Room-temperature-persistent magnetic interaction between coordination complexes and nanoparticles in maghemite-based nanohybrids.

Maghemite nanoparticles functionalised with Co(II) coordination complexes at their surface show a significant increase of their magnetic anisotropy, leading to a doubling of the blocking temperature and a sixfold increase of the coercive field. Magnetometric studies suggest an enhancement that is not related to surface disordering, and point to a molecular effect involving magnetic exchange interactions mediated by the oxygen atoms at the interface as its source. Field- and temperature-dependent X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) studies show that the magnetic anisotropy enhancement is not limited to surface atoms and involves the core of the nanoparticle. These studies also point to a mechanism driven by anisotropic exchange and confirm the strength of the magnetic exchange interactions. The coupling between the complex and the nanoparticle persists at room temperature. Simulations based on the XMCD data give an effective exchange field value through the oxido coordination bridge between the Co(II) complex and the nanoparticle that is comparable to the exchange field between iron ions in bulk maghemite. Further evidence of the effectiveness of the oxido coordination bridge in mediating the magnetic interaction at the interface is given with the Ni(II) analog to the Co(II) surface-functionalised nanoparticles. A substrate-induced magnetic response is observed for the Ni(II) complexes, up to room temperature.

Heterostructured Cobalt Silicide Nanocrystals: Synthesis in Molten Salts, Ferromagnetism, and Electrocatalysis.

Nanoscale heterostructures of covalent intermetallics should give birth to a wide range of interface-driven physical and chemical properties. Such a level of design however remains unattainable for most of these compounds, due to the difficulty to reach a crystalline order of covalent bonds at the moderate temperatures required for colloidal chemistry. Herein, we design heterostructured cobalt silicide nanoparticles to trigger magnetic and catalytic properties in silicon-based materials. Our strategy consists in controlling the diffusion of cobalt atoms into silicon nanoparticles, by reacting these particles in molten salts. By adjusting the temperature, we tune the conversion of the initial silicon particles toward homogeneous CoSi nanoparticles and core-shell nanoparticles made of a CoSi shell and a silicon-rich core. The increased interface-to-volume ratio of the CoSi component in the core-shell particles yields distinct properties compared to the bulk and homogeneous nanoparticles. First, the core-shell particles exhibit increased ferromagnetism, despite the bulk diamagnetic properties of cobalt monosilicide. Second, the core-shell nanoparticles act as efficient precatalysts for alkaline water oxidation, where the nanostructure is converted in situ into a layered cobalt silicon oxide/(oxy)hydroxide with high and stable oxygen evolution reaction (OER) electrocatalytic activity. This work demonstrates a route to design heterostructured nanocrystals of covalent intermetallic compounds and shows that these new structures exhibit very rich, yet poorly explored, interface-based physical properties and reactivity.

A natural experiment to assess how urban interventions in lower socioeconomic areas influence health behaviors: the UrbASanté study.

BACKGROUND: Mechanisms underlying the associations between changes in the urban environment and changes in health-related outcomes are complex and their study requires specific approaches. We describe the protocol of the interdisciplinary UrbASanté study, which aims to explore how urban interventions can modify environmental exposures (built, social, and food environments; air quality; noise), health-related behaviors, and self-reported health using a natural experiment approach. METHODS: The study is based on a natural experiment design using a before/after protocol with a control group to assess changes in environmental exposures, health-risk behaviors, and self-reported health outcomes of a resident adult population before and after the implementation of a time series of urban interventions in four contiguous neighborhoods in Paris (France). The changes in environmental exposures, health-related behaviors, and self-reported health outcomes of a resident adult population will be concurrently monitored in both intervention and control areas. We will develop a mixed-method framework combining substantial fieldwork with quantitative and qualitative analytical approaches. This study will make use of (i) data relating to exposures and health-related outcomes among all participants and in subsamples and (ii) interviews with residents regarding their perceptions of their neighborhoods and with key stakeholders regarding the urban change processing, and (iii) existing geodatabases and field observations to characterize the built, social, and food environments. The data collected will be analyzed with a focus on interrelationships between environmental exposures and health-related outcomes using appropriate approaches (e.g., interrupted time series, difference-in-differences method). DISCUSSION: Relying on a natural experiment approach, the research will provide new insights regarding issues such as close collaboration with urban/local stakeholders, recruitment and follow-up of participants, identification of control and intervention areas, timing of the planned urban interventions, and comparison of subjective and objective measurements. Through the collaborative work of a consortium ensuring complementarity between researchers from different disciplines and stakeholders, the UrbASanté study will provide evidence-based guidance for designing future urban planning and public health policies. TRIAL REGISTRATION: This research was registered at the ClinicalTrial.gov (NCT05743257).

