Magnetic Study of CuFe2O4-SiO2 Aerogel and Xerogel Nanocomposites.

CuFe2O4 is an example of ferrites whose physico-chemical properties can vary greatly at the nanoscale. Here, sol-gel techniques are used to produce CuFe2O4-SiO2 nanocomposites where copper ferrite nanocrystals are grown within a porous dielectric silica matrix. Nanocomposites in the form of both xerogels and aerogels with variable loadings of copper ferrite (5 wt%, 10 wt% and 15 wt%) were synthesized. Transmission electron microscopy and X-ray diffraction investigations showed the occurrence of CuFe2O4 nanoparticles with average crystal size ranging from a few nanometers up to around 9 nm, homogeneously distributed within the porous silica matrix, after thermal treatment of the samples at 900 °C. Evidence of some impurities of CuO and α-Fe2O3 was found in the aerogel samples with 10 wt% and 15 wt% loading. DC magnetometry was used to investigate the magnetic properties of these nanocomposites, as a function of the loading of copper ferrite and of the porosity characteristics. All the nanocomposites show a blocking temperature lower than RT and soft magnetic features at low temperature. The observed magnetic parameters are interpreted taking into account the occurrence of size and interaction effects in an ensemble of superparamagnetic nanoparticles distributed in a matrix. These results highlight how aerogel and xerogel matrices give rise to nanocomposites with different magnetic features and how the spatial distribution of the nanophase in the matrices modifies the final magnetic properties with respect to the case of conventional unsupported nanoparticles.

Thermally stable surfactant-free ceria nanocubes in silica aerogel.

Surfactant-mediated chemical routes allow one to synthesize highly engineered shape- and size-controlled nanocrystals. However, the occurrence of capping agents on the surface of the nanocrystals is undesirable for selected applications. Here, a novel approach to the production of shape-controlled nanocrystals which exhibit high thermal stability is demonstrated. Ceria nanocubes obtained by surfactant-mediated synthesis are embedded inside a highly porous silica aerogel and thermally treated to remove the capping agent. Powder X-ray Diffraction and Scanning Transmission Electron Microscopy show the homogeneous dispersion of the nanocubes within the aerogel matrix. Remarkably, both the size and the shape of the ceria nanocubes are retained not only throughout the aerogel syntheses but also upon thermal treatments up to 900 °C, while avoiding their agglomeration. The reactivity of ceria is measured by in situ High-Energy Resolution Fluorescence Detected - X-ray Absorption Near Edge Spectroscopy at the Ce L3 edge, and shows the reversibility of redox cycles of ceria nanocubes when they are embedded in the aerogel. This demonstrates that the enhanced reactivity due to their prominent {100} crystal facets is preserved. In contrast, unsupported ceria nanocubes begin to agglomerate as soon as the capping agent decomposes, leading to a degradation of their reactivity already at 275 °C.

Growing CeO2 Nanoparticles Within the Nano-Porous Architecture of the SiO2 Aerogel.

In this study, new CeO2-SiO2 aerogel nanocomposites obtained by controlled growth of CeO2 nanoparticles within the highly porous matrix of a SiO2 aerogel are presented. The nanocomposites have been synthesized via a sol-gel route, employing cerium (III) nitrate as the CeO2 precursor and selected surfactants to control the growth of the CeO2 nanoparticles, which occurs during the supercritical drying of the aerogels. Samples with different loading of the CeO2 dispersed phase, ranging from 5 to 15%, were obtained. The nanocomposites showed the morphological features typical of the SiO2 aerogels such as open mesoporosity with surface area values up to 430 m2·g-1. TEM and XRD characterizations show that nanocrystals of the dispersed CeO2 nanophase grow within the aerogel already during the supercritical drying process, with particle sizes in the range of 3 to 5 nm. TEM in particular shows that the CeO2 nanoparticles are well-distributed within the aerogel matrix. We also demonstrate the stability of the nanocomposites under high temperature conditions, performing thermal treatments in air at 450 and 900°C. Interestingly, the CeO2 nanoparticles undergo a very limited crystal growth, with sizes up to only 7 nm in the case of the sample subjected to a 900°C treatment.

