L-Lysine-Coated Magnetic Core-Shell Nanoparticles for the Removal of Acetylsalicylic Acid from Aqueous Solutions.

Nanotechnologies based on magnetic materials have been successfully used as efficient and reusable strategies to remove pharmaceutical residuals from water. This paper focuses on the fabrication, characterization, and application of ferrite-based magnetic nanoparticles functionalized with L-lysine as potential nanoadsorbents to remove acetylsalicylic acid (ASA) from water. The proposed nanomaterials are composed of highly magnetic and chemically stable core-shell nanoparticles covered with an adsorptive layer of L-lysine (CoFe2O4-γ-Fe2O3-Lys). The nanoadsorbents were elaborated using the coprecipitation method in an alkaline medium, leading to nanoparticles with two different mean sizes (13.5 nm and 8.5 nm). The samples were characterized by XRD, TEM, FTIR, XPS, Zetametry, BET, and SQUID magnetometry. The influence of time, pH, and pollutant concentration was evaluated from batch studies using 1.33 g/L of the nanoadsorbents. The Freundlich isotherm best adjusted the adsorption data. The adsorption process exhibited a pseudo-second-order kinetic behavior. The optimal pH for adsorption was around 4-6, with a maximum adsorption capacity of 16.4 mg/g after 150 min of contact time. Regeneration tests also showed that the proposed nanomaterials are reusable. The set of results proved that the nanoadsorbents can be potentially used to remove ASA from water and provide relevant information for their application in large-scale designs.

A numerical study on the interplay between the intra-particle and interparticle characteristics in bimagnetic soft/soft and hard/soft ultrasmall nanoparticle assemblies.

A mesoscopic scale approach and the Monte Carlo (MC) method have been employed to study the exchange bias behaviour of MnFe2O4 (soft)/maghemite (soft) and CoFe2O4 (hard)/maghemite (soft) nanoparticles (NPs) of size ∼ 3 nm in dense and diluted assemblies at low temperatures. The analysis of our MC results clearly shows that in the powder samples the contribution to the exchange bias field (H ex) and the coercivity (H c) comes mainly from the intraparticle core/shell structure in the hard/soft sample and that the interplay between the internal characteristics and the interparticle interactions is more important in the soft/soft samples where the dipolar strength is enhanced. In the diluted frozen ferrofluid samples where interparticle exchange interactions are absent and the role of the dipolar interactions is not significant the exchange bias effects are reduced, and they come from the intra particle structure. The variation of H ex and H c with the applied cooling field well reproduces the experimental findings and sheds light on the key mechanisms of the observed magnetic behaviour. Our results demonstrate the possibility to control the magnetic behaviour of nanostructures by using properly chosen core/shell bimagnetic nanoparticles.

Hybrid magnetic CoFe2O4@γ-Fe2O3@CTAB nanocomposites as efficient and reusable adsorbents for Remazol Brilliant Blue R dye.

The main goal of the present survey was to elaborate, characterize and evaluate the efficiency of ferrite-based nanoparticles modified with cetyltrimethylammonium bromide (CTAB) as potential magnetic nanoadsorbents to remove Remazol Brilliant Blue R (RBBR) from water. It is proposed an innovative nanomaterial architecture based on highly magnetic and chemically stable core@shell nanoparticles covered by an adsorptive surface layer of CTAB (CoFe2O4@γ-Fe2O3@CTAB). Samples of two different mean sizes (7.5 and 14.6 nm) were synthesized using a hydrothermal coprecipitation followed by surface treatment and functionalization. Batch tests were performed to evaluate the influence of contact time, temperature, pH, shaking rate, presence of interferents and mean size on the performance of the proposed nanomaterials. The kinetics of the adsorption process followed the pseudo-second-order model with an equilibrium time of 20 min. The adsorption capacity was estimated by the Langmuir isotherm model and was found to be 56.3 mg/g (smaller size) and 45.6 mg/g (larger size) at pH = 3 and a shaking rate of 400 rpm. The process was spontaneous, exothermic, and showed increased randomness. Sulphate ions negatively impacted the removal of RBBR. The best performance of the nanoadsorbent based on smaller mean sizes can be correlated to its larger surface area. Regeneration and readsorption tests showed that the nanoadsorbents retain more than 80% of their original removal capacity, therefore they can be effectively recycled and reused.

Colloidal Stability and Concentration Effects on Nanoparticle Heat Delivery for Magnetic Fluid Hyperthermia.

The heat produced by magnetic nanoparticles, when they are submitted to a time-varying magnetic field, has been used in many auspicious biotechnological applications. In the search for better performance in terms of the specific power absorption (SPA) index, researchers have studied the influence of the chemical composition, size and dispersion, shape, and exchange stiffness in morphochemical structures. Monodisperse assemblies of magnetic nanoparticles have been produced using elaborate synthetic procedures, where the product is generally dispersed in organic solvents. However, the colloidal stability of these rough dispersions has not received much attention in these studies, hampering experimental determination of the SPA. To investigate the influence of colloidal stability on the heating response of ferrofluids, we produced bimagnetic core@shell NPs chemically composed of a ZnMn mixed ferrite core covered by a maghemite shell. Aqueous ferrofluids were prepared with these samples using the electric double layer (EDL) as a strategy to maintain colloidal stability. By starting from a proper sample, ultrastable concentrated ferrofluids were achieved by both tuning the ion/counterion ratio and controlling the water content. As the colloidal stability mainly depends on the ion configuration on the surface of the magnetic nanoparticles, different levels of nanoparticle clustering are achieved by changing the ionic force and pH of the medium. Thus, the samples were submitted to two procedures of EDL destabilization, which involved dilution with an alkaline solution and a neutral pH viscous medium. The SPA results of all prepared ferrofluid samples show a reduction of up to half the efficiency of the standard sample when the ferrofluids are in a neutral pH or concentrated regime. Such results are explained in terms of magnetic dipolar interactions. Our results point to the importance of ferrofluid colloidal stability in a more reliable experimental determination of the NP heat generation performance.

Core-Shell Bimagnetic Nanoadsorbents for Hexavalent Chromium Removal from Aqueous Solutions.

Novel nanoadsorbents based on core-shell bimagnetic nanoparticles (CoFe2O4@É£-Fe2O3) with two different mean sizes were elaborated, characterized and applied as potential sorbents for Cr(VI) removal from aqueous solutions through magnetically assisted chemical separation. The nanoadsorbents were characterized by XRD, TEM, FTIR, XPS, potentiometric-conductometric titrations, BET and vibrating sample magnetometry. The influence of contact time, shaking rate, pH, pollutant concentration, temperature and competing ions on Cr(VI) adsorption were evaluated. The results were analyzed in the framework of Langmuir and Freundlich models to evaluate the maximum adsorption capacity and the extent of affinity. The nanoadsorbents showed a good selectivity for Cr(VI) adsorption and were more effective at pH = 2.5, with a shaking rate of 400 RPM. The adsorption process was spontaneous, endothermic and presented an increased randomness. The contact time required to reach the equilibrium was relatively short and the kinetic date followed the pseudo-second-order model. The maximum adsorption capacity was nearly 40% higher for the nanoadsorbent of smaller mean size due to its higher surface area. Regeneration studies revealed that the nanoadsorbents can be recovered for reuse. These results indicate that prepared nanoadsorbents can be used as a powerful tool for Cr(VI) removal from contaminated water.