Magnetic Hyperthermia on γ-Fe2O3@SiO2 Core-Shell Nanoparticles for mi-RNA 122 Detection.

Magnetic hyperthermia on core-shell nanoparticles bears promising achievements, especially in biomedical applications. Here, thanks to magnetic hyperthermia, γ-Fe2O3 cores are able to release a DNA target mimicking the liver specific oncotarget miRNA-122. Our silica coated magnetic nanoparticles not only allow the grafting at their surface of a significant number of oligonucleotides but are also shown to be as efficient, by local heating, as 95 °C global heating when submitted to an alternative magnetic field, while keeping the solution at 28 °C, crucial for biological media and energy efficiency. Moreover, a slight modification of the silica coating process revealed an increased heating power, well adapted for the release of small oligonucleotides such as microRNA.

Bad neighbour, good neighbour: how magnetic dipole interactions between soft and hard ferrimagnetic nanoparticles affect macroscopic magnetic properties in ferrofluids.

Fluids responding to magnetic fields (ferrofluids) offer a scene with no equivalent in nature to explore long-range magnetic dipole interactions. Here, we studied the very original class of binary ferrofluids, embedding soft and hard ferrimagnetic nanoparticles. We used a combination of X-ray magnetic spectroscopy measurements supported by multi-scale experimental techniques and Monte-Carlo simulations to unveil the origin of the emergent macroscopic magnetic properties of the binary mixture. We found that the association of soft and hard magnetic nanoparticles in the fluid has a considerable influence on their inherent magnetic properties. While the ferrofluid remains in a single phase, magnetic interactions at the nanoscale between both types of particles induce a modification of their respective coercive fields. By connecting the microscopic properties of binary ferrofluids containing small particles, our findings lay the groundwork for the manipulation of magnetic interactions between particles at the nanometer scale in magnetic liquids.

Release and Detection of microRNA by Combining Magnetic Hyperthermia and Electrochemistry Modules on a Microfluidic Chip.

The heating of a biologic solution is a crucial part in an amplification process such as the catalytic detection of a biological target. However, in many situations, heating must be limited in microfluidic devices, as high temperatures can cause the denaturation of the chip components. Local heating through magnetic hyperthermia on magnetic nano-objects has opened the doors to numerous improvements, such as for oncology where a reduced heating allows the synergy of chemotherapy and thermotherapy. Here we report on the design and implementation of a lab on chip without global heating of samples. It takes advantage of the extreme efficiency of DNA-modified superparamagnetic core-shell nanoparticles to capture complementary sequences (microRNA-target), uses magnetic hyperthermia to locally release these targets, and detects them through electrochemical techniques using ultra-sensitive channel DNA-modified ultramicroelectrodes. The combination of magnetic hyperthermia and microfluidics coupled with on-chip electrochemistry opens the way to a drastic reduction in the time devoted to the steps of extraction, amplification and nucleic acids detection. The originality comes from the design and microfabrication of the microfluidic chip suitable to its insertion in the millimetric gap of toric inductance with a ferrite core.

Heteropolytungstate-decorated core-shell magnetic nanoparticles: A covalent strategy for polyoxometalate-based hybrid nanomaterials.

Amino-functionalized core-shell magnetic nanoparticles have been covalently grafted with Polyoxometalates (POMs). These multifunctional nanocomposites have been obtained through the coupling of heteropolytungstate-based hybrids bearing carboxylic acid functions with aminopropyl functions that decorate the core-shell nanoparticles. The physical properties of the resulting materials have been studied by a large set of techniques. The very good nanostructuration of the POMs at the surface of the obtained nanoparticles have thus been directly observed by high-resolution transmission electronic microscopy (HR-TEM). Furthermore, the hyperthermia properties of these nanocomposites have been also considered as a function of the size of the magnetic core. Finally, the stability of these suspensions in organic media makes them particularly interesting in the frame of their processing or their potential use as nanocatalysts.

Oriented Gold Nanorods and Gold Nanorod Chains within Smectic Liquid Crystal Topological Defects.