Assembly of Multicomponent Nano-Bioconjugates Composed of Mesoporous Silica Nanoparticles, Proteins, and Gold Nanoparticles.

The purpose of this work was the assembly of multicomponent nano-bioconjugates based on mesoporous silica nanoparticles (MSNs), proteins (bovine serum albumin, BSA, or lysozyme, LYZ), and gold nanoparticles (GNPs). These nano-bioconjugates may find applications in nanomedicine as theranostic devices. Indeed, MSNs can act as drug carriers, proteins stabilize MSNs within the bloodstream, or may have therapeutic or targeting functions. Finally, GNPs can either be used as contrast agents for imaging or for photothermal therapy. Here, amino-functionalized MSNs (MSN-NH2) were synthesized and characterized through various techniques (small angle X-rays scattering TEM, N2 adsorption/desorption isotherms, and thermogravimetric analysis (TGA)). BSA or lysozyme were then grafted on the external surface of MSN-NH2 to obtain MSN-BSA and MSN-LYZ bioconjugates, respectively. Protein immobilization on MSNs surface was confirmed by Fourier transform infrared spectroscopy, ζ-potential measurements, and TGA, which also allowed the estimation of protein loading. The MSN-protein samples were then dispersed in a GNP solution to obtain MSN-protein-GNPs nano-bioconjugates. Transmission electron microscopy (TEM) analysis showed the occurrence of GNPs on the MSN-protein surface, whereas almost no GNPs occurred in the protein-free control samples. Fluorescence and Raman spectroscopies suggested that proteins-GNP interactions involve tryptophan residues.

The Role of Ligands in the Chemical Synthesis and Applications of Inorganic Nanoparticles.

The design of nanoparticles is critical for their efficient use in many applications ranging from biomedicine to sensing and energy. While shape and size are responsible for the properties of the inorganic nanoparticle core, the choice of ligands is of utmost importance for the colloidal stability and function of the nanoparticles. Moreover, the selection of ligands employed in nanoparticle synthesis can determine their final size and shape. Ligands added after nanoparticle synthesis infer both new properties as well as provide enhanced colloidal stability. In this article, we provide a comprehensive review on the role of the ligands with respect to the nanoparticle morphology, stability, and function. We analyze the interaction of nanoparticle surface and ligands with different chemical groups, the types of bonding, the final dispersibility of ligand-coated nanoparticles in complex media, their reactivity, and their performance in biomedicine, photodetectors, photovoltaic devices, light-emitting devices, sensors, memory devices, thermoelectric applications, and catalysis.

Uncommon Optical Properties and Silver-Responsive Turn-Off/On Luminescence in a PtII Heteroleptic Dithiolene Complex.

Complex [Pt(iPr2 pipdt)(Quinoxdt)] (iPr2 pipdt=1,4-diisopropyl-piperazine-2,3-dithione; Quinoxdt=[1,4]dithiino[2,3-b]quinoxaline-2,3-dithiolate) exhibits a remarkable green emission at 570 nm (room temperature), which is above the lowest excited state. The complex is characterized by negative solvatochromism as well as a high second-order polarizability. Addition of AgI ions induces 1) hypsochromic shift of the lowest frequencies and 2) reversible quenching of luminescence. The corresponding Ni and Pd complexes have also been prepared and investigated to assist interpretation of optical properties within the triad. Computational studies based on DFT and time-dependent DFT highlight the electronic properties of [Pt(iPr2 pipdt)(Quinoxdt)]. The preferential site of interaction between the Pt complex and incoming AgI is evidenced by the shape of the Fukui functions, pointing to the thiolic sulfur and platinum atoms as the most reactive sites towards a soft cation. Calculated optical properties are in agreement with experimental findings. This study sheds light on the structure-property relationship for this class of compounds.

Evidence of a cubic iron sub-lattice in t-CuFe2O4 demonstrated by X-ray Absorption Fine Structure.

