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.

Impact of airborne iron oxide nanoparticles on Tillandsia usneoides as a model plant to assess pollution in heavy traffic areas.

Due to the increasing evidence of widespread sub-micron pollutants in the atmosphere, the impact of airborne nanoparticles is a subject of great relevance. In particular, the smallest particles are considered the most active and dangerous, having a higher surface/volume ratio. Here we tested the effect of iron oxide (Fe3O4) nanoparticles (IONPs) with different mean diameter and size distribution on the model plant Tillandsia usneoides. Strands were placed in home-built closed boxes and exposed to levels of airborne IONPs reported for the roadside air, i.e. in the order of 107 - 108 items m-2. Plant growth and other morpho-physiological parameters were monitored for two weeks, showing that exposure to IONPs significantly reduced the length increment of the treated strands with respect to controls. A dose-dependence of this impairing effect was found only for particles with mean size of a few tens of nanometers. These were also proved to be the most toxic at the highest concentration tested. The IONP-induced hamper in growth was correlated with altered concentration of macro- and micronutrients in the plant, while no significant variation in photosynthetic activity was detected in treated samples. Microscopy investigation showed that IONPs could adhere to the plant surface and were preferentially located on the trichome wings. Our results report, for the first time, evidence of the negative effects of airborne IONP pollution on plant health, thus raising concerns about related environmental risks. Future research should be devoted to other plant species and pollutants to assess the impact of airborne pollution on plants and devise suitable attenuation practices.

Adsorption of Organic Dyes on Magnetic Iron Oxide Nanoparticles. Part I: Mechanisms and Adsorption-Induced Nanoparticle Agglomeration.

This series of two papers is devoted to the effect of organic dye (methylene blue, MB; or methyl orange, MO) adsorption on the surface of either bare or citrate-coated magnetic iron oxide nanoparticles (IONPs) on their primary agglomeration (in the absence of an applied magnetic field) and secondary field-induced agglomeration. The present paper (Part I) is focused on physicochemical mechanisms of dye adsorption and adsorption-induced primary agglomeration of IONPs. Dye adsorption to oppositely charged IONPs is found to be mostly promoted by electrostatic interactions and is very sensitive to pH and ionic strength variations. The shape of adsorption isotherms is correctly reproduced by the Langmuir law. For the particular MB/citrated IONP pair, the maximum surface density of adsorbed MB seems to correspond to the packing density of an adsorbed monolayer rather than to the surface density of the available adsorption sites. MB is shown to form H-aggregates on the surface of citrate-coated IONPs. The effective electric charge on the IONP surface remains nearly constant in a broad range of surface coverages by MB due to the combined action of counterion exchange and counterion condensation. Primary agglomeration of IONPs (revealed by an exponential increase of hydrodynamic size with surface coverage by MB) probably comes from correlation attractions or π-stacking aromatic interactions between adsorbed MB molecules or H-aggregates. From the application perspective, the maximum adsorption capacity is 139 ± 4 mg/g for the MB/citrated IONP pair (pH = 4-11) and 257 ± 16 mg/g for the MO/bare IONP pair (pH ∼ 4). Citrated IONPs have shown a good potential for their reusability in water treatment, with the adsorption efficiency remaining about 99% after nine adsorption/desorption cycles.

Interaction of fibrinogen-magnetic nanoparticle bioconjugates with integrin reconstituted into artificial membranes.

Magnetic nanoparticles have a broad spectrum of biomedical applications including cell separation, diagnostics and therapy. One key issue is little explored: how do the engineered nanoparticles interact with blood components after injection? The formation of bioconjugates in the bloodstream and subsequent reactions are potentially toxic due to the ability to induce an immune response. The understanding of the underlying processes is of major relevance to design not only efficient, but also safe nanoparticles for e.g. targeted drug delivery applications. In this study, we report on maghemite nanoparticles functionalized with citrate-, dextran- and polyethylene glycol coatings and their interaction with the clotting protein fibrinogen. Further, we investigate using biophysical tools (e.g. dynamic light scattering, circular dichroism spectroscopy and quartz crystal microbalance) the interaction of the magnetic nanoparticles-fibrinogen bioconjugates with artificial cell membranes as a model system for blood platelets. We found that fibrinogen corona formation provides colloidal stability to maghemite nanoparticles. In addition, bioconjugates of fibrinogen with dextran- and citrate-coated NPs interact with integrin-containing lipid bilayer, especially upon treatment with divalent ions, whereas PEG-coating reveals minor interaction. Our study at the interface of protein-conjugated nanoparticles and artificial cell membranes is essential for engineering safe nanoparticles for drug delivery applications.

Maghemite nanoparticles stabilize the protein corona formed with transferrin presenting different iron-saturation levels.