We show that the use of oriented linear arrays of smectic A defects, the so-called smectic oily streaks, enables the orientation of gold nanorods (GNRs) for a large range of GNR diameters, ranging from 7 to 48 nm, and for various ligands. For the small GNRs it enables oriented end-to-end small chains of GNRs when the density is increased from around 2 GNRs/µm2 to around 6 GNRs/µm2. We have characterized the orientation of single GNRs by spectrophotometry and two-photon luminescence (TPL). A strongly anisotropic absorption of the composites and an on-off switching of GNR luminescence, both controlled by incident light polarization, are observed, revealing an orientation of the GNRs mostly parallel to the oily streaks. A more favorable trapping of GNRs by smectic dislocations with respect to ribbon-like defects is thus demonstrated. The dislocations appear to be localized at a specific localization, namely, the summit of rotating grain boundaries. Combining plasmonic absorption measurements, TPL measurements, and simulation of the plasmonic absorption, we show that the end-to-end GNR chains are both dimers and trimers, all parallel to each other, with a small gap between the coupled GNRs, on the order of 1.5 nm, thus associated with a large red-shift of 110 nm of the longitudinal plasmonic mode. A motion of the GNRs along the dislocations appears as a necessary ingredient for the formation of end-to-end GNR chains, the gap value being driven by the balance between the attracting van der Waals interactions and the steric repulsion between the GNRs and leading to interdigitation of the neighboring ligands. We thus obtain electromagnetic coupling of nanorods controlled by light polarization.

Influence of a dispersion of magnetic and nonmagnetic nanoparticles on the magnetic Fredericksz transition of the liquid crystal 5CB.

A long time ago, Brochard and de Gennes predicted the possibility of significantly decreasing the critical magnetic field of the Fredericksz transition (the magnetic Fredericksz threshold) in a mixture of nematic liquid crystals and ferromagnetic particles, the so-called ferronematics. This phenomenon is rarely measured to be large, due to soft homeotropic anchoring induced at the nanoparticle surface. Here we present an optical study of the magnetic Fredericksz transition combined with a light scattering study of the classical nematic liquid crystal: the pentylcyanobiphenyl (5CB), doped with 6 nm diameter magnetic and nonmagnetic nanoparticles. Surprisingly, for both nanoparticles, we observe at room temperature a net decrease of the threshold field of the Fredericksz transition at low nanoparticle concentrations, which appears associated with a coating of the nanoparticles by a brush of polydimethylsiloxane copolymer chains inducing planar anchoring of the director on the nanoparticle surface. Moreover, the magnetic Fredericksz threshold exhibits nonmonotonic behavior as a function of the nanoparticle concentration for both types of nanoparticles, first decreasing down to a value from 23% to 31% below that of pure 5CB, then increasing with a further increase of nanoparticle concentration. This is interpreted as an aggregation starting at around 0.02 weight fraction that consumes more isolated nanoparticles than those introduced when the concentration is increased above c=0.05 weight fraction (volume fraction 3.5×10^{-2}). This shows the larger effect of isolated nanoparticles on the threshold with respect to aggregates. From dynamic light scattering measurements we deduced that, if the decrease of the magnetic threshold when the nanoparticle concentration increases is similar for both kinds of nanoparticles, the origin of this decrease is different for magnetic and nonmagnetic nanoparticles. For nonmagnetic nanoparticles, the behavior may be associated with a decrease of the elastic constant due to weak planar anchoring. For magnetic nanoparticles there are non-negligible local magnetic interactions between liquid crystal molecules and magnetic nanoparticles, leading to an increase of the average order parameter. This magnetic interaction thus favors an easier liquid crystal director rotation in the presence of external magnetic field, able to reorient the magnetic moments of the nanoparticles along with the molecules.

New approach for understanding experimental NMR relaxivity properties of magnetic nanoparticles: focus on cobalt ferrite.

Relaxivities r1 and r2 of cobalt ferrite magnetic nanoparticles (MNPs) have been investigated in the aim of improving the models of NMR relaxation induced by magnetic nanoparticles. On one hand a large set of relaxivity data has been collected for cobalt ferrite MNP dispersions. On the other hand the relaxivity has been calculated for dispersions of cobalt ferrite MNPs with size ranging from 5 to 13 nm, without using any fitting procedure. The model is based on the magnetic dipolar interaction between the magnetic moments of the MNPs and the 1H nuclei. It takes into account both the longitudinal and transversal contributions of the magnetic moments of MNPs leading to three contributions in the relaxation equations. The comparison of the experimental and theoretical data shows a good agreement of the NMR profiles as well as the temperature dependence.

Enhancing the magnetic anisotropy of maghemite nanoparticles via the surface coordination of molecular complexes.

