Dimpled SiO₂@γ-Fe₂O₃ nanocomposites – fabrication and use for arsenic adsorption in aqueous medium

We report the synthesis of nanocomposites made of silica nanoparticles whose six surface dimples are decorated with magnetic maghemite nanoparticles and their use for detection and recovery of arsenic in aqueous media. Precursor silica nanoparticles have aminated polystyrene chains at the bottom of their dimples and the maghemite nanoparticles are surface functionalized with carboxylic acid groups in two steps: amination with 3-aminopropyltrimethoxysilane, then derivatization with succinic anhydride in the presence of triethylamine. In the end, the colloidal assembly consists of the regioselective grafting of the carboxylic acid-modified iron oxide nanoparticles onto the 6-dimple silica nanoparticles. Several characterization techniques such as transmission electron microscopy (TEM), Fourier-transform infrared spectroscopy (FTIR), dynamic light scattering (DLS) are employed to assess the grafting process and study the influence of the maghemite functional groups on the quality of the composites formed. The resulting magnetic nanocomposites are used for the environmentally benign detection and removal of arsenic from aqueous medium, being readily extracted through means of magnetic separation

Conditions determining the morphology and nanoscale magnetism of Co nanoparticles: Experimental and numerical studies

Co-based nanostructures ranging from core-shell to hollow nanoparticles were produced by varying the reaction time and the chemical environment during the thermal decomposition of Co2(CO)8. Both structural characterization and kinetic model simulation illustrate that the diffusivities of Co and oxygen determine the growth ratio and the final morphology of the nanoparticles. Exchange coupling between Co and Co-oxide in core/shell nanoparticles induced a shift of field-cooled hysteresis loops that is proportional to the shell thickness, as verified by numerical studies. The increased nanocomplexity when going from core/shell to hollow particles, also leads to the appearance of hysteresis above 300 K due to an enhancement of the surface anisotropy resulting from the additional spin-disordered surfaces.Comment: 29 pages including 11 figures embedded. Submitted to Phys. Rev.

Enhanced biomedical heat-triggered carriers via nanomagnetism tuning in ferrite-based nanoparticles

Biomedical nanomagnetic carriers are getting a higher impact in therapy and diagnosis schemes while their constraints and prerequisites are more and more successfully confronted. Such particles should possess a well-defined size with minimum agglomeration and they should be synthesized in a facile and reproducible high-yield way together with a controllable response to an applied static or dynamic field tailored for the specific application. Here, we attempt to enhance the heating efficiency in magnetic particle hyperthermia treatment through the proper adjustment of the core–shell morphology in ferrite particles, by controlling exchange and dipolar magnetic interactions at the nanoscale. Thus, core–shell nanoparticles with mutual coupling of magnetically hard (CoFe2O4) and soft (MnFe2O4) components are synthesized with facile synthetic controls resulting in uniform size and shell thickness as evidenced by high resolution transmission electron microscopy imaging, excellent crystallinity and size monodispersity. Such a magnetic coupling enables the fine tuning of magnetic anisotropy and magnetic interactions without sparing the good structural, chemical and colloidal stability. Consequently, the magnetic heating efficiency of CoFe2O4 and MnFe2O4 core–shell nanoparticles is distinctively different from that of their counterparts, even though all these nanocrystals were synthesized under similar conditions. For better understanding of the AC magnetic hyperthermia response and its correlation with magnetic-origin features we study the effect of the volume ratio of magnetic hard and soft phases in the bimagnetic core−shell nanocrystals. Eventually, such particles may be considered as novel heating carriers that under further biomedical functionalization may become adaptable multifunctional heat-triggered nanoplatforms

Controlling Magnetization Reversal and Hyperthermia Efficiency in Core-Shell Iron-Iron Oxide Magnetic Nanoparticles by Tuning the Interphase Coupling

