Dual-responsive magnetic nanodroplets for controlled oxygen release via ultrasound and magnetic stimulation.

Magnetic oxygen-loaded nanodroplets (MOLNDs) are a promising class of nanomaterials dually sensitive to ultrasound and magnetic fields, which can be employed as nanovectors for drug delivery applications, particularly in the field of hypoxic tissue treatment. Previous investigations were primarily focused on the application of these hybrid systems for hyperthermia treatment, exploiting magnetic nanoparticles for heat generation and nanodroplets as carriers and ultrasound contrast agents for treatment progress monitoring. This work places its emphasis on the prospect of obtaining an oxygen delivery system that can be activated by both ultrasound and magnetic fields. To achieve this goal, Fe3O4 nanoparticles were employed to decorate and induce the magnetic vaporization of OLNDs, allowing oxygen release. We present an optimized method for preparing MOLNDs by decorating nanodroplets made of diverse fluorocarbon cores and polymeric coatings. Furthermore, we performed a series of characterizations for better understanding how magnetic decoration can influence the physicochemical properties of OLNDs. Our comprehensive analysis demonstrates the efficacy of magnetic stimulation in promoting oxygen release compared to conventional ultrasound-based methods. We emphasize the critical role of selecting the appropriate fluorocarbon core and polymeric coating to optimize the decoration process and enhance the oxygen release performance of MOLNDs.

Strain-Driven Bidirectional Spin Orientation Control in Epitaxial High Entropy Oxide Films.

High entropy oxides (HEOs), based on the incorporation of multiple-principal cations into the crystal lattice, offer the possibility to explore previously inaccessible oxide compositions and unconventional properties. Here it is demonstrated that despite the chemical complexity of HEOs external stimuli, such as epitaxial strain, can selectively stabilize certain magneto-electronic states. Epitaxial (Co0.2 Cr0.2 Fe0.2 Mn0.2 Ni0.2 )3 O4 -HEO thin films are grown in three different strain states: tensile, compressive, and relaxed. A unique coexistence of rocksalt and spinel-HEO phases, which are fully coherent with no detectable chemical segregation, is revealed by transmission electron microscopy. This dual-phase coexistence appears as a universal phenomenon in (Co0.2 Cr0.2 Fe0.2 Mn0.2 Ni0.2 )3 O4 epitaxial films. Prominent changes in the magnetic anisotropy and domain structure highlight the strain-induced bidirectional control of magnetic properties in HEOs. When the films are relaxed, their magnetization behavior is isotropic, similar to that of bulk materials. However, under tensile strain, the hardness of the out-of-plane (OOP) axis increases significantly. On the other hand, compressive straining results in an easy OOP magnetization and a maze-like magnetic domain structure, indicating the perpendicular magnetic anisotropy. Generally, this study emphasizes the adaptability of the high entropy design strategy, which, when combined with coherent strain engineering, opens additional prospects for fine-tuning properties in oxides.

Electrochemical Synthesis, Magnetic and Optical Characterisation of FePd Dense and Mesoporous Nanowires.

Dense and mesoporous FePd nanowires (NWs) with 45 to 60 at.% Pd content were successfully fabricated by template- and micelle-assisted pulsed potentiostatic electrodeposition using nanoporous anodic alumina and polycarbonate templates of varying pore sizes. An FePd electrolyte was utilized for obtaining dense NWs while a block copolymer, P-123, was added to this electrolyte as the micelle-forming surfactant to produce mesoporous NWs. The structural and magnetic properties of the NWs were investigated by electron microscopy, X-ray diffraction, and vibrating sample magnetometry. The as-prepared NWs were single phase with a face-centered cubic structure exhibiting 3.1 µm to 7.1 µm of length. Mesoporous NWs revealed a core-shell structure where the porosity was only witnessed in the internal volume of the NW while the outer surface remained non-porous. Magnetic measurements revealed that the samples displayed a soft ferromagnetic behavior that depended on the shape anisotropy and the interwire dipolar interactions. The mesoporous core and dense shell structure of the NWs were seen to be slightly affecting the magnetic properties. Moreover, mesoporous NWs performed excellently as SERS substrates for the detection of 4,4'-bipyridine, showing a low detection limit of 10-12 M. The signal enhancement can be attributed to the mesoporous morphology as well as the close proximity of the embedded NWs being conducive to localized surface plasmon resonance.