Copper ferrite, belonging to the wide and technologically relevant class of spinel ferrites, was grown in the form of t-CuFe2O4 nanocrystals within a porous matrix of silica in the form of either an aerogel or a xerogel, and compared to a bulk sample. Extended X-ray absorption fine structure (EXAFS) spectroscopy revealed the presence of two different sub-lattices within the crystal structure of t-CuFe2O4, one tetragonal and one cubic, defined by the Cu2+ and Fe3+ ions respectively. Our investigation provides evidence that the Jahn-Teller distortion, which occurs on the Cu2+ ions located in octahedral sites, does not affect the coordination geometry of the Fe3+ ions, regardless of their location in octahedral or tetrahedral sites.

Manganese doped-iron oxide nanoparticle clusters and their potential as agents for magnetic resonance imaging and hyperthermia.

A simple, one pot method to synthesize water-dispersible Mn doped iron oxide colloidal clusters constructed of nanoparticles arranged into secondary flower-like structures was developed. This method allows the successful incorporation and homogeneous distribution of Mn within the nanoparticle iron oxide clusters. The formed clusters retain the desired morphological and structural features observed for pure iron oxide clusters, but possess intrinsic magnetic properties that arise from Mn doping. They show distinct performance as imaging contrast agents and excellent characteristics as heating mediators in magnetic fluid hyperthermia. It is expected that the outcomes of this study will open up new avenues for the exploitation of doped magnetic nanoparticle assemblies in biomedicine.

Getting order in mesostructured thin films, from pore organization to crystalline walls, the case of 3-glycidoxypropyltrimethoxysilane.

A new type of mesostructured hybrid organic-inorganic film has been synthesised by evaporation-induced self-assembly using 3-glycidoxypropyltrimethoxysilane as the precursor and a tri-block copolymer, Pluronic F127, as the template. The chemistry has been tuned to form bridged polysilsesquioxanes that self-organise into ordered lamellar structures. Controlled aging under highly basic conditions, which has been monitored by Raman and infrared spectroscopy, has been used to obtain the layered ordered hybrid structures in the precursor sol. The pH of the sol has been adjusted to form the micelles that act as templates during solvent evaporation. The self-assembly of the system has been studied in situ by small and wide angle X-ray scattering using a synchrotron light source, which has confirmed both the formation of hybrid layered structures and the long-range organization of the mesophase in the hybrid films. The present approach allows ordering the hybrid film on two different length scales; at the end of film processing, hybrid crystals are incorporated into the pore walls and the micelles are arranged within the films with long range order.

Adsorption of lysozyme on hyaluronic acid functionalized SBA-15 mesoporous silica: a possible bioadhesive depot system.

Silica-based ordered mesoporous materials are very attractive matrices to prepare smart depot systems for several kinds of therapeutic agents. This work focuses on the well-known SBA-15 mesoporous silica and lysozyme, an antimicrobial protein. In order to improve the bioadhesion properties of SBA-15 particles, the effect of hyaluronic acid (HA) functionalization on lysozyme adsorption was investigated. SBA-15 samples having high (H-SBA) and low (L-SBA) levels of functionalization were analyzed during the three steps of the preparations: (1) introduction of the -NH2 groups to obtain the SBA-NH2 samples; (2) functionalization with HA to obtain the SBA-HA matrices; (3) adsorption of lysozyme. All silica matrices were characterized through N2-adsorption/desorption isotherms, small-angle X-ray scattering, transmission electron microscopy, thermogravimetric analysis, and Fourier transform infrared spectroscopy. The whole of the experimental data suggests that a high level of functionalization of the silica surface allows for a negligible lysozyme adsorption mainly due to unfavorable electrostatic interactions (H-SBA-NH2) or steric hindrance (H-SBA-HA). A low degree of functionalization of the silica surface brings about a very good performance toward lysozyme adsorption, being 71% (L-SBA-NH2) and 63% (L-SBA-HA) respectively, compared to that observed for original SBA-15. Finally, two different kinetic models--a "pseudo-second order" and a "intraparticle diffusion"--were compared to fit lysozyme adsorption data, the latter being more reliable than the former.

Graphene-mediated surface enhanced Raman scattering in silica mesoporous nanocomposite films.