Superparamagnetic nanoparticles are promising objects for data storage or medical applications. In the smallest--and more attractive--systems, the properties are governed by the magnetic anisotropy. Here we report a molecule-based synthetic strategy to enhance this anisotropy in sub-10-nm nanoparticles. It consists of the fabrication of composite materials where anisotropic molecular complexes are coordinated to the surface of the nanoparticles. Reacting 5 nm γ-Fe2O3 nanoparticles with the [Co(II)(TPMA)Cl2] complex (TPMA: tris(2-pyridylmethyl)amine) leads to the desired composite materials and the characterization of the functionalized nanoparticles evidences the successful coordination--without nanoparticle aggregation and without complex dissociation--of the molecular complexes to the nanoparticles surface. Magnetic measurements indicate the significant enhancement of the anisotropy in the final objects. Indeed, the functionalized nanoparticles show a threefold increase of the blocking temperature and a coercive field increased by one order of magnitude.

Controlling nanoparticles dispersion in ionic liquids by tuning the pH.

HYPOTHESIS: Getting colloidally stable dispersions of nanoparticles in ionic liquids is a challenging task. Indeed, long-range electrostatic repulsions often involved in molecular solvents are screened in ionic liquids and cannot counterbalance the interparticle attractions. Using a polyelectrolyte coating should provide a good stabilisation of the nanoparticles. Investigating the role of the polyelectrolyte charge on the dispersion state should yield to a better comprehension of the stabilisation mechanisms. EXPERIMENTS: Polyacrylate coated maghemite nanoparticles were transferred from water to ethylammonium nitrate, a protic ionic liquid, for various polymer chain length and nanoparticles size. Titrations of coated nanoparticles and of free polymer chains were performed in water and in ethylammonium nitrate. The dispersion state of the nanoparticles was monitored at different pH by small-angle X-ray scattering. FINDINGS: Polyacrylate coating stabilised the nanoparticles in ethylammonium nitrate. However, reversible aggregation with the pH was observed. Surprisingly, this control was not directly related to the surface charge like in water but to the solvent quality for the polyelectrolyte. This study is the first report on the use of the pH to tune the dispersion state of nanoparticles in an ionic liquid. It provides a better understanding of the mechanisms responsible for colloidal stability in ionic liquids.

Synthesis of Trimagnetic Multishell MnFe2 O4 @CoFe2 O4 @NiFe2 O4 Nanoparticles.

The synthesis and characterization of original ferrite multishell magnetic nanoparticles made of a soft core (manganese ferrite) covered with two successive shells, a hard one (cobalt ferrite) and then a soft one (nickel ferrite), are described. The results demonstrate the modulation of the coercivity when new magnetic shells are added.

Preparation of highly anisotropic cobalt ferrite/silica microellipsoids using an external magnetic field.

Magnetic cobalt ferrite/silica microparticles having both an original morphology and an anisotropic nanostructure are synthesized through the use of an external magnetic field and nanoparticles characterized by a high magnetic anisotropy. The association of these two factors implies that the ESE (emulsion and solvent evaporation) sol-gel method employed here allows the preparation of silica microellipsoids containing magnetic nanoparticles aggregated in large chains. It is clearly shown that without this combination, microspheres characterized by an isotropic distribution of the magnetic nanoparticles are obtained. While the chaining of the cobalt ferrite nanoparticles inside the silica matrix is related to the increase of their magnetic dipolar interactions, the ellipsoidal shape of the microparticles may be explained by the elongation of the sol droplets in the direction of the external magnetic field during the synthesis. Because of their highly anisotropic structure, these microparticles exhibit permanent magnetic moments, which are responsible, at a larger scale, for the existence of strong magnetic dipolar interactions. Therefore, when they are dispersed in water, the microellipsoids self-assemble into large and irregular chains. These interactions can be reinforced by the use of external magnetic field, allowing the preparation of very large permanent chains. This research illustrates how nanostructured particles exhibiting complex architectures can be elaborated through simple, fast, and low-cost methods, such as the use of external fields in combination with soft chemistry.

Chitosan/maghemite composite: a magsorbent for the adsorption of methyl orange.

In this study, magnetic beads were prepared by encapsulation of magnetic nanoparticles in epichlorohydrin cross-linked chitosan beads. Their adsorption characteristics were assessed by using methyl orange (MO) as an adsorbate. MO adsorption onto chitosan beads was found to be optimal in the pH range of 3-5. The adsorption isotherm was well described by the Langmuir model and showed high MO adsorption capacity (2.38 mmol/g, i.e. 779 mg/g). MO adsorption kinetics followed a pseudo-second-order kinetic model, indicating that adsorption was the rate-limiting step. At 0.305 mmol/L, only 19 min was required to reach 90% adsorption and 50% of the MO was adsorbed in 2 min. Desorption studies of MO using NaOH showed the reusability of the magsorbent. No release of iron species was observed at pH>2.4.

