Fractal structures and silica films formed by the Treignac water on inert and biological surfaces.

The Treignac water is a natural mineral water containing mainly orthosilicic acid. On inert substrates, it forms a silica film with fractal structures which cannot be reproduced in laboratory-reconstituted water. These structures form by condensation of orthosilicic acid monomers, following the Witten-Sander model of diffusion-limited aggregation. On biological surfaces, such as tomato leaves, the Treignac water forms a silica film with a different morphology and devoid of fractal structures. The filmogenic properties of this natural mineral water are here discussed in the context of crop protection, as the silica film can provide a barrier and a platform for the immobilization of elicitors of plant defense responses.

Shape-selective synthesis of nanoceria for degradation of paraoxon as a chemical warfare simulant.

Repeated attacks using organophosphorus compounds, in military conflicts or terrorist acts, necessitate developing inexpensive and readily available decontamination systems. Nanosized cerium oxide is a suitable candidate, acting as a heterogeneous catalyst for the degradation of organophosphorus compounds such as VX agent or sarin. However, the reaction mechanism of the phosphatase mimetic activity of CeO2 nanoparticles is not fully described. Adsorption, surface-promoted hydrolysis, and desorption cycles strongly depend on the physico-chemical characteristics of the facets. In this study, CeO2 nanoparticles with different shapes were elaborated by hydrothermal synthesis. Nano-octahedra, nanocubes, or nanorods were selectively obtained under different conditions (temperature, concentration and nature of the precursors). The degradation activity according to the crystal faces was evaluated in vitro by measuring the degradation kinetics of paraoxon organophosphate in the presence of CeO2 nanoparticles. The results show an influence of both specific surface area and crystal faces of the nanoparticles, with higher activity for {111} facets compared to {100} facets at 32 °C. The relative activity between the facets is ascribed to the adsorption probability, assuming coordination between the phosphoryl oxygen and cerium atoms, but also to the surface density of the Ce doublets with relevant spacing for phosphatase mimetic activity.

Functionalized and grafted TiO2, CeO2, and SiO2 nanoparticles-ecotoxicity on Daphnia magna and relevance of ecofriendly polymeric networks.

Effects of functionalization and grafting of TiO2, CeO2, and SiO2 nanoparticles (NPs) were investigated, and toxicity of pristine, functionalized, and grafted NP towards Daphnia magna was measured. Surface functionalization of NP with amine groups decreased hydrophobicity of NP. When NPs were hydrophilic, they were less toxic than hydrophobic NP towards D. magna. Grafting agents influenced toxicity: no toxicity of NP was observed when bio-based and hydrogenated synthetic polymers were used, whereas perfluorinated polymers induced a higher toxicity.

Model-based optimization of parameters for degradation reaction of an organophosphorus pesticide, paraoxon, using CeO2 nanoparticles in water media.

Degradation and body surface decontamination is vital to prevent the skin penetration of paraoxon (POX), an organophosphorus pesticide, and victims poisoning. CeO2 demonstrated a good efficacy for the degradation of POX. The aim of the study was to develop a model which includes the impact of weight of CeO2, POX and diluent volumes on the degradation kinetics. The modelling was realized with rapid and simple experiments carried out in tubes, in aqueous diluent which contained ions in order to be in accordance with in vitro skin decontamination conditions. CeO2 had degraded from 5% (in case of 7.5mmol of POX per gram of CeO2) to 100% (0.002mmol of POX per gram of CeO2) of POX. Different kinetic models were tested. Using the particle aggregation kinetic model, the simulated and experimental data were in a good accordance. It highlighted the importance of particles aggregation due to salts and consistency of the mix on the degradation efficiency of CeO2. The model worked also really well to predict the degradation efficiency of CeO2 powders during in vitro skin experiments. However, it did not correctly forecast with an aqueous decontaminant, containing CeO2.

Barrier cream based on CeO2 nanoparticles grafted polymer as an active compound against the penetration of organophosphates.

Due to their small size, nanoparticles possess unique properties. Cerium oxide nanoparticles have been already studied for their capacity to adsorb and neutralize toxic compounds including organophosphates. By covalently grafting these nanoparticles to a thickening polymer, their potential aggregation resulting in a loss of surface area and their potential toxicity are avoided. Indeed, copolymers easily form gels in water at neutral pH thanks to low interactions occurring between polymeric chains; thus, gels can be spread on membrane supports to afford protective barriers. However, as we demonstrated previously, a formulation step of these hydride nanoparticle-polymeric compounds is necessary to overcome the cracking of the coating during drying. This work reports the impact of many factors on the efficiency of a new active Topical Skin Protectant (aTSP) including: (1) the presence of CeO2 nanoparticles in the protective coating and their amount, (2) their grafting to a perfluorocarbon thickening polymer and (3) the formulation of the CeO2 nanoparticle-grafted polymer. The combination of all the benefit parameters led to a very effective new aTSP against paraoxon penetration. The major in vitro diffusion studies were performed in Franz-type diffusion cells on two artificial membranes (silicone and Strat-M) and final validation on ex vivo human skin. The comparison of 24 h-exposure between membrane results indicated a difference in the behavior between the two artificial supports and the biological model; Strat-M membranes seeming closer to human skin results. Therefore, positive results regarding occlusive conditions should be confirmed with human skin.

In vitro skin decontamination of the organophosphorus pesticide Paraoxon with nanometric cerium oxide CeO2.