Silica mesoporous nanocomposite films containing graphene nanosheets and gold nanoparticles have been prepared via a one-pot synthesis using silicon tetrachloride, gold(III) chloride tetrahydrate, a 1-N-vinyl-2-pyrrolidone dispersion of exfoliated graphene and Pluronic F127 as a structuring agent. The composite films have shown graphene-mediated surface-enhanced Raman scattering (G-SERS). Graphene has been introduced as dispersed bilayer sheets while gold has been thermally reduced in situ to form nanoparticles of around 6 nm which preferentially nucleate on the surface of the graphene nanosheets. The presence of graphene and gold nanoparticles does not interfere with the self-assembly process and the formation of silica mesoporous films ordered as 2D hexagonal structures. The material has shown a remarkable analytical enhancement factor ranging from 80 up to 136 using rhodamine 6G as a Raman probe. The films have been characterised by grazing incidence X-ray diffraction, FTIR and UV-vis spectroscopy studies; transmission electron microscopy and spectroscopic ellipsometry have been used to study the morphology, thickness and porosities of the samples. Raman spectroscopy has been employed to characterise the graphene nanosheets embedded into the mesoporous films and the enhanced Raman scattering.

PEGylated versus non-PEGylated magnetic nanoparticles as camptothecin delivery system.

Camptothecin (CPT; (S)-(+)-4-ethyl-4-hydroxy-1H-pyrano[3',4':6,7]indolizino[1,2-b]quinoline-3,14-(4H,12H)-dione) is a highly cytotoxic natural alkaloid that has not yet found use as chemotherapeutic agent due to its poor water-solubility and chemical instability and, as a consequence, no effective administration means have been designed. In this work, camptothecin has been successfully loaded into iron oxide superparamagnetic nanoparticles with an average size of 14 nm. It was found that surface modification of the nanoparticles by polyethylene glycol enables loading a large amount of camptothecin. While the unloaded nanoparticles do not induce apoptosis in the H460 lung cancer cell line, the camptothecin-loaded nanoparticle formulations exhibit remarkable pro-apoptotic activity. These results indicate that camptothecin retains its biological activity after loading onto the magnetic nanoparticles. The proposed materials represent novel materials based on naturally occurring bioactive molecules loaded onto nanoparticles to be used as chemotherapeutic formulations. The procedure seems apt to be extended to other active molecules extracted from natural products. In addition, these materials offer the potential of being further implemented for combined imaging and therapeutics, as magnetic nanoparticles are known to be multifunctional tools for biomedicine.

Exfoliated graphene into highly ordered mesoporous titania films: highly performing nanocomposites from integrated processing.

To fully exploit the potential of self-assembly in a single step, we have designed an integrated process to obtain mesoporous graphene nanocomposite films. The synthesis allows incorporating graphene sheets with a small number of defects into highly ordered and transparent mesoporous titania films. The careful design of the porous matrix at the mesoscale ensures the highest diffusivity in the films. These exhibit an enhanced photocatalytic efficiency, while the high order of the mesoporosity is not affected by the insertion of the graphene sheets and is well-preserved after a controlled thermal treatment. In addition, we have proven that the nanocomposite films can be easily processed by deep X-ray lithography to produce functional arrays.

Biological applications of magnetic nanoparticles.

In this review an overview about biological applications of magnetic colloidal nanoparticles will be given, which comprises their synthesis, characterization, and in vitro and in vivo applications. The potential future role of magnetic nanoparticles compared to other functional nanoparticles will be discussed by highlighting the possibility of integration with other nanostructures and with existing biotechnology as well as by pointing out the specific properties of magnetic colloids. Current limitations in the fabrication process and issues related with the outcome of the particles in the body will be also pointed out in order to address the remaining challenges for an extended application of magnetic nanoparticles in medicine.

Raman active jagged-shaped gold-coated magnetic particles as a novel multimodal nanoprobe.

The creation of novel engineered multimodal nanoparticles (NPs) is a key focus in bionanotechnology and can lead to deep understanding of biological processes at the molecular level. Here, we present a multi-component system made of gold-coupled core-shell SPIONs, as a new nanoprobe with signal enhancement in surface Raman spectroscopy, due to its jagged-shaped gold shell coating.

Synthesis and characterization of multiwalled carbon nanotube/FeCo nanocomposites.