Electroless Cobalt Deposition on Dealloyed Nanoporous Gold Substrate: A Versatile Technique to Control Morphological and Magnetic Properties.

The connection of multidisciplinary and versatile techniques capable of depositing and modeling thin films in multistep complex fabrication processes offers different perspectives and additional degrees of freedom in the realization of patterned magnetic materials whose peculiar physical properties meet the specific needs of several applications. In this work, a fast and cost-effective dealloying process is combined with a fast, low-cost, scalable electroless deposition technique to realize hybrid magnetic heterostructures. The gold nanoporous surface obtained by the dealloying of an Au40Si20Cu28Ag7Pd5 ribbon is used as a nanostructured substrate for the electrodeposition of cobalt. In the first steps of the deposition, the Co atoms fill the gold pores and arrange themselves into a patterned thin film with harder magnetic properties; then they continue their growth into an upper layer with softer magnetic properties. The structural characterization of the hybrid magnetic heterostructures is performed using an X-ray diffraction technique and energy-dispersive X-ray spectroscopy, while the morphology of the samples as a function of the electrodeposition time is characterized by images taken in top and cross-section view using scanning electron microscopy. Then, the structural and morphologic features are correlated with the room-temperature magnetic properties deduced from an alternating-gradient magnetometer's measurements of the hysteresis loop and first order reversal curves.

Cellular Contact Guidance on Liquid Crystalline Networks with Anisotropic Roughness.

Cell contact guidance is widely employed to manipulate cell alignment and differentiation in vitro. The use of nano- or micro-patterned substrates allows efficient control of cell organization, thus opening up to biological models that cannot be reproduced spontaneously on standard culture dishes. In this paper, we explore the concept of cell contact guidance by Liquid Crystalline Networks (LCNs) presenting different surface topographies obtained by self-assembly of the monomeric mixture. The materials are prepared by photopolymerization of a low amount of diacrylate monomer dissolved in a liquid crystalline solvent, not participating in the reaction. The alignment of the liquid crystals, obtained before polymerization, determines the scaffold morphology, characterized by a nanometric structure. Such materials are able to drive the organization of different cell lines, e.g., fibroblasts and myoblasts, allowing for the alignment of single cells or high-density cell cultures. These results demonstrate the capabilities of rough surfaces prepared from the spontaneous assembly of liquid crystals to control biological models without the need of lithographic patterning or complex fabrication procedures. Interestingly, during myoblast differentiation, also myotube structuring in linear arrays is observed along the LCN fiber orientation. The implementation of this technology will open up to the formation of muscular tissue with well-aligned fibers in vitro mimicking the structure of native tissues.

Improvement of Hyperthermia Properties of Iron Oxide Nanoparticles by Surface Coating.

Magnetic hyperthermia is an oncological therapy that exploits magnetic nanoparticles activated by radiofrequency magnetic fields to produce a controlled temperature increase in a diseased tissue. The specific loss power (SLP) of magnetic nanoparticles or the capability to release heat can be improved using surface treatments, which can reduce agglomeration effects, thus impacting on local magnetostatic interactions. In this work, Fe3O4 nanoparticles are synthesized via a coprecipitation reaction and fully characterized in terms of structural, morphological, dimensional, magnetic, and hyperthermia properties (under the Hergt-Dutz limit). Different types of surface coatings are tested, comparing their impact on the heating efficacy and colloidal stability, resulting that sodium citrate leads to a doubling of the SLP with a substantial improvement in dispersion and stability in solution over time; an SLP value of around 170 W/g is obtained in this case for a 100 kHz and 48 kA/m magnetic field.

Magnetic properties of FeGa/Kapton for flexible electronics.

