Asymmetric binary nanocrystals (BNCs) formed by a spherical gamma-Fe(2)O(3) magnetic domain epitaxially grown onto a lateral facet of a rodlike anatase TiO(2) nanorod have been functionalized with PEG-terminated phospholipids, resulting in a micellar system that enables the BNC dispersion in aqueous solution. The further processability of the obtained water-soluble BNC including PEG lipid micelles and their use in bioconjugation experiments has been successfully demonstrated by covalently binding to bovine serum albumin (BSA). The whole process has also been preliminarily performed on spherical iron oxide nanocrystals (NCs) and TiO(2) nanorods (NRs), which form single structural units in the heterostructures. Each step has been thoroughly monitored by using optical, structural, and electrophoretic techniques. In addition, an investigation of the magnetic behavior of the iron oxide NCs and BNCs, before and after incorporation into PEG lipid micelles and subsequently bioconjugation, has been carried out, revealing that the magnetic characteristics are mostly retained. The proposed approach to achieving water-soluble anisotropic BNCs and their bioconjugates has a large potential in catalysis and biomedicine and offers key functional building blocks for biosensor applications.

The fabrication of highly monodisperse silica coated Au NPs by the microemulsion approach and the selection of the nanostructure morphology have been described. Several experimental conditions, synthetic parameters and post-preparative strategies such as reaction time, precursor concentration, size selection techniques and NP surface treatments have been suitably investigated in order to fabricate Au and Au@SiO2 NPs with peculiar and tuneable plasmonic properties that strongly depend on the specific size distribution and nanostructure morphology. In particular, size selected precipitation of oleylaminecapped Au NPs by antisolvent titration has successfully offered a strategy to discriminate and collect monodisperse fractions with different average size and narrow size distribution. Moreover, for the first time, a deep insight into the microemulsion mechanism for the silica shell growth has been provided, highlighting the critical role played by the density of oleylamine at the Au NP surface. Specifically the capping agent has been demonstrated to strongly determine the multiplicity of the core in the final Au@SiO2 nanostructures. Density gradient centrifugation has been finally performed to sort the achieved Au@SiO2 NPs with different morphologies, which was ultimately able to recover a significant fraction formed of two Au NPs in one silica shell. A systematic characterization of the Au and Au@SiO2 NPs has been carried out by complementary morphological and spectroscopic techniques. These deeply investigated materials, with tuneable plasmonic properties, have been proposed as versatile building blocks useful for the design and fabrication of plasmonic and photonic structures as well as metamaterials for device applications.

In this work a genuine combination of a bottom-up approach, which is based on synthesis andfunctionalization of emitting nanocrystals (NCs), with a top-down strategy, which relies on aflexible and versatile cold plasma process, is shown. Luminescent semiconducting colloidalNCs consisting of a CdSe core coated with a ZnS shell (CdSe@ZnS) are directly assembledonto micro-patterned substrates previously functionalized by means of glow dischargesperformed through physical masks. The NC assembly is driven by electrostatic interactionsthat led to their successful organization into spatially resolved domains. Two distinct protocolsare tested, the former using a plasma deposition process combined with an electrostaticlayer-by-layer procedure, the latter based on a two-step plasma deposition/treatment process.The procedures are thoroughly monitored with fluorescence microscopy, atomic forcemicroscopy, x-ray photoelectron spectroscopy, Fourier transform infrared spectroscopy,transmission electron microscopy and scanning electron microscopy. The two-step plasmaprotocol is demonstrated to be more efficient in directing a uniform and specific assembly ofluminescent NCs with respect to the hybrid procedure. The presented 'mix and match'approach offers great potential for integrating NCs, with their unique size-dependentproperties, into microstructures, providing a universal platform for the fabrication of sensors,biochips, displays and switches.

Organic capped Au nanoparticles (NPs) and PbS quantum dots (QDs), synthesized with high control on size and size distribution, were used as building blocks for fabricating solid crystals by solvent evaporation. The superlattice formation process for the two types of nano-objects was investigated as a function of concentration by means of electron microscopy and X-ray techniques. The effect of building block composition, size, geometry, and concentration and the role of the organic coordinating molecules was related to the degree of order in the superlattices. A convenient combination of different complementary X-ray techniques, namely in situ and ex situ GISAXS and GIWAXS, allowed elucidating the most reliable signatures of the superlattices at various stages of the self-assembly process, since their early stage of formation and up to few months of aging. Significantly different assembly behaviour was assessed for the two types of NPs, clearly explained on the basis of their chemical composition, ultimately reflecting on the assembling process and on the final structure characteristics.

