Albert Figuerola

From iron oxide nanoparticles towards advanced iron-based inorganic materials designed for biomedical applications.

In the last decade the progress achieved on the synthesis of inorganic nanostructures has been accompanied by the parallel exploitation of these systems in various fields, among them are biology and medicine. We provide here an overview of the iron-based inorganic nanostructured materials that have been developed and tested in these fields. We will highlight the major concepts on the preparation, physical properties and applications of such nanostructures, starting from the most investigated iron oxide nanoparticles. We will describe then the new generation of inorganic hybrid nanostructures, which are structures that integrate in each nano-object multiple inorganic nanocrystals of different materials. In our discussion we will focus on those works that have provided a sound proof of concept on the potential of the various systems as diagnostic and therapeutic agents.

One-Pot Synthesis and Characterization of Size-Controlled Bimagnetic FePt−Iron Oxide Heterodimer Nanocrystals

A one-pot, two-step colloidal strategy to prepare bimagnetic hybrid nanocrystals (HNCs), comprising size-tuned fcc FePt and inverse spinel cubic iron oxide domains epitaxially arranged in a heterodimer configuration, is described. The HNCs have been synthesized in a unique surfactant environment by temperature-driven sequential reactions, involving the homogeneous nucleation of FePt seeds and the subsequent heterogeneous growth of iron oxide. This self-regulated mechanism offers high versatility in the control of the geometric features of the resulting heterostructures, circumventing the use of more elaborate seeded growth techniques. It has been found that, as a consequence of the exchange coupling between the two materials, the HNCs exhibit tunable single-phase-like magnetic behavior, distinct from that of their individual components. In addition, the potential of the heterodimers as effective contrast agents for magnetic resonance imaging techniques has been examined.

Epitaxial CdSe-Au Nanocrystal Heterostructures by Thermal Annealing

The thermal evolution of a collection of heterogeneous CdSe-Au nanosystems (Au-decorated CdSe nanorods, networks, vertical assemblies) prepared by wet-chemical approaches was monitored in situ in the transmission electron microscope. In contrast to interfaces that are formed during kinetically controlled wet chemical synthesis, heating under vacuum conditions results in distinct and well-defined CdSe/Au interfaces, located at the CdSe polar surfaces. The high quality of these interfaces should make the heterostructures more suitable for use in nanoscale electronic devices.

Water solubilization of hydrophobic nanocrystals by means of poly(maleic anhydride-alt-1-octadecene)

Poly(maleic anhydride-alt-1-octadecene), a cheap and commercially available polymer, was used to water-solubilize colloidal nanocrystals with various compositions, morphologies, and sizes. Highly pure nanoparticles with homogeneous distributions of sizes and surface charges were obtained after a single purification step of the polymer-coated particles by ultracentrifugation, saving precious time as compared to a previously published and similar polymer coating procedure. This simple strategy proved also to be generally applicable and represents a valid methodology to water-solubilize nanoparticles.

The One Year Fate of Iron Oxide Coated Gold Nanoparticles in Mice

Safe implementation of nanotechnology and nanomedicine requires an in-depth understanding of the life cycle of nanoparticles in the body. Here, we investigate the long-term fate of gold/iron oxide heterostructures after intravenous injection in mice. We show these heterostructures degrade in vivo and that the magnetic and optical properties change during the degradation process. These particles eventually eliminate from the body. The comparison of two different coating shells for heterostructures, amphiphilic polymer or polyethylene glycol, reveals the long lasting impact of initial surface properties on the nanocrystal degradability and on the kinetics of elimination of magnetic iron and gold from liver and spleen. Modulation of nanoparticles reactivity to the biological environment by the choice of materials and surface functionalization may provide new directions in the design of multifunctional nanomedicines with predictable fate.