Organophosphorus compounds (OP), which mainly penetrate via the percutaneous pathway, represent a threat for both military and civilians. Body surface decontamination is vital to prevent victims poisoning. The development of a cost-effective formulation, which could be efficient and easy to handle in case of mass contamination, is therefore crucial. Metal oxides nanoparticles, due their large surface areas and the large amount of highly reactive sites, present high reactivity towards OP. First, this study aimed at evaluating the reaction of CeO2 nanoparticles, synthetized by microwave path and calcined at 500 or 600 °C, with Paraoxon (POX) in aqueous solution. Results showed that both nanoparticles degraded 60%-70% of POX. CeO2 calcined at 500 °C, owing to its larger specific area, was the most effective. Moreover, the degradation was significantly increased under Ultra-Violet irradiation (initial degradation rate doubled). Then, skin decontamination was studied in vitro using the Franz cell method with pig-ear skin samples. CeO2 powder and an aqueous suspension of CeO2 (CeO2-W) were applied 1 h after POX exposure. The efficiency of decontamination, including removal and/or degradation of POX, was compared to Fuller's earth (FE) and RSDL lotion which are, currently, the most efficient systems for skin decontamination. CeO2-W and RSDL were the most efficient to remove POX from the skin surface and decrease skin absorption by 6.4 compared to the control not decontaminated. FE reduced significantly (twice) the absorbed fraction of POX, contrarily to CeO2 powder. Considering only the degradation rate of POX, the products ranged in the order CeO2 > RSDL > CeO2-W > FE (no degradation). This study showed that CeO2 nanoparticles are a promising material for skin decontamination of OP if formulated as a dispersion able to remove POX like CeO2-W and to degrade it as CeO2 powder.

New CeO2 nanoparticles-based topical formulations for the skin protection against organophosphates.

To reinforce skin protection against organophosphates (OPs), the development of new topical skin protectants (TSP) has received a great interest. Nanoparticles like cerium dioxide (CeO2) known to adsorb and neutralize OPs are interesting candidates for TSP. However, NPs are difficult to disperse into formulations and they are suspected of toxicological issues. Thus, we want to study: (1) the effect of the addition of CeO2 NPs in formulations for the skin protection (2) the impact of the doping of CeO2 NPs by calcium; (3) the effect of two methods of dispersion of CeO2 NPs: an O/W emulsion or a suspension of a fluorinated thickening polymer (HASE-F) grafted with these NPs. As a screening approach we used silicone membranes as a skin equivalent and Franz diffusion cells for permeation tests. The addition of pure CeO2 NPs in both formulations permits the penetration to decrease by a 3-4-fold factor. The O/W emulsion allows is the best approach to obtain a film-forming coating with a good reproducibility of the penetration results; whereas the grafting of NPs to a thickener is the best way to obtain an efficient homogenous suspension of CeO2 NPs with a decreased of toxicological impact but the coating is less film-forming which slightly impacts the reproducibility of the penetration results.

Synthesis and characterization of Fe doped CeO2 nanoparticles for pigmented ultraviolet filter applications.

Iron doped CeO2 nanoparticles with doping concentrations between 0 and 30 mol% were synthesized by the co-precipitation method for potential application as a pigmented ultraviolet filtration material. Each sample was calcined in air and in argon. The iron solubility limit in the CeO2 lattice was found to be between 10 and 20 mol%. Raman spectroscopy results revealed that both iron doping and argon calcination increase the concentration of oxygen vacancies in the CeO2 lattice. Iron doping causes a blue-shift of the absorbance spectrum, which can be linked to the decreased crystallite size, as obtained by XRD peak broadening using the Scherrer formula. The undoped samples showed weak ferromagnetic behaviour whereas the doped samples were all paramagnetic.

Synthesis of nano-hematite for possible use in sunscreens.

Hematite nanoparticles were synthesized for ultraviolet filtration application by the precipitation method followed by calcination at different temperatures. A range of crystallite sizes between 37 and 85 nm (as determined by the Scherrer formula) was obtained, according to the temperature used for the calcination. An increase in the absorbance with increasing crystallite size was observed over the whole ultraviolet B and A range. The experimental band gap was 2.94 eV for the sample calcined at 500 degrees C and 3.08 eV for the sample calcined at 300 degrees C. The in vitro sun protection factor and protection factor-ultraviolet A of a water-in-oil emulsion made with the sample calcined at 500 degrees C as active ingredient were 9.21 and 8.81, respectively, which is higher than the protection factor-ultraviolet A values obtained for titanium dioxide and zinc oxide at the same mass concentration. The emulsion was found to be photostable.

Rapid electroplating of insulators.

Electrochemical techniques for depositing metal films and coatings have a long history. Such techniques essentially fall into two categories, with different advantages and disadvantages. The first, and oldest, makes use of spontaneous redox reactions to deposit a metal from solution, and can be used on both insulating and metallic substrates. But the deposition conditions of these processes are difficult to control in situ, in part because of the variety of salts and additives present in the solution. The second approach-electroplating-uses an electric current to reduce metal ions in solution, and offers control over the quantity (and, to some extent, grain size) of deposited metal. But application of this technique has hitherto been restricted to conducting substrates. Here we describe an electroplating technique that permits coating of insulating substrates with metals having controlled grain size, thickness and growth speed. The basis of our approach is the progressive outward growth of the metal from an electrode in contact with the substrate, with the cell geometry chosen so that the electron current providing the reduction passes through the growing deposit. Such an approach would normally form dendritic or powdery deposits, but we identify a range of conditions in which uniform films rapidly form.