Flexible materials have brought up a new era of application-based research in stretchable electronics and wearable devices in the last decade. Tuning of magnetic properties by changing the curvature of devices has significant impact in the new generation of sensor-based technologies. In this work, magnetostrictive FeGa thin films have been deposited on a flexible Kapton sheet to exploit the magneto-elastic coupling effect and modify the magnetic properties of the sample. The FeGa alloy has high magnetostriction constant and high tensile strength making its properties susceptible to external stress. Tensile or compressive strain generated by the convex or concave states influence the uniaxial magnetic anisotropy of the system. Low temperature measurements show a hard magnetic behavior and the presence of exchange-bias effect after field cooling to 2 K. The results obtained in this study prove essential for the development of flexible electronics.

Effect of the Substrate Crystallinity on Morphological and Magnetic Properties of Fe70Pd30 Nanoparticles Obtained by the Solid-State Dewetting.

Advances in nanofabrication techniques are undoubtedly needed to obtain nanostructured magnetic materials with physical and chemical properties matching the pressing and relentless technological demands of sensors. Solid-state dewetting is known to be a low-cost and "top-down" nanofabrication technique able to induce a controlled morphological transformation of a continuous thin film into an ordered nanoparticle array. Here, magnetic Fe70Pd30 thin film with 30 nm thickness is deposited by the co-sputtering technique on a monocrystalline (MgO) or amorphous (Si3N4) substrate and, subsequently, annealed to promote the dewetting process. The different substrate properties are able to tune the activation thermal energy of the dewetting process, which can be tuned by depositing on substrates with different microstructures. In this way, it is possible to tailor the final morphology of FePd nanoparticles as observed by advanced microscopy techniques (SEM and AFM). The average size and height of the nanoparticles are in the ranges 150-300 nm and 150-200 nm, respectively. Moreover, the induced spatial confinement of magnetic materials in almost-spherical nanoparticles strongly affects the magnetic properties as observed by in-plane and out-of-plane hysteresis loops. Magnetization reversal in dewetted FePd nanoparticles is mainly characterized by a rotational mechanism leading to a slower approach to saturation and smaller value of the magnetic susceptibility than the as-deposited thin film.

Experimental and Modelling Analysis of the Hyperthermia Properties of Iron Oxide Nanocubes.

The ability of magnetic nanoparticles (MNPs) to transform electromagnetic energy into heat is widely exploited in well-known thermal cancer therapies, such as magnetic hyperthermia, which proves useful in enhancing the radio- and chemo-sensitivity of human tumor cells. Since the heat release is ruled by the complex magnetic behavior of MNPs, a careful investigation is needed to understand the role of their intrinsic (composition, size and shape) and collective (aggregation state) properties. Here, the influence of geometrical parameters and aggregation on the specific loss power (SLP) is analyzed through in-depth structural, morphological, magnetic and thermometric characterizations supported by micromagnetic and heat transfer simulations. To this aim, different samples of cubic Fe3O4 NPs with an average size between 15 nm and 160 nm are prepared via hydrothermal route. For the analyzed samples, the magnetic behavior and heating properties result to be basically determined by the magnetic single- or multi-domain configuration and by the competition between magnetocrystalline and shape anisotropies. This is clarified by micromagnetic simulations, which enable us to also elucidate the role of magnetostatic interactions associated with locally strong aggregation.

Nanostructured Molybdenum Oxides from Aluminium-Based Intermetallic Compound: Synthesis and Application in Hydrogen Evolution Reaction.

Characterized by a large surface area to volume ratio, nanostructured metal oxides possess unique chemical and physical properties with applications in electronics, catalysis, sensors, etc. In this study, Mo3Al8, an intermetallic compound, has been used as a precursor to obtain nanostructured molybdenum oxides. It was prepared into ribbons by arc-melting and melt-spinning techniques. Single and double-step free corrosion of the as-quenched material have been studied in 1 M KOH, 1 M HF and 1.25 M FeCl3 at room temperature. In both cases, nanostructured molybdenum oxides were obtained on a surface layer a few microns thick. Two of the as-prepared samples were tested for their electrocatalytic capability for hydrogen evolution reaction (HER) in 0.5 M H2SO4 giving low onset potential (-50 mV, -45 mV), small Tafel slopes (92 mV dec-1, 9 mV dec-1) and high exchange current densities (0.08 mA cm-2, 0.35 mA cm-2 respectively). The proposed nanostructured molybdenum oxides are cost-effective and sustainable due to the cheap and abundant starting material used and the simple synthetic route, paving the way for their possible application as HER electrocatalysts.

