Marcela B. Fernández van Raap

Effect of Nanoclustering and Dipolar Interactions in Heat Generation for Magnetic Hyperthermia.

Biomedical magnetic colloids commonly used in magnetic hyperthermia experiments often display a bidisperse structure, i.e., are composed of stable nanoclusters coexisting with well-dispersed nanoparticles. However, the influence of nanoclusters in the optimization of colloids for heat dissipation is usually excluded. In this work, bidisperse colloids are used to analyze the effect of nanoclustering and long-range magnetic dipolar interaction on the magnetic hyperthermia efficiency. Two kinds of colloids, composed of magnetite cores with mean sizes of around 10 and 18 nm, coated with oleic acid and dispersed in hexane, and coated with meso-2,3-dimercaptosuccinic acid and dispersed in water, were analyzed. Small-angle X-ray scattering was applied to thoroughly characterize nanoparticle structuring. We proved that the magnetic hyperthermia performances of nanoclusters and single nanoparticles are distinctive. Nanoclustering acts to reduce the specific heating efficiency whereas a peak against concentration appears for the well-dispersed component. Our experiments show that the heating efficiency of a magnetic colloid can increase or decrease when dipolar interactions increase and that the colloid concentration, i.e., dipolar interaction, can be used to improve magnetic hyperthermia. We have proven that the power dissipated by an ensemble of dispersed magnetic nanoparticles becomes a nonextensive property as a direct consequence of the long-range nature of dipolar interactions. This knowledge is a key point in selecting the correct dose that has to be injected to achieve the desired outcome in intracellular magnetic hyperthermia therapy.

Hybrid nanomaterials based on gum Arabic and magnetite for hyperthermia treatments

In this study, one-step co-precipitation method was conveniently adapted to obtain novel nanomaterials based on Gum Arabic and magnetite. Two synthesis procedures were evaluated: one employing the solid biopolymer in the co-precipitation media; a second using an aqueous solution of the polysaccharide. An exhaustive characterization of both formulations was performed using several specific techniques. The obtained data confirmed the successful incorporation of the gum Arabic on the magnetic core. Values of hydrodynamic diameters, measured by dynamic light scattering, in aqueous dispersions were about 70-80nm, while sizes lower than 20nm were registered by TEM microscopy. Surface charge of gum Arabic coated magnetic nanoparticles was significantly different from the corresponding to raw materials (magnetite and GA). This fact confirmed the formation of hybrid nanosystems with novel and specific properties. The potential utility of these materials was tested regarding to magnetic hyperthermia therapy under radiofrequency fields. Magnetocalorimetric measurements were performed in a wide range of field amplitude and frequency. Specific absorption rate of 218W/gFe was determined at field frequency of 260kHz and amplitude of 52kA/m. These results demonstrate their viability to be applied in tumor ablation treatments. Using the linear response theory and restricting field parameters to the accepted biomedical window, maximum useful value of 74w/gFe is predicted at 417kHz and 12kA/m.

Magnetically Assembled SERS Substrates Composed of Iron-Silver Nanoparticles Obtained by Laser Ablation in Liquid.

The widespread application of surface-enhanced Raman scattering (SERS) would benefit from simple and scalable self-assembly procedures for the realization of plasmonic arrays with a high density of electromagnetic hot-spots. To this aim, the exploitation of iron-doped silver nanoparticles (NPs) synthesized by laser ablation of a bulk bimetallic iron-silver target immersed in ethanol is described. The use of laser ablation in liquid is key to achieving bimetallic NPs in one step with a clean surface available for functionalization with the desired thiolated molecules. These iron-silver NPs show SERS performances, a ready response to external magnetic fields and complete flexibility in surface coating. All these characteristics were used for the magnetic assembly of plasmonic arrays which served as SERS substrates for the identification of molecules of analytical interest. The magnetic assembly of NPs allowed a 28-fold increase in the SERS signal of analytes compared to not-assembled NPs. The versatility of substrate preparation and the SERS performances were investigated as a function of NPs surface coating among different thiolated ligands. These results show a simple procedure to obtain magnetically assembled regenerable plasmonic arrays for repeated SERS investigation of different samples, and it can be of inspiration for the realization of other self-assembled and reconfigurable magnetic-plasmonic devices.

