Magnetothermally-responsive nanocarriers using confined phosphorylated halloysite nanoreactor for in situ iron oxide nanoparticle synthesis: a MW-assisted solvothermal approach

A family of easily recoverable magnetic and thermally responsive composite materials, with nanoscale dimensions, were synthesized by a rapid and simple solvothermal approach. The synthesis was thermally activated, accelerated, and controlled using a coaxial antenna to directly apply the microwave energy inside the solvothermal reactor. The composite materials were made up by a confined phosphorylated nanoreactor, namely halloysite nanotubes grafted on the inner lumen with phosphoric acid (HNTs-(H+-PO4)), that promoted the urea hydrolysis thus favoring the formation of a local alkaline environment to catalyze the homogeneous in situ precipitation of superparamagnetic iron oxide nanoparticles (IONs) selectively on their inner or outer surface. Two new MW-assisted solvothermal methodologies were used: 1) in the first the solvent is directly loaded into the MW-assisted reactor together with HNTs-(H+-PO4) mechanically preloaded with iron chloride and urea in the lumen 2) in the second the synthesis is preceded by a further pre-functionalization step of the iron salt with clove essential oil (EO) as a green functionalization agent. Structural, morphological, textural, and magnetic properties were assessed by TEM, N2 physisorption, TG-FTIR, ICP, XRD, magnetic and magnetic hyperthermia measurements. The MW-assisted solvothermal deposition of IONs was fully controlled using the phosphorylated nanoreactor, in short synthesis times, by a simple methodology following the principles of sustainable chemistry. IONs were selectively deposited on the outer surface or in the inner lumen of HNTs yielding easily recoverable superparamagnetic and thermally responsive nanocarriers suitable for applications like targeted hyperthermia therapy

Seeded Growth Synthesis of Au-Fe3O4 Heterostructured Nanocrystals : Rational Design and Mechanistic Insights

Multifunctional hybrid nanoparticles comprising two or more entities with different functional properties are gaining ample significance in industry and research. Due to its combination of properties, a particularly appealing example is Au-FeO composite nanoparticles. Here we present an in-depth study of the synthesis of Au-FeO heterostructured nanocrystals (HNCs) by thermal decomposition of iron precursors in the presence of preformed 10 nm Au seeds. The role of diverse reaction parameters on the HNCs formation was investigated using two different precursors: iron pentacarbonyl (Fe(CO)) and iron acetylacetonate (Fe(acac)). The reaction conditions promoting the heterogeneous nucleation of FeO onto Au seeds were found to significantly differ depending on the precursor chosen, where Fe(acac) is considerably more sensitive to the variation of the parameters than Fe(CO) and more subject to homogeneous nucleation processes with the consequent formation of isolated iron oxide nanocrystals (NCs). The role of the surfactants was also crucial in the formation of well-defined and monodisperse HNCs by regulating the access to the Au surface. Similarly, the variations of the [Fe]/[Au] ratio, temperature, and employed solvent were found to act on the mean size and the morphology of the obtained products. Importantly, while the optical properties are rather sensitive to the final morphology, the magnetic ones are rather similar for the different types of obtained HNCs. The surface functionalization of dimer-like HNCs with silica allows their dispersion in aqueous media, opening the path to their use in biomedical applications

Assessing the hyperthermic properties of magnetic heterostructures: the case of gold-iron oxide composites

Gold-iron oxide composites were obtained by in situ reduction of an Au(III) precursor by an organic reductant (either potassium citrate or tiopronin) in a dispersion of preformed iron oxide ultrasmall magnetic (USM) nanoparticles. X-ray diffraction,transmission electron microscopy,chemical analysis and mid-infrared spectroscopy show the successful deposition of gold domains on the preformed magnetic nanoparticles,and the occurrence of either citrate or tiopronin as surface coating. The potential of the USM@Au nanoheterostructures as heat mediators for therapy through magnetic fluid hyperthermia was determined by calorimetric measurements under sample irradiation by an alternating magnetic field with intensity and frequency within the safe values for biomedical use. The USM@Au composites showed to be active heat mediators for magnetic fluid hyperthermia,leading to a rapid increase in temperature under exposure to an alternating magnetic field even under the very mild experimental conditions adopted,and their potential was assessed by determining their specific absorption rate (SAR) and compared with the pure iron oxide nanoparticles. Calorimetric investigation of the synthesized nanostructures enabled us to point out the effect of different experimental conditions on the SAR value,which is to date the parameter used for the assessment of the hyperthermic efficiency.This work was partially funded by the Regione Autonoma della Sardegna under the R&D project ‘Chitostrip’ and by Fondazione CARIPLO (project BaTMAN, no. 2013-0752).Peer Reviewe