Structural, Wetting and Magnetic Properties of Sputtered Fe70Pd30 Thin Film with Nanostructured Surface Induced by Dealloying Process.

FePd alloys in the thin film form represent a multipurpose and versatile material with relevant chemical and physical properties studied in different research fields. Moreover, the ability to manipulate and fine-tune the film surface with nanometric scale precision represents a degree of freedom useful to adapt these thin film properties to the demands of different desired applications. In this manuscript, Fe70Pd30 (at. %) thin films are prepared with a thickness of 50 and 200 nm by means of the widely used co-sputtering deposition technique. Subsequently, selective removal of the iron element from the alloy and the consequent surface diffusion of the palladium was induced by a dealloying treatment under free corrosion conditions in hydrochloric acid. The size and shape of the grains of the as-deposited thin films determine the dissolution rate of the iron element with a direct consequence not only on the surface morphology and the stoichiometry of the alloy but also on the wetting and magnetic properties of the sample. X-ray diffraction, Scanning Electron Microscopy (SEM) images, contact angle and magnetic measurements have been performed to provide a thorough characterisation of the fundamental properties of these nanostructured bimetallic thin films.

A comparative study of the influence of the deposition technique (electrodeposition versus sputtering) on the properties of nanostructured Fe70Pd30 films.

Sputtering and electrodeposition are among the most widespread techniques for metallic thin film deposition. Since these techniques operate under different principles, the resulting films typically show different microstructures even when the chemical composition is kept fixed. In this work, films of Fe70Pd30 were produced in a thickness range between 30 and 600 nm, using both electrodeposition and sputtering. The electrodeposited films were deposited under potentiostatic regime from an ammonia sulfosalicylic acid-based aqueous solution. Meanwhile, the sputtered films were deposited from a composite target in radio frequency regime. Both approaches were proven to yield high quality and homogenous films. However, their crystallographic structure was different. Although all films were polycrystalline and Fe and Pd formed a solid solution with a body-centered cubic structure, a palladium hydride phase was additionally detected in the electrodeposited films. The occurrence of this phase induced internal stress in the films, thereby influencing their magnetic properties. In particular, the thickest electrodeposited Fe70Pd30 films showed out-of-plane magnetic anisotropy, whereas the magnetization easy axis lied in the film plane for all the sputtered films. The domain pattern of the electrodeposited films was investigated by magnetic force microscopy. Finally, nanoindentation studies highlighted the high quality of both the sputtered and electrodeposited films, the former exhibiting higher reduced Young's modulus and Berkovich hardness values.

Specific Loss Power of Co/Li/Zn-Mixed Ferrite Powders for Magnetic Hyperthermia.

An important research effort on the design of the magnetic particles is increasingly required to optimize the heat generation in biomedical applications, such as magnetic hyperthermia and heat-assisted drug release, considering the severe restrictions for the human body's exposure to an alternating magnetic field. Magnetic nanoparticles, considered in a broad sense as passive sensors, show the ability to detect an alternating magnetic field and to transduce it into a localized increase of temperature. In this context, the high biocompatibility, easy synthesis procedure and easily tunable magnetic properties of ferrite powders make them ideal candidates. In particular, the tailoring of their chemical composition and cation distribution allows the control of their magnetic properties, tuning them towards the strict demands of these heat-assisted biomedical applications. In this work, Co0.76Zn0.24Fe2O4, Li0.375Zn0.25Fe2.375O4 and ZnFe2O4 mixed-structure ferrite powders were synthesized in a 'dry gel' form by a sol-gel auto-combustion method. Their microstructural properties and cation distribution were obtained by X-ray diffraction characterization. Static and dynamic magnetic measurements were performed revealing the connection between the cation distribution and magnetic behavior. Particular attention was focused on the effect of Co2+ and Li+ ions on the magnetic properties at a magnetic field amplitude and the frequency values according to the practical demands of heat-assisted biomedical applications. In this context, the specific loss power (SLP) values were evaluated by ac-hysteresis losses and thermometric measurements at selected values of the dynamic magnetic fields.

