Magnetic nanoparticles in square-wave fields for breakthrough performance in hyperthermia and magnetic particle imaging.

Driving immobilized, single-domain magnetic nanoparticles at high frequency by square wave fields instead of sinusoidal waveforms leads to qualitative and quantitative improvements in their performance both as point-like heat sources for magnetic hyperthermia and as sensing elements in frequency-resolved techniques such as magnetic particle imaging and magnetic particle spectroscopy. The time evolution and the frequency spectrum of the cyclic magnetization of magnetite nanoparticles with random easy axes are obtained by means of a rate-equation method able to describe time-dependent effects for the particle sizes and frequencies of interest in most applications to biomedicine. In the presence of a high-frequency square-wave field, the rate equations are shown to admit an analytical solution and the periodic magnetization can be therefore described with accuracy, allowing one to single out effects which take place on different timescales. Magnetic hysteresis effects arising from the specific features of the square-wave driving field results in a breakthrough improvement of both the magnetic power released as heat to an environment in magnetic hyperthermia treatments and the magnitude of the third harmonic of the frequency spectrum of the magnetization, which plays a central role in magnetic particle imaging.

The beneficial role of nano-sized Fe3O4 entrapped in ultra-stable Y zeolite for the complete mineralization of phenol by heterogeneous photo-Fenton under solar light.

Highly efficient, separable, and stable magnetic iron-based-photocatalysts produced from ultra-stable Y (USY) zeolite were applied, for the first time, to the photo-Fenton removal of phenol under solar light. USY Zeolite with a Si/Al molar ratio of 385 was impregnated under vacuum with an aqueous solution of Fe2+ ions and thermally treated (500-750 °C) in a reducing atmosphere. Three catalysts, Fe-USY500°C-2h, Fe-USY600°C-2h and Fe-USY750°C-2h, containing different amounts of reduced iron species entrapped in the zeolitic matrix, were obtained. The catalysts were thoroughly characterized by absorption spectrometry, X-ray powder diffraction with synchrotron source, followed by Rietveld analysis, X-ray photoelectron spectroscopy, N2 adsorption/desorption at -196 °C, high-resolution transmission electron microscopy and magnetic measurements at room temperature. The catalytic activity was evaluated in a recirculating batch photoreactor irradiated by solar light with online analysis of evolved CO2. Photo-Fenton results showed that the catalyst obtained by thermal treatment at 500 °C for 2 h under a reducing atmosphere (FeUSY-500°C-2h) was able to completely mineralize phenol in 120 min of irradiation time at pH = 4 owing to the presence of a higher content of entrapped nano-sized magnetite particles. The latter promotes the generation of hydroxyl radicals in a more efficient way than the Fe-USY catalysts prepared at 600 and 750 °C because of the higher Fe3O4 content in ultra-stable Y zeolite treated at 500 °C. The FeUSY-500°C-2h catalyst was recovered from the treated water through magnetic separation and reused five times without any significant worsening of phenol mineralization performances. The characterization of the FeUSY-500°C-2h after the photo-Fenton process demonstrated that it was perfectly stable during the reaction. The optimized catalyst was also effective in the mineralization of phenol in tap water. Finally, a possible photo-Fenton mechanism for phenol mineralization was assessed based on experimental tests carried out in the presence of scavenger molecules, demonstrating that hydroxyl radicals play a major role.

Multifunctional effects in magnetic nanoparticles for precision medicine: combining magnetic particle thermometry and hyperthermia.

An effective combination of magnetic hyperthermia and thermometry is shown to be implementable by using magnetic nanoparticles which behave either as a heat sources or as temperature sensors when excited at two different frequencies. Noninteracting magnetite nanoparticles are modeled as double-well systems and their magnetization is obtained by solving rate equations. Two temperature sensitive properties derived from the cyclic magnetization and exhibiting a linear dependence on temperature are studied and compared for monodisperse and polydisperse nanoparticles. The multifunctional effects enabling the combination of magnetic hyperthermia and thermometry are shown to depend on the interplay among nanoparticle size, intrinsic magnetic properties and driving-field frequency. Magnetic hyperthermia and thermometry can be effectively combined by properly tailoring the magnetic properties of nanoparticles and the driving-field frequencies.

