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This study presents the fabrication possibilities of ultra-high-temperature ceramics of ZrB2-30 vol.%SiC and (ZrB2-HfB2)-30 vol.% SiC composition using the reaction spark plasma sintering of composite powders ZrB2(HfB2)-(SiO2-C) under two-stage heating conditions. The phase composition and microstructure of the obtained ceramic materials have been subjected to detailed analysis, their electrical conductivity has been evaluated using the four-contact method, and the electron work function has been determined using Kelvin probe force microscopy. The thermal analysis in the air, as well as the calcination of the samples at temperatures of 800, 1000, and 1200 °C in the air, demonstrated a comparable behavior of the materials in general. However, based on the XRD data and mapping of the distribution of elements on the oxidized surface (EDX), a slightly higher oxidation resistance of the ceramics (ZrB2-HfB2)-30 vol.% SiC was observed. The I-V curves of the sample surfaces recorded with atomic force microscopy demonstrated that following oxidation in the air at 1200 °C, the surfaces of the materials exhibited a marked reduction in current conductivity due to the formation of a dielectric layer. However, data obtained from Kelvin probe force microscopy indicated that (ZrB2-HfB2)-30 vol.% SiC ceramics also demonstrated enhanced resistance to oxidation.

The unique redox properties of nanoscale cerium dioxide determine its diverse application in biology and medicine as a regulator of oxidative metabolism. Lipid modifiers of the nanoparticle surface change their biochemical properties and bioavailability. Complexes with lipids can be formed upon contact of the nanoparticles with the membrane. The effects of lipid coating on nanoceria have not been studied yet. Here, we assessed the effect of bare and cardiolipin-coated CeO2 on the expression of oxidative metabolism genes in human embryonic lung fibroblasts. Cell viability, mitochondrial activity, intracellular reactive oxygen species, NOX4, NRF2, and NF-κB expression, oxidative DNA damage/repair, autophagy, and cell proliferation were studied. We used an MTT assay, fluorescence microscopy, real-time reverse transcription polymerase chain reaction, and flow cytometry. At a concentration of 1.5 μM, bare and cardiolipin-coated nanoceria penetrated into cells within 1–3 h. Cell survival, mitochondrial activity, and the proliferative effect were similar for bare and cardiolipin-coated nanoceria. Intracellular ROS, activation of NOX4, NRF2, and NF-kB, DNA oxidative damage, and DNA break/repair were different. Cardiolipin-coated nanoceria induced intracellular oxidative stress and short-term activation of these genes and DNA damage/break/repair. Unlike bare nanoceria, cardiolipin-coated nanoceria induced autophagy. Thus, the effects of cardiolipin-coated nanoceria are determined by both the nanoceria itself and cardiolipin. Presumably, the differences in properties are due to lipid peroxidation of cardiolipin. This effect needs to be taken into account when developing nanoceria-based drugs targeting mitochondria.

X-ray-induced photodynamic therapy (X-PDT) represents a promising new method of cancer treatment. A novel type of nanoscintillator based on cerium fluoride (CeF3) nanoparticles (NPs) modified with flavin mononucleotide (FMN) has been proposed. A method for synthesizing CeF3-FMN NPs has been developed, enabling the production of colloidal, spherical NPs with an approximate diameter of 100 nm, low polydispersity, and a high fluorescence quantum yield of 0.42. It has been demonstrated that CeF3-FMN NPs exhibit pH-dependent radiation-induced redox activity when exposed to X-rays. This activity results in the generation of reactive oxygen species, which is associated with the scintillation properties of cerium and the transfer of electrons to FMN. The synthesized NPs have been demonstrated to exhibit minimal cytotoxicity towards normal cells (NCTC L929 fibroblasts) but are more toxic to tumor cells (epidermoid carcinoma A431). Concurrently, the synthesized NPs (CeF3 and CeF3-FMN NPs) demonstrate a pronounced selective radiosensitizing effect on tumor cells at concentrations of 10−7 and 10−3 M, resulting in a significant reduction in their clonogenic activity, increasing radiosensitivity for cancer cells by 1.9 times following X-ray irradiation at a dose of 3 to 6 Gy. In the context of normal cells, these nanoparticles serve the function of antioxidants, maintaining a high level of clonogenic activity. Functional nanoscintillators on the basis of cerium fluoride can be used as part of the latest technologies for the treatment of tumors within the framework of X-PDT.