Optical and Magnetic Properties of Fe Nanoparticles Fabricated by Femtosecond Laser Ablation in Organic and Inorganic Solvents

Magnetic nanoparticles have attracted much interest due to their broad applications in biomedicine and pollutant remediation. In this work, the optical, magnetic, and structural characteristics of colloids produced by ultrashort pulsed laser ablation of a solid Fe target were studied in four different media: HPLC water, an aqueous solution of trisodium citrate, acetone, and ethanol. Optical extinction spectroscopy revealed an absorption band in the UV region for all, in contrast to the results obtained with nanosecond lasers. Micro-Raman spectroscopy showed that the samples are heterogeneous in their composition, with hematite, maghemite, and magnetite nanoparticles in all four solvents. Similar results were obtained by electron diffraction, which also found α-Fe. Magnetic properties were studied by vibrating-sample magnetometry, and showed nanoparticles in the superparamagnetic state. Under certain experimental conditions, submicrometer-sized iron oxide nanoparticles agglomerate into fractal patterns that show self-similar properties. Self-assembled annular structures on the nanometer scale were also observed and are reported for the first time.

Selective contrast agents with potential to the earlier detection of tumors: Insights on synthetic pathways, physicochemical properties and performance in MRI assays

Magnetic iron oxide nanoparticles (MNPs) have been prepared and stabilized with three organic acids (tartaric, malic and ascorbic) in order to obtain biocompatible and water dispersible MNPs with potential to bind specifically to tumoral cancer cells. An in deep characterization was performed aiming to verify the presence and effect of the coating and stabilizer on MNPs surface. Besides the mechanisms followed by the different acids to bind MNPs were elucidated and used to justify the differences in the physicochemical properties of each formulation. Data related to characterization revealed that MNPs coated with ascorbic acid (MNPs-AA) resulted the most suitable in terms of their size, surface charge and stability along the time. Besides, ascorbic acid may be recognized by GLUTs receptors that are overexpressed in several kinds of tumoral cells. Therefore, MNPs-AA was selected to explore its performance in both MRI and in vitro assays using human colon cancer cells HCT 116. MRI experiments were performed in clinical equipment using a series of aqueous dispersions of MNPs-AA that were evaluated as T2 contrast agent. The T2- weighted images obtained as well as the calculated r2, indicated that MNPs-AA could act as efficient T2 contrast agent for MRI. Regarding in vitro assays, MNPs-AA did not alter the cellular function neither exert cytotoxicity using the three explored doses. The internalization of the nanoparticles on the cellular structure was confirmed quanti and qualitatively using atomic absorption spectroscopy and Prussian blue techniques respectively. From these results, it emerges that ascorbic acid coated-magnetite nanoparticles may be used as alternative contrast agent to avoid or minimize some toxicological issues related to the widely used gadolinium.

Nanoscale Dielectric Function of Fe, Pt, Ti, Ta, Al, and V: Application to Characterization of Al Nanoparticles Synthesized by Fs Laser Ablation

Development and applications of new nanomaterials and nanocomposites that include metal nanoparticles have received much attention in the last years. However, there are relatively few studies concerning basic physical characteristics of the dielectric function at the nanoscale, which is needed for predicting their optical and plasmonic response. The size-dependent complex dielectric function of metal Fe, Pt, Ti, Ta, Al, and V nanoparticles (NPs) is calculated for the first time for an extended wavelength range from UV to FIR, based on experimental bulk complex refractive index measurements in the mentioned range at room temperature. Calculation is based on a “top-down” approach, based on a stepwise modification of the Drude model. Bulk plasma frequency (ωp) and damping constant (γfree) in this model are determined using a method that improves the relative uncertainties in their values and provide an insight about the wavelength range over which the metal may be considered Drude like. Validation of ωp and γfree values is demonstrated by the improved accuracy with which the experimental bulk dielectric function is reproduced. For nanometric and subnanometric scales, dielectric function is made size dependent considering size-corrective terms for free and bound electron contributions to the bulk dielectric function. These results are applied to analyze the synthesis of Al NP suspensions using a 120-fs pulse laser to ablate an Al solid target in n-heptane and water. The presence of Al, Al-Al2O3, and air-Al core-shell structures is also reported for the first time in these type of colloids. Analysis of the structure, configuration, sizing, and relative abundance was carried out using optical extinction spectroscopy (OES). Sizing results are compared with those provided by atomic force microscopy (AFM) studies.