Addressing the Influence of Localized Plasmon Resonance on the Magneto-Optical Properties of Cobalt Ferrite Nanoparticles

The optical and magneto-optical (MO) properties of magneto-plasmonic nanocomposite films made up of a transparent polymer with a dispersion of cobalt ferrite (CFO) nanoparticles (NPs) and different concentrations of Au NPs are investigated. The volumetric concentrations of CFO and Au NPs, around 3%, and below 7‰ respectively, are below the percolation limit, and hence the nanocom-posite films constitute models for investigating the influence of the electromagnetic field generated at the surface plasmon resonance of Au NPs on the magneto-optical properties of CFO NPs. The plasmon resonance is present in these magneto-plasmonic composites, red-shifted with respect to the bare Au NPs and covering the spectral region where charge-transfer and crystal field MO transitions can be excited. Moreover, the magneto-optical hysteresis loops were measured in the whole spectral region. We observe that the hysteresis loops shape is a fingerprint of the different MO transitions of the CFO NPs. The strength of the MO peak around 750 nm, corresponding to the Crystal Field transition is damped respect to the corresponding peak of the CFO NPs. The strength of this peak evolves non-monotonically with the Au NPs concentration. On the other hand, the MO band around 550 nm, excited by Charge Transfer transitions, changes sign when Au NPs are present. In addition, a second MO contribution is observed. Our results demonstrate that the interactions between plasmon resonance and MO effects are not only determined by the stronger local electromagnetic fields at the resonance but they depend on the type MO transition that is involved in these oxides. This study helps to understand and design the magneto plasmonic nano-structures and applications, for example in biomedicine and sensing, in which random and weak dipolar interparticle interactions between plasmonic and magnetic nanostructures are present

Modulation of the magnetic properties of gold-spinel ferrite heterostructured nanocrystals

[EN] The rational design of complex nanostructures is of paramount importance to gain control over their chemical and physical properties. Recently, magnetic-plasmonic heterostructured nanocrystals have been recognized as key players in nanomedicine as multifunctional therapeutic-diagnostic tools and in catalysis. Here we show how the properties of gold-iron oxide heterostructured nanocrystals can be tuned by chemical doping of the magnetic subunit. The divalent cations in the iron oxide were substituted with cobalt and manganese to obtain a general formula Au-MFe2O4 (M = Fe, Co, Mn). Magnetic properties of the heterostructures could be tuned, while maintaining well-defined plasmon resonance signatures, confirming the dual magnetic-plasmonic functional capability of these nanostructures.The financial support of European Union’s Horizon 2020 Research and Innovation program under Grant agreements No. 737093 (FEMTOTERABYTE, http://www.physics.gu.se/ femtoterabyte) and No. 720853 (AMPHIBIAN, http://amphibianproject.eu/), University of Pisa through project PRA_ 2017_25 and INFN through HADROMAG project is gratefully acknowledged. E. F. thanks the support of the “Galileo Galilei” fellowship from the University of Pisa.Peer reviewe

A hybrid hyperthermia device, and methods using the same

The present invention provides a hybrid hyperthermia system or device capable of generating, simultaneously or sequentially, optical and magnetic treatment by using materials with dispersed, embedded or anchored particles for applications where it is necessary to heat a specific area or material in a safer way, and for applications where it is necessary to characterize the properties of a specific area or material subjected to optical and/or magnetic heating. The invention is also directed to its uses for combined hyperthermia treatment, and for characterization of optical and magneto-optical properties of a specific area or material.Peer reviewedFundació Institut Català de Nanociència i Nanotecnología, Consejo Superior de Investigaciones Científicas (España), Institució Catalana de Recerca i Estudis AvançactsA3 Informe de búsqueda internaciona