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.

Curcumin is a natural polyphenol with anti-oxidative, anti-inflammatory and anti-cancer properties but its therapeutic potential is substantially hindered by the rather low water solubility and bioavailability. Thus, in this work, a new soluble inclusion complex of curcumin with sulfobutylether--cyclodextrin (SBE-β-CD) was prepared in solution and at the solid state using different preparation techniques and characterized by FT-IR, NMR, DSC, SEM, phase solubility studies and Job’s plot method. Results clearly indicate that curcumin reacts with SBE-β-CD to form a host-guest complex with an apparent formation constant of 1455 M-1. Moreover, SBE-β-CD strongly increases water solubility of curcumin (from 0.56 to 102.78 g/ml, at 25◦C) and lyophilization method seems to be the best preparation technique to obtain the complex at the solid state. Finally, an in vitro test on a human hepatic cancer cell line (HepG-2) shows that complexation positively influences curcumin anticancer and antioxidant activity

Nanoparticles (NPs) emitting in the second biological near infrared (NIR) window of the electromagnetic spectrum have been successfully synthesized by growing a silica shell on the hydrophobic surface of OLEA/TOP PbS nanocrystals (NCs), by means of a reverse microemulsion approach, and subsequently decorated with biotin molecules. The fabrication of very uniform and monodisperse NPs, formed of SiO2 shell coated single core PbS NCs, has been demonstrated by means of a set of complementary optical and structural techniques (Vis-NIR absorption and photoluminescence spectroscopy, transmission electron microscopy) that have highlighted how experimental parameters, such as PbS NC and silica precursor concentration, are crucial to direct the morphology and optical properties of silica coated PbS NPs. Subsequently, the silica surface of the core-shell NPs has been grafted with amino groups, in order to achieve covalent binding of biotin to NIR emitting silica coated NPs. Finally the successful reaction with a green-fluorescent labelled streptavidin has verified the molecular recognition response of the biotin molecules decorating the PbS@SiO2 NP surface. Dynamic light scattering (DLS) and zeta-potential techniques have been used to monitor the hydrodynamic diameter and colloidal stability of both PbS@SiO2 and biotin decorated NPs, showing their high colloidal stability in physiological media, as needed for biomedical applications. Remarkably the obtained biotinylated PbS@SiO2 NPs have been found to retain emission properties in the 'second optical window' of the NIR region of the electromagnetic spectrum, thus representing attractive receptor-targeted NIR fluorescent probes for in vivo tumour imaging.

Nanostructured films based on Au nanorods (NRs) have been obtained by layer-by-layer (LbL) assembly driven by electrostatic interaction between metal nanoparticles and polyelectrolytes. Multilayer films have been fabricated by using LbL assembly of poly(sodium styrenesulfonate) (PSS) and positively charged Au NRs on a polyelectrolyte-modified substrate. The effect of fabrication parameters, including the nature of the substrate, the polyelectrolyte initial anchoring layer, and the number of layers has been investigated by means of UV vis absorbance spectroscopy and atomic force microscopy (AFM). The results demonstrated the dependence of morphology and plasmonic features in the multilayered nanostructured architectures from the nature of the anchoring polyelectrolyte on the substrate, the number of layers, and the kind of NR mutual assembly. In addition, a study of the electrochemical activity at the solid/liquid interface has been carried out in order to assess charge transport through the NR multilayer by using two molecular probes in solution, namely, potassium ferricyanide, a common and well-established redox mediator with reversible behavior, and cytochrome C, a robust model redox protein. The presented systematic study of the immobilization of Au NRs opens the venue to several application areas, such as (bio)chemical sensing.

