A Comparative Study of Cerium(III) and Cerium(IV) Phosphates for Sunscreens.

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.

Gadolinium Doping Modulates the Enzyme-like Activity and Radical-Scavenging Properties of CeO2 Nanoparticles.

Their unique physicochemical properties and multi-enzymatic activity make CeO2 nanoparticles (CeO2 NPs) the most promising active component of the next generation of theranostic drugs. When doped with gadolinium ions, CeO2 NPs constitute a new type of contrast agent for magnetic resonance imaging, possessing improved biocatalytic properties and a high level of biocompatibility. The present study is focused on an in-depth analysis of the enzyme-like properties of gadolinium-doped CeO2 NPs (CeO2:Gd NPs) and their antioxidant activity against superoxide anion radicals, hydrogen peroxide, and alkylperoxyl radicals. Using an anion-exchange method, CeO2:Gd NPs (~5 nm) with various Gd-doping levels (10 mol.% or 20 mol.%) were synthesized. The radical-scavenging properties and biomimetic activities (namely SOD- and peroxidase-like activities) of CeO2:Gd NPs were assessed using a chemiluminescent method with selective chemical probes: luminol, lucigenin, and L-012 (a highly sensitive luminol analogue). In particular, gadolinium doping has been shown to enhance the radical-scavenging properties of CeO2 NPs. Unexpectedly, both bare CeO2 NPs and CeO2:Gd NPs did not exhibit SOD-like activity, acting as pro-oxidants and contributing to the generation of reactive oxygen species. Gadolinium doping caused an increase in the pro-oxidant properties of nanoscale CeO2. At the same time, CeO2:Gd NPs did not significantly inhibit the intrinsic activity of the natural enzyme superoxide dismutase, and CeO2:Gd NPs conjugated with SOD demonstrated SOD-like activity. In contrast to SOD-like properties, peroxidase-like activity was observed for both bare CeO2 NPs and CeO2:Gd NPs. This type of enzyme-like activity was found to be pH-dependent. In a neutral medium (pH = 7.4), nanoscale CeO2 acted as a prooxidant enzyme (peroxidase), while in an alkaline medium (pH = 8.6), it lost its catalytic properties; thus, it cannot be regarded as a nanozyme. Both gadolinium doping and conjugation with a natural enzyme were shown to modulate the interaction of CeO2 NPs with the key components of redox homeostasis.

Coating of Filter Materials with CeO2 Nanoparticles Using a Combination of Aerodynamic Spraying and Suction.

Textiles and nonwovens (including those used in ventilation systems as filters) are currently one of the main sources of patient cross-infection. Healthcare-associated infections (HAIs) affect 5-10% of patients and stand as the tenth leading cause of death. Therefore, the development of new methods for creating functional nanostructured coatings with antibacterial and antiviral properties on the surfaces of textiles and nonwoven materials is crucial for modern medicine. Antimicrobial filter technology must be high-speed, low-energy and safe if its commercialization and mass adoption are to be successful. Cerium oxide nanoparticles can act as active components in these coatings due to their high antibacterial activity and low toxicity. This paper focuses on the elaboration of a high-throughput and resource-saving method for the deposition of cerium oxide nanoparticles onto nonwoven fibrous material for use in air-conditioning filters. The proposed spraying technique is based on the use of an aerodynamic emitter and simultaneous suction. Cerium oxide nanoparticles have successfully been deposited onto the filter materials used in air conditioning systems; the antibacterial activity of the ceria-modified filters exceeded 4.0.

Heavily Gd-Doped Non-Toxic Cerium Oxide Nanoparticles for MRI Labelling of Stem Cells.

Recently, human mesenchymal stem cells (hMSc) have attracted a great deal of attention as potential therapeutic agents in the treatment of socially significant diseases. Despite substantial advances in stem-cell therapy, the biological mechanisms of hMSc action after transplantation remain unclear. The use of magnetic resonance imaging (MRI) as a non-invasive method for tracking stem cells in the body is very important for analysing their distribution in tissues and organs, as well as for ensuring control of their lifetime after injection. Herein, detailed experimental data are reported on the biocompatibility towards hMSc of heavily gadolinium-doped cerium oxide nanoparticles (Ce0.8Gd0.2O2-x) synthesised using two synthetic protocols. The relaxivity of the nanoparticles was measured in a magnetic field range from 1 mT to 16.4 T. The relaxivity values (r1 = 11 ± 1.2 mM-1 s-1 and r1 = 7 ± 1.2 mM-1 s-1 in magnetic fields typical of 1.5 and 3 T MRI scanners, respectively) are considerably higher than those of the commercial Omniscan MRI contrast agent. The low toxicity of gadolinium-doped ceria nanoparticles to hMSc enables their use as an effective theranostic tool with improved MRI-contrasting properties.