Magnetic particle hyperthermia, in which colloidal nanostructures are exposed to an alternating magnetic field, is a promising approach to cancer therapy. Unfortunately, the clinical efficacy of hyperthermia has not yet been optimized. Consequently, routes to improve magnetic particle hyperthermia, such as designing hybrid structures comprised of different phase materials, are actively pursued. Here, we demonstrate enhanced hyperthermia efficiency in relatively large spherical Fe/Fe-oxide core-shell nanoparticles through the manipulation of interactions between the core and shell phases. Experimental results on representative samples with diameters in the range 30-80 nm indicate a direct correlation of hysteresis losses to the observed heating with a maximum efficiency of around 0.9 kW/g. The absolute particle size, the core-shell ratio, and the interposition of a thin wüstite interlayer are shown to have powerful effects on the specific absorption rate. By comparing our measurements to micromagnetic calculations, we have unveiled the occurrence of topologically nontrivial magnetization reversal modes under which interparticle interactions become negligible, aggregates formation is minimized and the energy that is converted into heat is increased. This information has been overlooked until date and is in stark contrast to the existing knowledge on homogeneous particles

How size, shape and assembly of magnetic nanoparticles give rise to different hyperthermia scenarios

The use of magnetic nanoparticles (MNPs) to locally increase the temperature at the nanoscale under the remote application of alternating magnetic fields (magnetic particle hyperthermia, MHT) has become an important subject of nanomedicine multidisciplinary research, focusing among other topics on the optimization of the heating performance of MNPs and their assemblies under the effect of the magnetic field. We report experimental data of heat released by MNPs using a wide range of anisometric shapes and their assemblies in different media. We outline a basic theoretical investigation, which assists the interpretation of the experimental data, including the effect of the size, shape and assembly of MNPs on the MNPs' hysteresis loops and the maximum heat delivered. We report heat release data of anisometric MNPs, including nanodisks, spindles (elongated nanoparticles) and nanocubes, analysing, for a given shape, the size dependence. We study the MNPs either acting as individuals or assembled through a magnetic-field-assisted method. Thus, the physical geometrical arrangement of these anisometric particles, the magnetization switching and the heat release (by means of the determination of the specific adsorption rate, SAR values) under the application of AC fields have been analysed and compared in aqueous suspensions and after immobilization in agar matrix mimicking the tumour environment. The different nano-systems were analysed when dispersed at random or in assembled configurations. We report a systematic fall in the SAR for all anisometric MNPs randomly embedded in a viscous environment. However, certain anisometric shapes will have a less marked, an almost total preservation or even an increase in SAR when embedded in a viscous environment with certain orientation, in contrast to the measurements in water solution. Discrepancies between theoretical and experimental values reflect the complexity of the systems due to the interplay of different factors such as size, shape and nanoparticle assembly due to magnetic interactions. We demonstrate that magnetic assembly holds great potential for producing materials with high functional and structural diversity, as we transform our nanoscale building blocks (anisometric MNPs) into a material displaying enhanced SAR properties

Learning form Nature to improve the heat generation of iron-oxide nanoparticles for magnetic hyperthermia applications.

The performance of magnetic nanoparticles is intimately entwined with their structure, mean size and magnetic anisotropy. Besides, ensembles offer a unique way of engineering the magnetic response by modifying the strength of the dipolar interactions between particles. Here we report on an experimental and theoretical analysis of magnetic hyperthermia, a rapidly developing technique in medical research and oncology. Experimentally, we demonstrate that single-domain cubic iron oxide particles resembling bacterial magnetosomes have superior magnetic heating efficiency compared to spherical particles of similar sizes. Monte Carlo simulations at the atomic level corroborate the larger anisotropy of the cubic particles in comparison with the spherical ones, thus evidencing the beneficial role of surface anisotropy in the improved heating power. Moreover we establish a quantitative link between the particle assembling, the interactions and the heating properties. This knowledge opens new perspectives for improved hyperthermia, an alternative to conventional cancer therapies