Here a luminescent hybrid nanostructure based on functionalized quantum dots (QDs) is used as a fluorescent imaging agent able to target selectively mitochondria thanks to the molecular recognition of the translocator protein (TSPO). The selective targeting of such an 18 kDa protein mainly located in the outer mitochondrial membrane and overexpressed in several pathological states including neurodegenerative diseases and cancers may provide valuable information for the early diagnosis and therapy of human disorders. In particular, the rational design of amino functionalized luminescent silica coated QD nanoparticles (QD@SiO2 NPs) provides a versatile nanoplatform to anchor a potent and selective TSPO ligand, characterized by a 2-phenyl-imidazo[1,2-a] pyridine acetamide structure along with a derivatizable carboxylic end group, useful to conjugate the TSPO ligand and achieve TSPO-QD@SiO2 NPs by means of a covalent amide bond. The colloidal stability and optical properties of the proposed nanomaterials are comprehensively investigated and their potential as mitochondrial imaging agents is fully assessed. Subcellular fractionation, together with confocal laser scanning fluorescence microscopy and co-localization analysis of targeted TSPO-QD@SiO2 NPs in C6 glioma cells overexpressing the TSPO, proves the great potential of these multifunctional nanosystems as in vitro selective mitochondrial imaging agents.

Binary asymmetric nanocrystals (BNCs), composed of a photoactive TiO2 nanorod joined with a superparamagnetic gamma-Fe2O3 spherical domain, were embedded in polyethylene glycol modified phospholipid micelle and successfully bioconjugated to a suitably designed peptide containing an RGD motif. BNCs represent a relevant multifunctional nanomaterial, owing to the coexistence of two distinct domains in one particle, characterized by high photoactivity and magnetic properties, that is particularly suited for use as a phototherapy and hyperthermia agent as well as a magnetic probe in biological imaging. We selected the RGD motif in order to target integrin expressed on activated endothelial cells and several types of cancer cells. The prepared RGD-peptide/BNC conjugates, comprehensively monitored by using complementary optical and structural techniques, demonstrated a high stability and uniform dispersibility in biological media. The cytotoxicity of the RGD-peptide/BNC conjugates was studied in vitro. The cellular uptake of RGD-peptide conjugates in the cells, assessed by means of two distinct approaches, namely confocal microscopy analysis and emission spectroscopy determination in cell lysates, displayed selectivity of the RGD-peptide-BNC conjugate for the alpha v beta 3 integrin. These RGD-peptide-BNC conjugates have a high potential for theranostic treatment of cancer.

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.

The photocatalytic properties of anatase TiO(2) nanorods (NRs) and noble metal-semiconductor nanocomposites (TiO(2) NRs/Ag) prepared by colloidal chemistry routes and immobilized onto suitable substrates were investigated. Photocatalytic experiments were performed under UV irradiation in order to test the degradation of a target compound (the azo dye, methyl red) in aqueous solution using TiO(2) P25 Degussa as a reference material. Absorbance spectroscopy and liquid chromatography/mass spectrometry (LC/MS) measurements pointed out that, according to pH conditions, TiO(2) NRs and TiO(2) NRs/Ag presented a photoactivity up to 1.3 and 2 times higher than TiO(2) P25 Degussa, respectively. Notably, the TiO(2) NRs/Ag-based catalysts demonstrated a photocatalytic activity 2-fold higher than bare TiO(2) NRs. Remarkably, only a negligible dependence on pH conditions was detected for the nanocomposite catalyst, whereas both TiO(2) NRs and TiO(2) P25 Degussa showed much higher photoactivity at acidic pH. In all the investigated cases, the identified byproducts pointed out the occurrence of the same reaction mechanism, basically relying on the hydroxyl radical attaching on the benzene ring and on the homolytic rupture of the nitrogen-carbon bond of the dimethyl-amino moiety.

Two different nanosized TiO2-based catalysts supported onto glass with tailored photocatalytic properties upon irradiation by UV light were successfully employed for the degradation of nalidixid acid, a widely diffused antibacterial agent of environmental relevance known to be non-biodegradable. Anatase rod-like TiO2 nanocrystals (TiO(2)NRs) and a semiconductor oxide-noble metal nanocomposite TiO2 NRs/Ag nanoparticles (NPs), synthesized by colloidal chemistry routes, were cast onto glass slide and employed as photocatalysts. A commercially available catalyst (TiO2 P25), also immobilized onto a glass slide, was used as a reference material. It was found that both TiO2 NRs/Ag NPs composite and TiO2 NRs demonstrated a photocatalytic efficiency significantly higher than the reference TiO2 P25. Specifically, TiO2 NRs/Ag NPs showed a photoactivity in nalidixic acid degradation 14 times higher than TiO2 P25 and 4 times higher than bare TiO2 NRs in the first 60 min of reaction. Several by-products were identified by HPLC-MS along the nalidixic acid degradation, thus getting useful insight on the degradation pathway. All the identified by-products resulted completely removed after 6 h of reaction. (C) 2013 Elsevier Ltd. All rights reserved.