Removal of sulfanilamide by tailor-made magnetic metal-ceramic nanocomposite adsorbents.

Three tailor-made magnetic metal-ceramic nanocomposites, obtained from zeolite A (ZA1 and ZA2) and a natural clinoptilolite (LB1), have been used as adsorbents to remove sulfanilamide (SA), a sulfonamide antibiotic of common use, from water. A patented process for the synthesis of nanocomposites has been suitably modified to maximize the efficiency of the SA removal, as well as to extend the applicability of the materials. The role played by the main process parameters (kinetic, pH, initial concentration of SA) has been characterized. The significant effect of the pH on the SA removal has been explained identifying two possibly coexisting mechanisms of SA adsorption, based on polar and hydrophobic interactions, respectively. The adsorption kinetics have been in all cases described by the pseudo second-order model. The adsorption isotherms obtained with ZA1 have been satisfactorily described by the Langmuir model, suggesting a monolayer adsorption of SA on the magnetic nanocomposites resulting from a uniform surface energy. The isotherms obtained with LB1 could be described by a more complex approach, deriving by the additive superposition of Langmuir and Sips models. In order to ensure an effective removal of the antibiotic and a proper recycle of the magnetic adsorbents, a sustainable regeneration procedure of the exhausted adsorbent has been developed, based on the treatment with a dilute solution of NaOH.

Dipolar interactions among magnetite nanoparticles for magnetic hyperthermia: a rate-equation approach.

Rate equations are used to study the dynamic magnetic properties of interacting magnetite nanoparticles viewed as double well systems (DWS) subjected to a driving field in the radio-frequency range. Dipole-dipole interaction among particles is modeled by inserting an ad-hoc term in the energy barrier to simulate the dependence of the interaction on both the interparticle distance and degree of dipole collinearity. The effective magnetic power released by an assembly of interacting nanoparticles dispersed in a diamagnetic host is shown to be a complex function of nanoparticle diameter, mean particle interdistance and frequency. Dipolar interaction markedly modifies the way a host material is heated by an assembly of embedded nanoparticles in magnetic hyperthermia treatments. Nanoparticle fraction and strength of the interaction can dramatically influence the amplitude and shape of the heating curves of the host material; the heating ability of interacting nanoparticles is shown to be either improved or reduced by their concentration in the host material. A frequency-dependent cut-off length of dipolar interactions is determined and explained. Particle polydispersity entailing a distribution of particle sizes brings about non-trivial effects on the heating curves depending on the strength of dipolar interaction.

Separation of Biological Entities From Human Blood by Using Magnetic Nanocomposites Obtained From Zeolite Precursors.

In this work, three novel magnetic metal-ceramic nanocomposites were obtained by thermally treating Fe-exchanged zeolites (either A or X) under reducing atmosphere at relatively mild temperatures (750-800 °C). The so-obtained materials were thoroughly characterized from the point of view of their physico-chemical properties and, then, used as magnetic adsorbents in the separation of the target gene factors V and RNASE and of the Staphylococcus aureus bacteria DNA from human blood. Such results were compared with those obtained by using a top ranking commercial separation system (namely, SiMAG-N-DNA by Chemicell). The results obtained by using the novel magnetic adsorbents were similar to (or even better than) those obtained by using the commercial system, both during manual and automated separations, provided that a proper protocol was adopted. Particularly, the novel magnetic adsorbents showed high sensitivity during tests performed with small volumes of blood. Finally, the feasible production of such magnetic adsorbents by an industrial process was envisaged as well.

Temperature-dependent heating efficiency of magnetic nanoparticles for applications in precision nanomedicine.

