Design of Fe3–xO4 raspberry decorated graphene nanocomposites with high performances in lithium-ion battery

Fe3–xO4 raspberry shaped nanostructures/graphene nanocomposites were synthesized by a one-step polyol-solvothermal method to be tested as electrode materials for Li-ion battery (LIB). Indeed, Fe3–xO4 raspberry shaped nanostructures consist of original oriented aggregates of Fe3–xO4 magnetite nanocrystals, ensuring a low oxidation state of magnetite and a hollow and porous structure, which has been easily combined with graphene sheets. The resulting nanocomposite powder displays a very homogeneous spatial distribution of Fe3–xO4 nanostructures at the surface of the graphene sheets. These original nanostructures and their strong interaction with the graphene sheets resulted in very small capacity fading upon Li+ ion intercalation. Reversible capacity, as high as 660 mAh/g, makes this material promising for anode in Li-ion batteries application

Metronidazole-functionalized iron oxide nanoparticles for molecular detection of hypoxic tissues

Being crucial under several pathological conditions, tumors, and tissue engineering, the MRI tracing of hypoxia within cells and tissues would be improved by the use of nanosystems allowing for direct recognition of low oxygenation and further treatment-oriented development. In the present study, we functionalized dendron-coated iron oxide nanoparticles (dendronized IONPs) with a bioreductive compound, a metronidazole-based ligand, to specifically detect the hypoxic tissues. Spherical IONPs with an average size of 10 nm were obtained and then decorated with the new metronidazole-conjugated dendron. The resulting nanoparticles (metro-NPs) displayed negligible effects on cell viability, proliferation, and metabolism, in both monolayer and 3D cell culture models, and a good colloidal stability in bio-mimicking media, as shown by DLS. Overtime quantitative monitoring of the IONP cell content revealed an enhanced intracellular retention of metro-NPs under anoxic conditions, confirmed by the in vitro MRI of cell pellets where a stronger negative contrast generation was observed in hypoxic primary stem cells and tumor cells after labeling with metro-NPs. Overall, these results suggest desirable properties in terms of interactions with the biological environment and capability of selective accumulation into the hypoxic tissue, and indicate that metro-NPs have considerable potential for the development of new nano-platforms especially in the field of anoxia-related diseases and tissue engineered models

Intracellular degradation of functionalized carbon nanotube/iron oxide hybrids is modulated by iron via Nrf2 pathway.

The in vivo fate and biodegradability of carbon nanotubes is still a matter of debate despite tremendous applications. In this paper we describe a molecular pathway by which macrophages degrade functionalized multi-walled carbon nanotubes (CNTs) designed for biomedical applications and containing, or not, iron oxide nanoparticles in their inner cavity. Electron microscopy and Raman spectroscopy show that intracellularly-induced structural damages appear more rapidly for iron-free CNTs in comparison to iron-loaded ones, suggesting a role of iron in the degradation mechanism. By comparing the molecular responses of macrophages derived from THP1 monocytes to both types of CNTs, we highlight a molecular mechanism regulated by Nrf2/Bach1 signaling pathways to induce CNT degradation via NOXjournal article2017 Jan 252017 01 25importe

Transformations in oxides induced by high-energy ball-milling.

International audienceThis paper, by no means exhaustive, focuses on high-energy ball-milling of oxides, on their mechanically induced changes and on the consequences of such changes on their physical and chemical properties. High-energy ball-milling offers a fortunate combination of technical simplicity and of complexity both of physical mechanisms which act during milling and of mechanosynthesized materials. Its basic interest, which stems from the large diversity of routes it offers to prepare oxides either directly or indirectly, is illustrated with various families of oxides. The direct path is to be favoured when as-milled oxides are of interest per se because of their nanocrystalline characteristics, their defects or their modified structures which result from mechanically driven phase transformations. The indirect path consists of a sequence of steps starting with mechanically activated oxides which may be subsequently just annealed or submitted to a combination of thermal treatments, with the possible occurrence of various chemical reactions, to prepare the sought-after materials with potential gains in processing temperatures and times. High energy ball-milling of oxides is more and more currently used to activate powders and to prepare nano-oxides at moderate temperatures. The interest of an activation step is well illustrated by the broad development of doped titania powders, synthesized by heat treatment of pre-ground reactants, for photocatalytic applications or to develop antibacterial materials. Another important class of applications of high-energy ball-milling is the formation of composites. It is exemplified here with the case of oxide-dispersed strengthened alloys whose properties are considerably improved by a dispersion of ultra-stable nanosized oxides whose formation mechanisms were recently described. The basic understanding of the mechanisms by which oxides or oxide mixtures evolve by high-energy ball-milling appears to be less advanced than it is for metallic materials essentially because of the overall complexity of the oxide structures, of their surfaces, of their defects and of their mechanical behavior

