms as indicators of environmental change and applied functional gene arrays (FGAs) using GeoChip 5.0S targeting 151 000 genes involved in ecologically relevant functions. We synthesized nanofungicides in which the active substance captan was bound to inorganic nanocarriers (ZnO and SiO2) to examine the functional capabilities of microbial communities. During a 100-day microcosm study, changes in soil were compared to the effect of pesticide and nanocarriers alone. Based on 72 functional gene diversity profiles, we conducted environmental risk assessment of nanopesticides. Nanoagrochemicals affected the alpha and beta diversity of microbial functional genes, and the most profound negative effect was detected for captan, impacting carbon cycling and the organic remediation process from day 30. Additionally, the effect of nanopesticides changed during the experiment. On day 42, the effect was nanocarrier-dependent, and an increase of genes involved in denitrification (nirS, norB), archaeal conversion of N2 to NH3 and fungal N-assimilation was observed, especially for SiO2-treated set-ups. After 100 days, the negative effect was mainly related to the active substance released from the nanocarrier impacting the nitrate reductase gene (narG) and genes from the denitrification and nitrogen fixation subcategory. Analysis of microarrays did not indicate a recovery process for carbon cycling. Moreover, pesticide and nanoagrochemicals affected arsenic detoxification (aoxB, arsM, arsC), which may lead to an elevation of toxic As(III) availability. Our study indicated that FGAs are a sensitive method, revealing long-term changes previously undetected by other methods, including next-generation sequencing (NGS). This is the first study to confirm the usefulness of GeoChips for the evaluation of microbial redundancy as an important factor for fair environmental risk assessment of nanopesticides.

The structural and physical properties of microencapsulated iron sucrose and their changes upon dissolution in saline were tested.For the undissolved sample, calcium alginate microcapsules with irregular shapes were registered via scanning electron microsco-py, inside which core-shell nanoparticles were identified by transmission electron microscopy micrographs. Magnetic studies DCand AC performed on the undissolved sample revealed the presence of a low temperature blocking process approximate to 10 K, andconfirmed its superparamagnetic state between 70- 250 K. X-ray photoelectron spectroscopy and Raman studies showed a variedcomposition of the undissolved sample in which organic compounds and SiO2 are the major phases, while the iron phase wasrecognized as iron oxyhydroxide FeOOH most probably the alpha polymorph. The dissolution procedure had significant influenceon structural and physical properties of the investigated compound, such as lowering of the blocking temperature with the dissolu-tion time. Electron paramagnetic resonance EPR studies performed on the completely dissolved sample revealed that some of theFe3+ ions became paramagnetic, while the rest remained exchange coupled into clusters. The nonintentional manganese contamina-tion was determined using EPR in the completely dissolved sample.