Structural and Magnetic Properties of FePd Thin Film Synthesized by Electrodeposition Method.

Bimetallic nanomaterials in the form of thin film constituted by magnetic and noble elements show promising properties in different application fields such as catalysts and magnetic driven applications. In order to tailor the chemical and physical properties of these alloys to meet the applications requirements, it is of great importance scientific interest to study the interplay between properties and morphology, surface properties, microstructure, spatial confinement and magnetic features. In this manuscript, FePd thin films are prepared by electrodeposition which is a versatile and widely used technique. Compositional, morphological, surface and magnetic properties are described as a function of deposition time (i.e., film thickness). Chemical etching in hydrochloric acid was used to enhance the surface roughness and help decoupling crystalline grains with direct consequences on to the magnetic properties. X-ray diffraction, SEM/AFM images, contact angle and magnetic measurements have been carried out with the aim of providing a comprehensive characterisation of the fundamental properties of these bimetallic thin films.

Influence of shape, size and magnetostatic interactions on the hyperthermia properties of permalloy nanostructures.

We present a detailed study of permalloy (Ni80Fe20) nanostructures with variable shape (disk, cylinder and sphere) for magnetic hyperthermia application, exploiting hysteresis losses for heat release. The study is performed modifying nanostructure aspect ratio and size (up to some hundreds of nanometres), to find the optimal conditions for the maximization of specific heating capabilities. The parameters are also tuned to guarantee negligible magnetic remanence and fulfilment of biophysical limits on applied field amplitude and frequency product, to avoid aggregation phenomena and intolerable resistive heating, respectively. The attention is first focused on disk-shaped nanostructures, with a comparison between micromagnetic simulations and experimental results, obtained on nanodisks still attached on the lithography substrate (2D array form) as well as dispersed in ethanol solution (free-standing). This analysis enables us to investigate the role of magnetostatic interactions between nanodisks and to individuate an optimal concentration for the maximization of heating capabilities. Finally, we study magnetization reversal process and hysteresis properties of nanocylinders (diameter between 150 nm and 600 nm, thickness from 30 nm up to 150 nm) and nanospheres (size between 100 nm and 300 nm), to give instructions on the best combination of geometrical parameters for the design of novel hyperthermia mediators.

Magnetic Shape Memory Turns to Nano: Microstructure Controlled Actuation of Free-Standing Nanodisks.

Magnetic shape memory materials hold a great promise for next-generation actuation devices and systems for energy conversion, thanks to the intimate coupling between structure and magnetism in their martensitic phase. Here novel magnetic shape memory free-standing nanodisks are proposed, proving that the lack of the substrate constrains enables the exploitation of new microstructure-controlled actuation mechanisms by the combined application of different stimuli-i.e., temperature and magnetic field. The results show that a reversible areal strain (up to 5.5%) can be achieved and tuned in intensity and sign (i.e., areal contraction or expansion) by the application of a magnetic field. The mechanisms at the basis of the actuation are investigated by experiments performed at different length scales and directly visualized by several electron microscopy techniques, including electron holography, showing that thermo/magnetomechanical properties can be optimized by engineering the martensitic microstructure through epitaxial growth and lateral confinement. These findings represent a step forward toward the development of a new class of temperature-field controlled nanoactuators and smart nanomaterials.

Tailoring magnetic properties of multicomponent layered structure via current annealing in FePd thin films.