Cerium dioxide sols stabilised with L-malic acid were shown to exhibit significant antioxidant activity towards alkyl peroxyl radicals in the range of ligand:CeO2 molar ratios of 0.2–1 (0.2:1, 0.4:1, 0.5:1, 0.6:1, 0.8:1 and 1:1). The antioxidant activity of cerium dioxide nanoparticles greatly depended on L-malic acid content and increased by 8 times when the ligand:CeO2 molar ratio increased from 0.2:1 to 0.4:1. An estimate of the ligand:CeO2 molar ratio required to ensure complete surface coverage of CeO2 nanoparticles with malate anions resulted in a value of 0.2. Aggregation degree of CeO2 nanoparticles depends on the ligand:CeO2 molar ratio. In the range of ligand:CeO2 molar ratios 0.2–0.4, the size of aggregates decreased by an order of magnitude. The antioxidant capacity of 1 mM malate-stabilised cerium dioxide (0.2:1) relative to sodium ascorbate was 0.012 ± 0.001 mM. The antioxidant activity of cerium dioxide stabilised with L-malic acid at a ligand:CeO2 molar ratio of 0.2:1 was 80 times less than the antioxidant activity of sodium ascorbate. Cerium dioxide nanoparticles stabilised with L-malic acid did not demonstrate a cytotoxic effect against human mesenchymal stem cells, in a wide range of concentrations (10−3–10−5 M), and their proliferation was stimulated after 72 h of cultivation. The results obtained show new possibilities for the design of biocompatible ceria-based nanomaterials with tunable pro- and antioxidant properties; these materials can further be assessed in view of their potential for treating oxidative stress-related disorders.

Crystalline cerium(III) phosphate (CePO4), cerium(IV) phosphates, and nanocrystalline ceria are considered to be promising components of sunscreen cosmetics. This paper reports on a study in which, for the first time, a quantitative comparative analysis was performed of the UV-shielding properties of CePO4, Ce(PO4)(HPO4)0.5(H2O)0.5, and CePO4/CeO2 composites. Both the sun protection factor and protection factor against UV-A radiation of the materials were determined. Ce(PO4)(HPO4)0.5(H2O)0.5 was shown to have a sun protection factor of 2.9, which is comparable with that of nanocrystalline ceria and three times higher than the sun protection factor of CePO4. Composites containing both cerium dioxide and CePO4 demonstrated higher sun protection factors (up to 1.8) than individual CePO4. When compared with the TiO2 Aeroxide P25 reference sample, cerium(III) and cerium(IV) phosphates demonstrated negligible photocatalytic activity. A cytotoxicity analysis performed using two mammalian cell lines, hMSc and NCTC L929, showed that CePO4, Ce(PO4)(HPO4)0.5(H2O)0.5, and nanocrystalline ceria were all non-toxic. The results of this comparative study indicate that cerium(IV) phosphate Ce(PO4)(HPO4)0.5(H2O)0.5 is more advantageous for use in sunscreens than either cerium(III) phosphate or CePO4/CeO2 composites, due to its improved UV-shielding properties and low photocatalytic activity.

The synthesis of multicomponent and high-entropy compounds has become a rapidly developing field in advanced inorganic chemistry, making it possible to combine the properties of multiple elements in a single phase. This paper reports on the synthesis of a series of novel high-entropy layered rare earth hydroxychlorides, namely, (Sm,Eu,Gd,Y,Er)2(OH)5Cl, (Eu,Gd,Tb,Y,Er)2(OH)5Cl, (Eu,Gd,Dy,Y,Er)2(OH)5Cl, and (Eu,Gd,Y,Er,Yb)2(OH)5Cl, using a homogeneous hydrolysis technique under hydrothermal conditions. Elemental mapping proved the even distribution of rare earth elements, while luminescence spectroscopy confirmed efficient energy transfer between europium and other rare earth cations, thus providing additional evidence of the homogeneous distribution of rare earth elements within the crystal lattice. The average rare earth cation radii correlated linearly with the unit cell parameters (0.868 < R2 < 0.982) of the high-entropy layered rare earth hydroxychlorides. The thermal stability of the high-entropy layered rare earth hydroxychlorides was similar to that of individual hydroxychlorides and their binary solid solutions.

In recent years, there has been an increasing interest in stimuli-responsive host–guest materials due to the high potential for their application in switchable devices. Light is the most convenient stimulus for operating these materials; a light-responsive guest affects the host structure and the functional characteristics of the entire material. UV-transparent layered rare earth hydroxides intercalated with UV-switchable anions are promising candidates as stimuli-responsive host–guest materials. The interlayer distance in the layered rare earth hydroxides depends on the size of the intercalated anions, which could be changed in situ, e.g., via anion isomerisation. Nevertheless, for layered rare earth hydroxides, the possibility of such changes has not been reported yet. A good candidate anion that is capable of intercalating into the interlayer space is the cinnamate anion, which undergoes UV-assisted irreversible trans–cis isomerisation. In this work, both trans- and cis-cinnamate anions were intercalated in layered yttrium hydroxide (LYH). Upon UV-irradiation, the interlayer distance of trans-cinnamate-intercalated layered yttrium hydroxide suspended in isopropanol changed from 21.9 to 20.6 Å. For the first time, the results obtained demonstrate the possibility of using layered rare earth hydroxides as stimuli-responsive materials.