The Strong Protective Action of Ce3+/F- Combined Treatment on Tooth Enamel and Epithelial Cells.

We studied the toxic effects of cerium and fluoride species on human dental pulp stem cells and epithelial cells of Cercopithecus aethiops as a surrogate for the human oral mucosa. The sequential use of CeCl3 and NH4F solutions in equimolar sub-toxic concentrations enabled the possible toxic effects of individual components to be avoided, ensuring the preservation of the metabolic activity of the cells due to the formation of CeF3 nanoparticles. Cerium fluoride nanoparticles and terbium-doped cerium fluoride nanoparticles exhibited neither cytotoxicity nor genotoxicity to dental pulp stem cells, even at high concentrations (10-4 M). In millimolar concentrations (from 10-5-10-6 M), these nanoparticles significantly increased the expression of genes responsible for the cell cycle, differentiation and proliferation. The formation of cerium fluoride on the surface of the mucous membrane and teeth provided protection against the development of carious lesions, periodontitis, ROS attacks and other inflammatory diseases of the oral cavity. Luminescent CeF3: Tb nanoparticles enabled the visualization of tooth enamel microcracks.

1D Ceric Hydrogen Phosphate Aerogels: Noncarbonaceous Ultraflyweight Monolithic Aerogels.

Ceric hydrogen phosphate gels possess a very unique spatial organization, being nearly amorphous materials with a fibrous structure. Using a sol-gel approach, we succeeded in preparing bulky gels containing as much as 20,000 molecules of water per cerium atom. Supercritical treatment of these gels made it possible to obtain the first ultralight monolithic noncarbonaceous aerogels with a density as low as 1 mg/cm3.

Meet the Cerium(IV) Phosphate Sisters: CeIV (OH)PO4 and CeIV 2 O(PO4 )2.

Two new cerium(IV) phosphates were obtained: cerium(IV) hydroxidophosphate, Ce(OH)PO4 , and cerium(IV) oxidophosphate, Ce2 O(PO4 )2 , which were shown to complement the classes of isostructural compounds M(OH)PO4 and R2 O(PO4 )2 , where M=Th, U and R=Th, U, Np, Zr. Ce2 O(PO4 )2 oxidophosphate is formed by elimination of H2 O from the crystal structure of Ce(OH)PO4 during its thermal decomposition. The structures of Ce(OH)PO4 and Ce2 O(PO4 )2 are related to each other with the same Cmce space group and similar unit cell parameters (a=6.9691(3) Å, b=9.0655(4) Å, c=12.2214(4) Å, V=772.13(8) Å3 , Z=8; a=7.0220(4) Å, b=8.9894(5) Å, c=12.544(1) Å, V=791.8(1) Å3 , Z=4, respectively).

Photochromic and Photocatalytic Properties of Ultra-Small PVP-Stabilized WO3 Nanoparticles.

Tungsten oxide-based bulk and nanocrystalline materials are widely used as photocatalytic and photo- and electrochromic materials, as well as materials for biomedical applications. In our work, we focused our attention on the effect of sodium cations on the structure and photochromic properties of the WO3@PVP aqueous sols. To establish the effect, the sols were synthesized by either simple pH adjusting of sodium or ammonium tungstates' solutions, or using an ion exchange technique to remove the cations from the materials to the greatest possible extent. We showed that the presence of sodium cations in WO3@PVP favors the formation of reduced tungsten species (W+5) upon UV irradiation of the materials, strongly affecting their photochromic and photocatalytic properties. The pronounced photoreductive properties of WO3@PVP sols in photocatalytic reactions were demonstrated. Due to photoreductive properties, photochromic sols of tungsten oxide can act as effective photoprotectors in photooxidation processes. We believe that our work provides a considerable contribution to the elucidation of photochromic and redox phenomena in WO3-based materials.