Serum Albumin Antifouling Effects of Hydroxypropylcellulose and Pluronic F127 Adsorbed on Isobutyramidegrafted Stellate Silica Nanoparticles

International audienceLimiting the serum protein fouling is a major challenge in the design of nanoparticles (NPs) for nanomedicine applications. Suitable chemical surface modification strategies allow to limit the interactions with adsorbing proteins. In this communication, we address the potential of isobutyramide (IBAM) groups grafted on stellate silica nanoparticles (STMS) for the immobilization of two biocompatible polymers renown for biomedical and low fouling applications: Hydroxypropylcellulose (HPC) and Pluronic F127 (PF127). We report that both polymers can be loaded on STMS@IBAM NPs surface with a maximum loading content close to 10 wt %. Regarding their antifouling properties, we report that the coatings of such HPC or PF127 polymers allow to reduce significantly the human serum albumin (HSA) adsorption in average by 70 % as compared to the surface of the free polymer STMS@IBAM. These results highlight the antifouling potential of these polymer pretreatments on IBAM-modified STMS NPs surface

A multiscale structural study of nanoparticle films prepared by the Langmuir-Blodgett technique

Équipe 401 : Nanomatériaux pour la vie et développement durableInternational audienceArrays of magnetic nanoparticles (NPs) represent a very interesting challenge toward the development of new devices for magnetic applications such as data storage and spintronic. The final properties of such assemblies depending essentially on the spatial arrangement of NPs, it is of first importance to investigate precisely their structure. Here, the structure of monolayer and multilayer films of magnetic iron oxide NPs assembled by the Langmuir-Blodgett (LB) technique has been studied by usual techniques such as SEM, AFM and ellipsometry and by a new and an easy to process enhanced optical technique: the Surface Enhancement Ellipsometry Contrast (SEEC) microscopy. This technique is based on the use of a new generation of microscope slides used as substrates which allow the strong enhancement of the sample contrast to a point where it becomes possible to visualize the structure of monolayer and multilayer films at the nanoscale with a conventional optical microscope. The SEEC microscopy is demonstrated to be complementary to usual characterization techniques to study the structure of NPs films, especially for films containing very small nanosized NPs which are more difficult to analyze by usual techniques. While the film structure is investigated with lateral resolution of microns, the layer thickness is analyzed at the nanoscale (with a precision of 0.3 nm) with a close fit to the experimental measurements on local (AFM) and on larger (ellipsometry) areas. This technique presents the advantage to visualize directly the topography of NPs assemblies on very large areas by extracting information such as the height profile, the film roughness and generating 3D images

Mechanically activated solid-state synthesis of hafnium carbide and hafnium nitride nanoparticles

International audienceNanocrystalline hafnium nitrides and hafnium carbides are synthesized, from powder mixtures based on partially hydrated hafnium tetrachloride, ph-HfCl4, and on magnesium, by a three-step process, namely a short mechanical activation step followed by a brief annealing step and a leaching step. Grinding of ph-HfCl4 + Mg leads to the formation of hafnium hydrides which decompose upon annealing in argon to give first metallic hafnium and then HfO2 at higher temperatures. Annealing of such ground ph-HfCl4 + Mg blends in flowing nitrogen yields HfN nanoparticles (average size between 10 and 30 nm). HfC carbides are directly mechanosynthesized from ph-HfCl4 + Mg + C powder mixtures. A subsequent heat treatment in flowing argon allows to better crystallize the grains of HfC (average size around 100 nm) and to decompose the intermediate products. The reaction mechanisms are discussed from results of thermogravimetric analyses and from infrared spectra of ph-HfCl4 + Mg based powder mixtures processed in various ways

Mechanically-activated solid-state synthesis of nanoparticles of HfB2, HfC and HfN from partially hydrated hafnium tetrachloride