Hydrophobic PbS nanocrystals (NCs) emitting in the near infrared spectral region were encapsulated in the core of micelles and in the bilayer of liposomes, respectively, to form polyethylene glycol (PEG)-grafted phospholipids. The phospholipid-based functionalization process of PbS NCs required the replacement of the pristine capping ligand at the NC surface with thiol molecules. The procedures carried out for two systems, micelles and liposomes, using PEG-modified phospholipids were carefully monitored by optical, morphological and structural investigations. The hydrodynamic diameter and the colloidal stability of both micelles and liposomes loaded with PbS NCs were evaluated using Dynamic Light Scattering (DLS) and ?-potential experiments, and both were satisfactorily stable in physiological media. The cytotoxicity of the resulting PbS NC-loaded nanovectors was assessed by the in vitro investigation on Saos-2 cells, indicating that the toxicity of the PbS NC loaded liposomes was lower than that of the micelles with the same NC cargo, which is reasonable due to the different overall composition of the two prepared nanocarriers. Finally, the cellular uptake in the Saos-2 cells of both the NC containing systems was evaluated by means of confocal microscopy studies by exploiting a visible fluorescent phospholipid and demonstrating the ability of both luminescent nanovectors to be internalized. The obtained results show the great potential of the prepared emitting nanoprobes for imaging applications in the second biological window.

Sorafenib is an orally active multikinase inhibitor and it is only anticancer drug that has proved to significantly prolong the survival time in patients with advanced hepatocellular carcinoma (HCC), when not candidates for potentially curative treatment or transarterial chemoembolization. However, sorafenib is characterized by severe toxic side effects limiting the possible therapeutic response (1,2). Nanoparticle (NP) based approaches offer a valuable alternative for cancer drug delivery, functioning as a carrier for entry through fenestrations in tumor vasculature, thus allowing direct cell access and ensuring the accumulation of high concentrations of drug to the targeted cancer cell, with a concomitant reduced toxicity of normal tissue. In this contest, superparamagnetic iron oxide NPs (SPIONs) are very attractive for delivery of therapeutic agents as they have been reported to enhance the drug delivery to specific locations in the body through the application of an external magnetic field (3,4). Here, solid lipid NPs (SLN) containing sorafenib and SPIONs have been prepared by a hot homogenization technique using cetyl palmitate as lipid matrix and polyethylene glycol modified phospholipids (PEG lipids), in order to achieve a PEG-based anti-fouling coating on SLN surface. These nanoformulations, thoroughly investigated by means of complementary techniques, have finally resulted effective drug delivery magnetic nanovectors with good stability in aqueous medium and high drug encapsulation efficiency (% EE>90%). In addition, the relaxometric characterization has proven that the magnetic SLN loaded with sorafenib are also very efficient contrast agents, with a great potential in magnetic resonance imaging (MRI) technique. The proposed magnetic SLNs loaded with sorafenib represent promising candidates for image guided and magnetic targeting of sorafenib to liver towards an efficacious treatment of HCC.

Advanced hepatocellular carcinoma (HCC) is a clinical challenge with limited treatment options. The orally activemultikinase inhibitor sorafenib is the only anticancer agent showing a survival benefit in these patients.As well as significant activity, sorafenib is characterized by severe toxic side effects limiting the possible therapeuticresponse (1). Nanoparticle (NP) based approaches offer a valuable alternative for cancer drug delivery,thus ensuring the accumulation of high concentrations of drug to the targeted cancer cell, with a concomitantreduced toxicity of normal tissue. Superparamagnetic iron oxide NPs (SPIONs) are very attractive for deliveryof therapeutic agents as they have been reported to enhance the drug delivery to specific locations in thebody through the application of an external magnetic field (2). Here, solid lipid NPs (SLNs) containing sorafeniband SPIONs have been prepared by a hot homogenization technique using cetyl palmitate as lipid matrix andpolyethylene glycol modified phospholipids (PEG lipids), in order to achieve a PEG-based anti-fouling coating onSLN surface. These nanoformulations, thoroughly investigated by means of complementary techniques, havefinally resulted effective drug delivery magnetic nanovectors with good stability in aqueous medium and highdrug encapsulation efficiency. In addition, the relaxometric characterization has proven that the magnetic SLNloaded with sorafenib are also very efficient contrast agents, with a great potential in magnetic resonance imagingtechnique. The proposed magnetic SLNs loaded with sorafenib represent promising candidates for imageguided and magnetic targeting of sorafenib to liver towards an efficacious treatment of HCC.

The fabrication of hierarchical architectures of colloidal nanoparticles (NPs) represents an increasingly relevant approach to obtain innovative mesoscale materials, thanks to the original size-dependent characteristics of the nanosized building blocks, as well as, the collective properties arising from their organization. Here, an unconventional patterning method, based on formation of "breath figures" (BF), has been used to fabricate highly ordered honeycomb structures in nanocomposite materials, obtained by blending pre-synthesized colloidal gold NPs (Au NPs) in a polymeric matrix. The cast nanocomposite solutions have successfully allowed the fabrication of highly regular microporous self standing films. Large scale iridescent and ordered micropatterns with an hexagonal symmetry have been prepared and the fundamental role of NPs in stabilizing the templating water droplets in BF formation has been demonstrated. The resulting structured arrays of NP decorated pores can have a great potential as efficient catalysts for chemical reactions, as well as, templates for fabrication of photonic and optoelectronic devices, sensors and membranes for separation and purification purposes. © 2014 by American Scientific Publishers.