Multiwalled carbon nanotube/FeCo nanocomposites were produced by Catalytic Chemical Vapour Deposition using highly porous FeCo-SiO2 aerogels with different loadings and dimensions of FeCo nanoparticles as catalysts. Multiwalled carbon nanotubes with average number of walls depending on the size of the catalyst nanoparticles were obtained. Inside the nanotubes spherical or elliptical FeCo nanoparticles are retained, and the magnetic properties of the resulting nanocomposites were characterized in detail.

Design of water-based ferrofluids as contrast agents for magnetic resonance imaging.

We report the synthesis, characterization and relaxometric study of ferrofluids based on iron oxide, with potential for use as magnetic resonance imaging (MRI) contrast agents (CAs). The effect of different cost-effective, water-based surface modification approaches which can be easily scaled-up for the large scale synthesis of the ferrofluids has been investigated. Surface modification was achieved by silanization, and/or coating with non-toxic commercial dispersants (a lauric polysorbate and a block copolymer with pigment affinic groups, namely Tween 20 and Disperbyk 190) which were added after or during iron oxide nanoparticle synthesis. It was observed that all the materials synthesized functioned as negative contrast agents at physiological temperature and at frequencies covered by clinical imagers. The relaxometric properties of the magnetic nanoparticles were significantly improved after surface coating with stabilizers compared to the original iron oxide nanoparticles, with particular reference to the silica-coated magnetic nanoparticles. The results indicate that the optimization of the preparation of colloidal magnetic ferrofluids by surface modification is effective in the design of novel contrast agents for MRI by enabling better or more effective interaction between the coated iron oxide nanoparticles and protons present in their aqueous environment.

Preparation of Mn, Ni, Co ferrite highly porous silica nanocomposite aerogels by an urea-assisted sol-gel procedure.

The preparation of highly porous MnFe2O4-SiO2 and NiFe2O4-SiO2 nanocomposite aerogels with high purity and homogeneity was successfully achieved by a sol-gel procedure involving urea-assisted co-gelation of the precursor phases firstly applied for the synthesis of CoFe2O4-SiO2. This method allows fast gelation, giving rise to aerogels with 97% porosity. The structural, morphological and textural characterization as a function of thermal treatments was carried out by a multitechnique approach confirming that, as in the case of CoFe2O4-SiO2, the formation of single nanocrystals of manganese ferrite and nickel ferrite with spinel structure occurs after heating at 750 degrees C and is complete at 900 degrees C when the high porosity typical of aerogels is still retained. Thermogravimetric analysis (TG), differential thermal analysis (DTA), N2-physisorption at 77 K, powder X-ray diffraction (XRD), and transmission electron microscopy (TEM) indicate that the compositional homogeneity, crystallite size, thermal stability, and porosity are controlled by the sol-gel parameters of the preparation.

Role of urea in the preparation of highly porous nanocomposite aerogels.

The preparation of highly porous CoFe2O4-SiO2 nanocomposite aerogels was successfully achieved by a novel sol-gel procedure involving urea-assisted co-gelation of the precursor phases. This method allows fast gelation, giving rise to an aerogel with 97% porosity. The formation of CoFe2O4 nanocrystals homogeneously distributed within the matrix occurs after calcination at 750 degrees C and is complete at 900 degrees C. Despite the high temperature required for the formation of the CoFe2O4 nanocrystals, the high porosity typical of aerogels is still retained.

The concept of delayed nucleation in nanocrystal growth demonstrated for the case of iron oxide nanodisks.

A comprehensive study of iron oxide nanocrystal growth through non-hydrolitic, surfactant-mediated thermal reaction of iron pentacarbonyl and an oxidizer has been conducted, which includes size control, anisotropic shape evolution, and crystallographic phase transition of monodisperse iron oxide colloidal nanocrystals. The reaction was monitored via in situ UV-vis spectroscopy, taking advantage of the color change accompanying the iron oxide colloid formation, allowing measurement of the induction time for nucleation. Features of the synthesis such as the size control and reproducibility are related to the occurrence of the observed delayed nucleation process. As a separate source of iron and oxygen is adopted, phase control could also be achieved by sequential injections of oxidizer.