International audienceNanocrystalline hafnium diboride, carbide and nitride are synthesised by a two-step process, namely a short mechanical activation step (∼1?2 h) of powder mixtures based on partially hydrated hafnium tetrachloride, ph-HfCl4, and on magnesium, followed by a brief annealing step (∼1 h) of the activated powders in flowing argon at 1100?C. HfCl4 is a by-product of the carbochlorination process of extraction of zirconium from ores. Magnesium has a strong reducing capacity and is insoluble in metallic hafnium. The unsought reaction products may then be eliminated during the additional heat treatment or by further leaching. Mechanically activated powder mixtures of ph-HfCl4 + B and of ph-HfCl4 + B + Mg yield either facetted grains or monocrystalline rods of HfB2 according to the composition of the initial mixtures and to the temperature and duration of the annealing treatment. The mean size of the facetted grains ranges between 100 nm and 300 nm. The growth direction of the rods is along the c-axis. Their mean diameters are around 100 nm and their mean lengths are in the range 500 nm?1 um. Hafnium carbide HfC is directly mechanosynthesised from ph-HfCl4 + Mg + C powder mixtures. A subsequent heat treatment in flowing argon allows to better crystallise the grains of HfC (∼100 nm) and to decompose the intermediate products. Annealing of ground ph-HfCl4 + Mg blends in flowing nitrogen for 1 h at 1100?C yields HfN nanoparticles whose size ranges between 10 nm and 30 nm. Characterisations of powders by X-ray diffraction, thermogravimetric analysis, scanning and transmission electron microscopy, Fourier Transform Infrared Spectroscopy were performed to follow the phase evolution and to clarify the reaction mechanisms

Simultaneous Monitoring of Outdoor PAHs and Particles in a French Peri-Urban Site during COVID Restrictions and the Winter Saharan Dust Event

International audienceThe presence of polycyclic aromatic hydrocarbons (PAHs) and particulate matter (PM) in air is known to provoke deleterious effects on human health. This work focused on the monitoring of PM and PAHs in the air over four weeks in a peri-urban site in Strasbourg (France), using a three-stage cascade impactor and a particle analyser allowing PM1, PM2.5 and PM10 discrimination. Meteorological conditions were monitored to study their influence on the pollutant levels. The average PM10 concentration of the cascade impactor and particle analyser varied from 11.8 to 80.2 µg/m3 and 10.6 to 220.2 µg/m3, respectively. The PAH total concentration ranged in 1.1–7.6 ng/m3 and a predominance of 5- and 6-ring PAHs was observed. PAHs were also more abundant in finer particles (PM1). Specifically, identified PAHs are traffic tracers suggesting that vehicular emission was one of its main sources. Two pollution episodes, associated with either a Saharan dust wind episode or traffic pollution, were observed, and led to PM10 and PM2.5 surpassing the daily limit values established by the European Union despite the traffic limitations according to the COVID restrictions. The total PAH concentrations were the highest during these periods suggesting PAHs might be bound to and transported via dust particles

Room Temperature Blocked Magnetic Nanoparticles Based on Ferrite Promoted by a Three-Step Thermal Decomposition Process

International audienceExchange coupled nanoparticles that combine hard and soft magnetic phases are very promising to enhance the effective magnetic anisotropy while preserving sizes below 20 nm. However, the core−shell structure is usually insufficient to produce rare earth-free ferro(i)-magnetic blocked nanoparticles at room temperature. We report on onion-type magnetic nanoparticles prepared by a three-step seed mediated growth based on the thermal decomposition method. The core@shell@shell structure consists of a core and an external shell of Fe 3−δ O 4 separated by an intermediate Co-doped ferrite shell. The double exchange coupling at both core@shell and shell@ shell interfaces results in such an increased of the magnetic anisotropy energy, that onion-type nanoparticles of 16 nm mainly based on iron oxide are blocked at room temperature. We envision that these results are very appealing for potential applications based on permanent magnets. H ard−soft coupled magnetic nanoparticles have gained a tremendous amount of interest during the past decade for short-term development of advanced applications related to spintronics (magnetoresistive sensors, magnetic recording, etc.). 1 Indeed, they are a potential alternative to produce permanent magnets 2 in order to circumvent supply storage caused by the critical need for rare earth elements in communications and mobility applications. With this purpose, the main goal is to overcome superparamagnetism, which results from size reduction to the nanoscale. 3 A very attractive approach is the design of core−shell nanoparticles that combine hard and soft magnetic phases in direct contact.