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.

A reliable strategy is presented to combine the preparation of functional building blocks based on polymer beads decorated with luminescent nanocrystals (NCs) and their precise positioning onto suitable patterns by capillary assembly technique. In particular, a layer-by-layer (LbL) polyelectrolyte (PE) deposition procedure has been implemented to provide uniform NC coverage on PS beads, thus conveying the optical properties of luminescent nanocrystals to highly processable PS beads. The latter have then been integrated into patterned stamps by means of template-driven capillary assembly. Their selective positioning has been directed by means of pattern geometry. The use of luminescent (CdSe)ZnS NCs offers a direct optical probe to evaluate the efficiency of the positioning procedure on the substrate, enabling the extension of the method to a wide range of materials, i.e., NCs with different compositions and specific geometry-dependent properties. Moreover, the precise control over the pattern geometry and the micrometer accuracy in positioning achieved by capillary assembly make such functional patterned structures excellent candidates for integration into devices exploiting specific size-dependent NC properties.

The increasing importance of sigma-2 receptor as target for the diagnosis and therapy of tumors paves the way for the development of innovative optically traceable fluorescent probes as tumor cell contrast and therapeutic agents. Here, a novel hybrid organic-inorganic nanostructure is developed by combining the superior fluorescent properties of inorganic quantum dots (QDs), coated with a hydrophilic silica shell (QD@SiO2 NPs), the versatility of the silica shell, and the high selectivity for sigma-2 receptor of the two synthetic ligands, namely, the 6-[(6-aminohexyl)oxy]-2-(3-(6,7-dimethoxy-3,4-dihydroisoquinolin-2(1H)-yl)propyl)-3,4-dihydroisoquinolin-1(2H)-one (MLP66) and 6-[1-[3-(4-cyclohexylpiperazin-1-yl)propyl]-1,2,3,4-tetrahydronaphthalen-5-yloxy]hexylamine (TA6). The proposed nanostructures represent a challenging alternative to all previously studied organic small fluorescent molecules, based on the same sigma-2 receptor affinity moieties. Flow cytometry and confocal fluorescence microscopy experiments, respectively, on fixed and living cancerous MCF7 cells, which overexpress the sigma-2 receptor, prove the ability of functionalized (QD@SiO2-TA6 and QD@SiO2-MLP66) NPs to be internalized and demonstrate their affinity to the sigma-2 receptor, ultimately validating the targeting properties conveyed to the NPs by sigma-2 ligand conjugation. The presented QD-based nanoprobes possess a great potential as in vitro selective sigma-2 receptor imaging agent and, consequently, could provide a significant impact to future theranostic applications.

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.

Au nanoparticles (NPs) self-assembled by means of a simple solvent evaporation strategy in a two-dimensional (2D) superlattice with a highly controlled geometry and extending over micrometers squared when drop cast onto a suitably functionalized silicon substrate. The assembly procedure was defined by carefully monitoring experimental parameters, namely, dispersing solvent, deposition temperature, Au NP concentration, and chemistry of supporting substrate. The investigated parameters were demonstrated to play a significant role on the delicate energetic balance of the mutual NPs as well as NP-substrate interactions, ultimately directing the NP assembly. Remarkably, substrate surface chemistry revealed to be decisive to control the extent of the organization. Scanning electron microscopy demonstrated that the 2D superlattice extends uniformly over hundreds of square micrometers. Grazing-incidence small-angle X-ray scattering investigation validated the Au NP organization in crystalline domains and confirmed the role played by the surface chemistry of the substrate onto the 2D lattice assembly. Finally, preliminary spectroscopic ellipsometry investigation allowed extraction of optical constants of NP assemblies. The localized surface plasmon resonance modes of the NP assemblies were studied through a combined analysis of reflection, transmission, and ellipsometric data that demonstrated that the plasmonic properties of the Au NP assemblies strongly depend on the substrate, which was found to influence NP ordering and near-field interactions between NPs.