Ultra magnetic liposomes for MR imaging, targeting, and hyperthermia.

Magnetic liposomes offer opportunities as theranostic systems. The prerequisite for efficient imaging, tissue targeting or hyperthermia is high magnetic load of these vesicles. Here we describe the preparation of Ultra Magnetic Liposomes (UMLs), which may encapsulate iron oxide nanoparticles in a volume fraction of up to 30%. This remarkable magnetic charge provides UMLs with high magnetic mobilities, MRI relaxivities, and heating capacities for magnetic hyperthermia. Moreover, these UMLs are rapidly and efficiently internalized by cultured tumor cells and, when they are administered to mice, they can be vectorized to tumors by an external magnet.

An eco-friendly route to magnetic silica microspheres and nanospheres.

A green and inexpensive alternative to existing methods for the preparation of magnetic iron oxide/silica nanocomposite particles has been investigated. The use of water-in oil emulsions based on vegetable oils instead of usual solvents led to microsized or nanosized magnetic silica spheres exhibiting similar characteristics to those of classical procedures. Furthermore this approach is very general since a large class of porous magnetic colloids differing in size or iron oxide fraction has been obtained. This work emphasizes the importance of the level of the shearing during the emulsification step with regard to the size and monodispersity of the prepared beads. All the materials prepared were fully characterized (SEM and TEM microscopies, SQUID magnetometry, N(2) sorption volumetry, etc.). In addition, samples functionalized by thiol groups have been synthesized and successfully tested for the removal of heavy metals in water-treatment.

Magnetic alginate beads for Pb(II) ions removal from wastewater.

A magnetic adsorbent (called magsorbent) was developed by encapsulation of magnetic functionalized nanoparticles in calcium-alginate beads. The adsorption of Pb(II) ions by these magnetic beads was studied and the effect of different parameters, such as initial concentration, contact time and solution pH value on the adsorption of Pb(II) ions was investigated. Our magsorbent was found to be efficient to adsorb Pb(II) ions and maximal adsorption capacity occurred at pH 2.3-6. The classical Langmuir model used to fit the experimental adsorption data showed a maximum sorption capacity close to 100 mg g(-1). The experimental kinetic data were well correlated with a pseudo second-order model, 50% of the Pb(II) ions were removed within 20 min and the equilibrium was attained around 100 min. Moreover our magsorbent was easily collected from aqueous media by using an external magnetic field. These results permitted to conclude that magnetic alginate beads could be efficiently used to remove heavy metals in a water treatment process.

Experimental evidence for violation of the fluctuation-dissipation theorem in a superspin glass.

We present the experimental observation of the fluctuation-dissipation theorem violation in an assembly of interacting magnetic nanoparticles in the low temperature superspin-glass phase. The magnetic noise is measured with a two-dimension electron gas Hall probe and compared to the out of phase ac susceptibility of the same ferrofluid. For "intermediate" aging times of the order of 1 h, the ratio of the effective temperature T(eff) to the bath temperature T grows from 1 to 6.5 when T is lowered from T(g) to 0.3 T(g), regardless of the noise frequency. These values are comparable to those measured in an atomic spin glass as well as those calculated for a Heisenberg spin glass.

Doxorubicin loaded magnetic polymersomes: theranostic nanocarriers for MR imaging and magneto-chemotherapy.

Hydrophobically modified maghemite (γ-Fe(2)O(3)) nanoparticles were encapsulated within the membrane of poly(trimethylene carbonate)-b-poly(l-glutamic acid) (PTMC-b-PGA) block copolymer vesicles using a nanoprecipitation process. This formation method gives simple access to highly magnetic nanoparticles (MNPs) (loaded up to 70 wt %) together with good control over the vesicles size (100-400 nm). The simultaneous loading of maghemite nanoparticles and doxorubicin was also achieved by nanoprecipitation. The deformation of the vesicle membrane under an applied magnetic field has been evidenced by small angle neutron scattering. These superparamagnetic hybrid self-assemblies display enhanced contrast properties that open potential applications for magnetic resonance imaging. They can also be guided in a magnetic field gradient. The feasibility of controlled drug release by radio frequency magnetic hyperthermia was demonstrated in the case of encapsulated doxorubicin molecules, showing the viability of the concept of magneto-chemotherapy. These magnetic polymersomes can be used as efficient multifunctional nanocarriers for combined therapy and imaging.