Magnetic nanoparticles are ideal candidates for biomedical applications given their potential use in magnetic resonance imaging, magnetic hyperthermia and targeted drug delivery. Understanding protein-nanoparticle interactions in the blood stream is of major importance due to their potential risks, especially immunogenicity (i.e. the ability to induce an immune response). Here, we report on the interaction of superparamagnetic maghemite (γ-Fe2O3) nanoparticles with human blood plasma protein transferrin presenting different iron-saturation levels: partially iron-saturated (i.e. transferrin) and iron-free transferrin (i.e. apotransferrin). The nanoparticle-protein interaction and the protein corona formation were studied using biophysical and chemical approaches based on dynamic light scattering, gel electrophoresis, circular dichroism spectroscopy and differential scanning fluorimetry. We found that iron content governs the protein corona formation and induces a strong effect on the thermal stability of the bound protein. Our results demonstrate a stabilizing effect of the nanoparticles with a change of the unfolding position of approximately 10 °C towards higher temperatures for transferrin. Our study may be relevant for the further development of magnetic nanoparticles as diagnostic and therapeutic tools.

Division of Ferrofluid Drops Induced by a Magnetic Field.

We report a comprehensive study of the division of ferrofluid drops caused by their interaction with a permanent magnet. As the magnet gradually approaches the sessile drop, the drop deforms into a spiked cone and then divides into two daughter droplets. This process is the result of a complex interplay between the polarizing effect caused by the magnetic field and the magnetic attraction due to the field gradient. As a first attempt to describe it, during each scan we identify two characteristic distances between the magnet and the drop: zmax, corresponding to the drop reaching its maximum height, and zsaddle, corresponding to the formation of a saddle point on the drop peak identifying the beginning of the drop breakup. We have investigated the location of these two points using sessile drops of ferrofluid water solutions at various concentrations and volumes, deposited on four surfaces of different wettability. An empirical scaling law based on dimensionless variables is found to accurately describe these experimental observations. We have also measured the maximum diameter of the drops right before the division and found that it is very close to a critical size, which depends on the magnetic attraction.

Static Magnetowetting of Ferrofluid Drops.

We report results of a comprehensive study of the wetting properties of sessile drops of ferrofluid water solutions at various concentrations deposited on flat substrates and subjected to the action of permanent magnets of different sizes and strengths. The amplitude and the gradient of the magnetic field experienced by the ferrofluid are changed by varying the magnets and their distance to the surface. Magnetic forces up to 100 times the gravitational one and magnetic gradients up to 1 T/cm are achieved. A rich phenomenology is observed, ranging from flattened drops caused by the magnetic attraction to drops extended normally to the substrate because of the normal traction of the magnetic field. We find that the former effect can be conveniently described in terms of an effective Bond number that compares the effective drop attraction with the capillary force, whereas the drop's vertical elongation is effectively expressed by a dimensionless number S, which compares the pressure jump at the ferrofluid interface because of the magnetization with the capillary pressure.

Influence of a cationic surfactant on adsorption of p-nitrophenol by a magsorbent based on magnetic alginate beads.

The paper focuses on the removal of p-nitrophenol by an adsorption process. A magnetic adsorbent was synthesized by encapsulation of magnetic functionalized nanoparticles using alginate as a green biopolymer matrix. A cationic surfactant, cetylpyridinium chloride (CPyCl), was used to confer a hydrophobic character to the magnetic beads and thus to promote their adsorption efficiency. The effect of different parameters such as initial concentrations of both PNP and CPyCl, contact time and solution pH value on the adsorption of PNP in the presence of CPyCl was investigated. It should be noted that combination of magnetic and adsorption properties in a same material is an interesting challenge which could overcome the recovery problems of pollutant-loaded adsorbent.

Adsorption of a cationic surfactant by a magsorbent based on magnetic alginate beads.

Adsorption of cetylpyridinium chloride (CPC), a cationic surfactant, by magnetic alginate beads (MagAlgbeads) was investigated. The magnetic adsorbent (called magsorbent) was prepared by encapsulation of magnetic functionalized nanoparticles in an alginate gel. The influence on CPC adsorption of several parameters such as contact time, pH and initial surfactant concentration was studied. The equilibrium isotherm shows that adsorption occurs through both electrostatic interactions with charge neutralization of the carboxylate groups of the beads and hydrophobic interactions inducing the formation of surfactant aggregates in the beads. The dosage of calcium ions released in the solution turns out to be a useful tool for understanding the adsorption mechanisms. Adsorption is accompanied by a shrinking of the beads that corresponds to a 45% reduction of the volume. Adsorption kinetic experiments show that equilibrium time is strongly dependent on the surfactant concentration, which monitors the nature of the interactions. On the other hand, since the pH affects the ionization state of adsorption sites, adsorption depends on the pH solution, maximum adsorption being obtained in a large pH range (3.2-12) in agreement with the pKa value of alginate (pKa=3.4-4.2). Finally, due to the formation of micelle-like surfactants aggregates in the magnetic alginate beads, they could be used as a new efficient magsorbent for hydrophobic pollutants.

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.

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.

Co(II) removal by magnetic alginate beads containing Cyanex 272.

In this study, a series of batch experiments is conducted to investigate the ability of magnetic alginate beads containing Cyanex 272 to remove Co(II) ions from aqueous solutions. Equilibrium sorption experiments show a Co(II) uptake capacity of 0.4 mmol g(-1). The data are successfully modelled with a Langmuir equation. A series of kinetics experiments is then carried out and a pseudo-second order equation is used to fit the experimental data. The effect of pH on the sorption of Co(II) ions is also investigated. Desorption experiments by elution of the loaded beads with nitric acid at pH 1 show that the magnetic alginate beads could be reused without significant losses of their initial properties even after 3 adsorption-desorption cycles.