Multicomponent layered systems with tailored magnetic properties were fabricated via current annealing from homogeneous Fe67Pd33 thin films, deposited via radio frequency sputtering on Si/SiO2 substrates from composite target. To promote spontaneous nano-structuring and phase separation, selected samples were subjected to current annealing in vacuum, with a controlled oxygen pressure, using various current densities for a fixed time and, as a consequence, different phases and microstructures were obtained. In particular, the formation of magnetite in different amount was observed beside other iron oxides and metallic phases. Microstructures and magnetic properties evolution as a function of annealing current were studied and interpreted with different techniques. Moreover, the temperature profile across the film thickness was modelled and its role in the selective oxidation of iron was analysed. Results show that is possible to topologically control the phases formation across the film thickness and simultaneously tailor the magnetic properties of the system.

Bi-Component Nanostructured Arrays of Co Dots Embedded in Ni80Fe20 Antidot Matrix: Synthesis by Self-Assembling of Polystyrene Nanospheres and Magnetic Properties.

A bi-component nanostructured system composed by a Co dot array embedded in a Ni80Fe20 antidot matrix has been prepared by means of the self-assembling polystyrene nanospheres lithography technique. Reference samples constituted by the sole Co dots or Ni80Fe20 antidots have also been prepared, in order to compare their properties with those of the bi-component material. The coupling between the two ferromagnetic elements has been studied by means of magnetic and magneto-transport measurements. The Ni80Fe20 matrix turned out to affect the vortex nucleation field of the Co dots, which in turn modifies the magneto-resistance behaviour of the system and its spinwave properties.

Hysteresis losses and specific absorption rate measurements in magnetic nanoparticles for hyperthermia applications.

BACKGROUND: Magnetic hysteresis loops areas and hyperthermia on magnetic nanoparticles have been studied with the aim of providing reliable and reproducible methods of measuring the specific absorption rate (SAR). METHODS: The SAR of Fe3O4 nanoparticles with two different mean sizes, and Ni1-xZnxFe2O4 ferrites with 0 ≤ x ≤ 0.8 has been measured with three approaches: static hysteresis loops areas, dynamic hysteresis loops areas and hyperthermia of a water solution. For dynamic loops and thermometric measurements, specific experimental setups have been developed, that operate at comparable frequencies (≈ 69kHz and ≈ 100kHz respectively) and rf magnetic field peak values (up to 100mT). The hyperthermia setup has been fully modelled to provide a direct measurement of the SAR of the magnetic nanoparticles by taking into account the heat exchange with the surrounding environment in non-adiabatic conditions and the parasitic heating of the water due to ionic currents. RESULTS: Dynamic hysteresis loops are shown to provide an accurate determination of the SAR except for superparamagnetic samples, where the boundary with a blocked regime could be crossed in dynamic conditions. Static hysteresis loops consistently underestimate the specific absorption rate but can be used to select the most promising samples. CONCLUSIONS: A means of reliably measure SAR of magnetic nanoparticles by different approaches for hyperthermia applications is presented and its validity discussed by comparing different methods. GENERAL SIGNIFICANCE: This work fits within the general subject of metrological traceability in medicine with a specific focus on magnetic hyperthermia. This article is part of a Special Issue entitled "Recent Advances in Bionanomaterials" Guest Editor: Dr. Marie-Louise Saboungi and Dr. Samuel D. Bader.

Surface modification and cellular uptake evaluation of Au-coated Ni80Fe20 nanodiscs for biomedical applications.

A nanofabrication technique based on self-assembling of polystyrene nanospheres is used to obtain magnetic Ni80Fe20 nanoparticles with a disc shape. The free-standing nanodiscs (NDs) have diameter and thickness of about 630 nm and 30 nm, respectively. The versatility of fabrication technique allows one to cover the ND surface with a protective gold layer with a thickness of about 5 nm. Magnetization reversal has been studied by room-temperature hysteresis loop measurements in water-dispersed free-standing NDs. The reversal shows zero remanence, high susceptibility and nucleation/annihilation fields due to spin vortex formation. In order to investigate their potential use in biomedical applications, the effect of NDs coated with or without the protective gold layer on cell growth has been evaluated. A successful attempt to bind cysteine-fluorescein isothiocyanate (FITC) derivative to the gold surface of magnetic NDs has been exploited to verify the intracellular uptake of the NDs by cytofluorimetric analysis using the FITC conjugate.