Size-Tunable, Hexagonal Plate-like Cu3P and Janus-like Cu–Cu3P Nanocrystals

We describe two synthesis approaches to colloidal Cu(3)P nanocrystals using trioctylphosphine (TOP) as phosphorus precursor. One approach is based on the homogeneous nucleation of small Cu(3)P nanocrystals with hexagonal plate-like morphology and with sizes that can be tuned from 5 to 50 nm depending on the reaction time. In the other approach, metallic Cu nanocrystals are nucleated first and then they are progressively phosphorized to Cu(3)P. In this case, intermediate Janus-like dimeric nanoparticles can be isolated, which are made of two domains of different materials, Cu and Cu(3)P, sharing a flat epitaxial interface. The Janus-like nanoparticles can be transformed back to single-crystalline copper particles if they are annealed at high temperature under high vacuum conditions, which makes them an interesting source of phosphorus. The features of the Cu-Cu(3)P Janus-like nanoparticles are compared with those of the striped microstructure discovered more than two decades ago in the rapidly quenched Cu-Cu(3)P eutectic of the Cu-P alloy, suggesting that other alloy/eutectic systems that display similar behavior might give origin to nanostructures with flat, epitaxial interface between domains of two diverse materials. Finally, the electrochemical properties of the copper phosphide plates are studied, and they are found to be capable of undergoing lithiation/delithiation through a displacement reaction, while the Janus-like Cu-Cu(3)P particles do not display an electrochemical behavior that would make them suitable for applications in batteries.

Magnetic Interactions and Magnetic Anisotropy in Exchange Coupled 4f–3d Systems: A Case Study of a Heterodinuclear Ce3+–Fe3+ Cyanide-Bridged Complex

We report here a detailed single-crystal EPR and magnetic study of a homologous series of complexes of the type Ln-M (Ln = La(III), Ce(III); M = Fe(III), Co(III)). We were able to obtain a detailed picture of the low-lying levels of Ce(III) and Fe(III) centres through the combined use of single-crystal EPR and magnetic susceptibility data. We show that classical ligand field theory can be of great help in rationalising the energies of the low-lying levels of both the transition-metal and rare-earth ions. The combined analysis of single-crystal EPR and magnetic data of the coupled system Ce-Fe confirmed the great complexity of the interactions involving rare-earth elements. With little uncertainty, it turned out clearly that the description of the interaction involving the lowest lying spin levels requires the introduction of the isotropic, anisotropic and antisymmetric terms.

On the discrimination between magnetite and maghemite by XANES measurements in fluorescence mode

We discuss here the quantification of magnetite and maghemite from x-ray absorption near edge spectroscopy at the Fe K-edge in fluorescence mode. We show that the modification of the spectral shape due to self-absorption effects can lead to erroneous results for certain thicknesses. However, for homogeneous samples containing just magnetite and maghemite without other phases, the quantification of magnetite and maghemite can be obtained from the spectra measured in fluorescence mode without correcting the spectra for the self-absorption effects. We describe the conditions to carry on this analysis that requires measuring the reference compounds exactly under the same conditions as the studied samples and using the appropriate thickness.

Chemical transformation of Au-tipped CdS nanorods into AuS/Cd core/shell particles by electron beam irradiation.

We demonstrate that electron irradiation of colloidal CdS nanorods carrying Au domains causes their evolution into AuS/Cd core/shell nanoparticles as a result of a concurrent chemical and morphological transformation. The shrinkage of the CdS nanorods and the growth of the Cd shell around the Au tips are imaged in real time, while the displacement of S atoms from the CdS nanorod to the Au domains is evidenced by high-sensitivity energy-dispersive X-ray (EDX) spectroscopy. The various nanodomains display different susceptibility to the irradiation, which results in nanoconfigurations that are very different from those obtained after thermal annealing. Such physical manipulations of colloidal nanocrystals can be exploited as a tool to access novel nanocrystal heterostructures.

Structure and magnetism of the first cyano-bridged hetero-one-dimensional GdIII–CrIII complexes

A reaction between Gd(NO3)3·6H2O, K3[Cr(CN)6] and dmf or bpy has allowed the synthesis of two new ferrimagnetic GdIII–CrIII chains which are the first low-dimensional 4f–CrIII systems; magnetic susceptibilty data indicate antiferromagnetic coupling between GdIII and CrIII.