A fundamental and systematic study on the fabrication of a supramolecularly assembled nanostructure of an organic ligand-capped CdS nanocrystal (NC) and multiple heptamine beta-cyclodextrin ((NH2)(7)beta CD) molecules in aqueous solution has been here reported. The functionalization process of presynthesized hydrophobic CdS NCs by means of (NH2)(7)beta CD has been extensively investigated by using different spectroscopic and structural techniques, as a function of different experimental parameters, such as the composition and the concentration of CD, the concentration of CdS NCs, the nature of the NC surface capping ligand (oleic acid and octylamine), and the organic solvent. The formation of a complex based on the direct coordination of the (NH2)(7)beta CD amine groups at the NC surface has been demonstrated and found responsible for the CdS NC phase transfer process. The amine functional group in (NH2)(7)beta CD and the appropriate combination of pristine capping agent coordinating the NC surface and a suitable solvent have been found decisive for the success of the CdS NC phase transfer process. Furthermore, a layer-by-layer assembly experiment has indicated that the obtained (NH2)(7)beta CD functionalized CdS NCs are still able to perform the host guest chemistry. Thus, they offer a model of a nanoparticle-based material with molecular receptors, useful for bio applications.

A flexible host has been selected to achieve, for the first time, functional nanocomposites based on CdSe@ZnS core-shell type quantum dots (QDs) and Au nanoparticles (NPs), simultaneously dispersed in a polymer matrix. Coherent interactions between QDs and plasmonic Au NPs embedded in PDMS films have been demonstrated to lead to a relevant enhancement of the absorption cross-section of the QDs, remarkably modifying the optical response of the entire system. Optical and time resolved spectroscopy studies revealed an active gain-plasmon feedback behind the super-absorbing overall effect.

The fabrication of uniform and patterned nanocrystal (NC) assemblies has been investigated by exploiting the possibility of carefully tailoring colloidal NC surface chemistry and the ability of polyelectrolyte (PE) to functionalize substrates through an electrostatic layer-by-layer (LbL) strategy. Appropriate deposition conditions, substrate functionalization, and post-preparative treatments were selected to tailor the substrate surface chemistry to effectively direct the homogeneous electrostatic-induced assembly of NCs. Water-dispersible luminescent NCs, namely, (CdSe)ZnS and CdS, were differently functionalized by (1) ligand-exchange reaction, (2) growth of a hydrophilic silica shell, and (3) formation of a hydrophilic inclusion complex, thus providing functional NCs stable in a defined pH range. The electrostatically charged functional NCs represent a comprehensive selection of examples of surface-functionalized NCs, which enables the systematic investigation of experimental parameters in NC assembly processes carried out by combining LbL procedures with microcontact printing and also exploiting NC emission, relevant for potential applications, as a prompt and effective probe for evaluating assembly quality. Thus, an ample showcase of combinations has been investigated, and the spectroscopic and morphological features of the resulting NC-based structures have been discussed.

Amphiphilic polystyrene-block-polyethylene oxide (PS-b-PEO) block copolymers (BCPs) have been demonstrated to be effective in directing organization of colloidal Au nanoparticles (NPs). Au NPs have been incorporated into the polymer and the different chemical affinity between the NP surface and the two blocks of the BCP has been used as a driving force of the assembling procedure. The morphology of the nanocomposites, prepared and fabricated as thin films, has been investigated by means of atomic force and scanning electron microscopies as a function of the NP content and BCP molecular weight. NPs have been effectively dispersed in PS-b-PEO hosts at any investigated content (up to 17 wt%) and a clear effect of the BCP properties on the final nanocomposite morphology has been highlighted. Finally, electrostatic force microscopy has demonstrated the conductive properties of the nanocomposite films, showing that the embedded Au NPs effectively convey their conductive properties to the film. The overall investigation has confirmed the selective confinement of the as-prepared surfactant-coated metal NPs in the PS block of PS-b-PEO, thus proposing a very simple and prompt assembling tool for nanopatterning, potentially suitable for optoelectronic, sensing and catalysis applications.

Colloidal white emitting nanostructures were successfully fabricated by covalently binding a blue emitting oligofluorene at the surface of silica beads, that incorporate orange luminescent colloidal CdSe@ZnS quantum dots (QDs). White light was achieved by carefully tuning the size of the QDs to complementarily match the emission color of the blue fluorophore and taking into account the delicate balance between the emission of the QDs in the core of the silica beads and the amount of the organic dye bound to the silica surface. The proposed approach is highly versatile as it can be extended to the fabrication of a variety of luminescent hybrid nano-objects, playing with the complementarity of the emission color of the inorganic and organic fluorophores at the nanoscale. This journal is © the Partner Organisations 2014.