The power released by magnetic nanoparticles submitted to an alternating driving field is temperature dependent owing to the variation of the fundamental magnetic properties. Therefore, the heating efficiency of magnetic nanoparticles for applications in precision nanomedicine (such as magnetic hyperthermia or heat-assisted drug delivery) can be significantly affected by the local instantaneous temperature of the host medium. A rate equation approach is used to determine the hysteretic properties and the power released by magnetite nanoparticles, and the heat transport equation is solved in a simple geometry with boundary conditions appropriate to both in-lab experiments and in vivo applications. Size plays a fundamental role in determining the heating efficiency of magnetic nanoparticles; above a critical size, nanoparticles remain inactive, although they can undergo secondary activation. The experimental conditions for optimal thermal efficiency are expressed by a thermal activity diagram for nanoparticles. In the light of the model's results, features, methods, advantages and dangers of magnetic-particle assisted precision nanomedicine ought to be reconsidered. In vivo antitumor applications should take into account the hazards arising from the heat generated by magnetic nanoparticles that diffuse into the neighboring healthy tissue.

Fine tuning and optimization of magnetic hyperthermia treatments using versatile trapezoidal driving-field waveforms.

Applying trapezoidal driving-field waveforms to activate magnetic nanoparticles optimizes their performance as heat generators in magnetic hyperthermia, with notable advantages with respect to the effects of harmonic magnetic fields of the same frequency and amplitude. A rate equation approach is used to determine the hysteretic properties and the power released by monodisperse and polydisperse magnetite nanoparticles with randomly oriented easy axes subjected to a radio-frequency trapezoidal driving field. The heating ability of the activated nanoparticles is investigated by means of a simple model in which the heat equation is solved in radial geometry with boundary conditions simulating in vivo applications. Changes of the inclination of the trapezoidal waveform's lateral sides are shown to induce controlled changes in the specific loss power generated by the activated nanoparticles. Specific issues typical of the therapeutic practice of hyperthermia, such as the need for fine tuning of the optimal treatment temperature in real time, the possibility of combining sequential treatments at different temperatures, and the ability to substantially reduce the heating transient in a hyperthermia treatment are suitably addressed and overcome by making use of versatile driving fields of a trapezoidal shape.

Magnetic states of nanostructures containing Ni2+ ions at the surface of SiO2 nanospheres.

Ultra-small magnetic particles containing Ni2+ ions were grown at the surface of SiO2 spheroidal nanoparticles (typical diameter: 50 nm) starting from NiCl2 solutions. Depending on preparation details, two samples characterized by magnetic sub-nanostructures or lamellar sub-nanoparticles at the SiO2 nanosphere surface were obtained. The decorated SiO2 nanospheres were submitted to physico-chemical and magnetic characterization. In both samples, a magnetically blocked phase is observed at low temperature. Below 5 K, discontinuities in isothermal magnetization loops and magnetic relaxation effects suggest the onset of coherent quantum tunneling of nanoparticle magnetization (QTM). Relaxation effects give are described by a field- and temperature-dependent magnetic viscosity SV(H,T); the total spin number of magnetic units is estimated by fitting the isothermal SV(H) curve to a model for an assembly of particles with random anisotropy axes. The mean number of aligned spins involved in the low-temperature relaxation is 32 and 15 in the two considered samples. Phonon-assisted QTM plays an increasingly important role with raising temperature and the quantum regime gradually merges with the classical behavior. Above the blocking temperature the magnetic units behave as classical superparamagnetic particles. When the intra-particle ferromagnetic order disappears the Ni2+ ions respond individually to the magnetic field.

Preparation and Characterization of Magnetic and Porous Metal-Ceramic Nanocomposites from a Zeolite Precursor and Their Application for DNA Separation.

In this work, metal-ceramic nanocomposites were obtained through short (up to 2 h) thermal treatments at relatively moderate temperatures (750­800 °C) under a reducing atmosphere, using Fe-exchanged zeolite A as the precursor. The as-obtained materials were characterized by X-ray powder diffraction analysis, N2 adsorption at ­196 °C, and highresolution transmission electron microscopy. The results of these analyses showed that the nanocomposites consisted of a dispersion of metallic Fe nanoparticles within a porous ceramic matrix, mainly based on amorphous silica and alumina. These nanocomposites were magnetically characterized, and their magnetic response was studied. Finally, the obtained metal-ceramic nanocomposite materials were used in the separation of Escherichia coli DNA from a crude cell lysate. The results of the DNA separation experiments showed that the obtained materials could perform this type of separation.