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.

We report on the preparation of luminescent collectors based on poly(methyl methacrylate) (PMMA) thin films doped with a red-emitting 2-amino-7-acceptor-9-silafluorene, where the amino group is -N(CH3)(2) and the acceptor is -CH=C(CN)(2). The results obtained from photophysical investigations of the dye in different solvents and in PMMA are very encouraging as the silafluorene dyes turn out to be highly dispersed in the solid matrix, stable upon irradiation and highly emissive. QY and lifetime investigations demonstrate that autoabsorption phenomena moderately occur with SilaFluo content, and the optical features still maintained very significant, also at the highest fluorophore concentration (QY similar to 65%). Study of the LSCs features yields excellent optical efficiencies of 9.6% attained for 25 mm thick PMMA films containing the 1.5 wt% of SilaFluo. This performance is at the top level with respect to the current state-of-art of similar devices based on perylene-based fluorophores such as Lumogen Red.

Rod-coil block copolymers (BCPs) can be powerful tools to achieve ideal morphologies in bulk heterojunction (BHJ) solar cells, which require an interprenetrating network between donor and acceptor material at the nanoscale. Their self-assembly behavior is strictly connected to the lenght of the two blocks and to the synthetic route to their preparation. Step-growth strategy implies the preparation of two blocks properly functionalized to covalently react. Chain-growth method consists, instead, of the preparation of a macroinitiator activated with an end-group directly capable to promote the polymerization of the second block or to be converted into a functional group able to do it.Many conjugated polymers were used as rigid moiety in BCPs for solar cells. For the fist time, we used a low band-gap copolymer, poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b:3.4-b']dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT) intesively studied as donor material into hybrid solar cells (HSCs). Poly-4-vynilpyridine (P4VP), was selected as flexible segment that allows the interaction with acceptor materials, in particular semiconducting inorganic nanoparticles, as CdSe nanocristals (NCs). Exploiting both synthetic approaches, with a proper combination of Suzuki Coupling and Nitroxide-Mediated Radical Polymerization (NMRP), two different series of BCPs were obtained, deeply investigated to elucidate their molecular structure, and then tested into the active layer of HSCs, as nanostructuring compatibilizer.

Low band gap (LGB) polymers are characterized by a band gap below 2 eV, thus absorbing light with wavelengths longer than 620 nm.1 Their polymeric chains are constituted by the alternating electron-rich and electron-poor units. LGB were widely studied in last decades to improve the efficiency of organic photovoltaics (OPVs) due to a better overlap with the solar spectrum, leading to a maximum photon harvesting in the devices.2Combining this intrinsic feature with the appealing capability of the block copolymers (BCPs) to nanosegregate, we obtained new rod-coil BCPs with a rigid segment constituted by a LBG polymer and a flexible one made up of poly-4vinylpyridine (P4VP) or a segmented poly(styrene-random-4-vynilpyridine). P4VP allows the interaction with commonly used acceptor materials for organic or hybrid PVs.3 Two strategies were applied to the preparation of the target polymers, combining a nitroxide-mediated radical polymerization and a Suzuki polycondensation. A step-growth like approach, consisting in the synthesis, purification, and characterization of the two blocks separately, that were then coupled through a further Suzuki reaction, and a chain-growth like method, constituted by the early synthesis of a properly activated rigid macroiniziator for the subsequent polymerization of the flexible block. The two pathways led to two series of materials differing particularly in controlling the coil block length. Due to the strong differences in chemical-physical properties of the two blocks, the purification and characterization procedures of the obtained materials have to be ad hoc tailored for a correct determination of their molecular structure, crossing the data from different techniques.4These materials showed, together with their self-assembling capability, interesting features exploitable for photovoltaic applications. Some of the obtained materials were successfully employed as nanostructuring additive in hybrid solar cells, with inorganic semiconductor nanoparticles of CdSe, as acceptor.5 New trials are in progress for the realization of composites nanostructures with PCBM in aqueous medium, to be used as active layers in bulk heterojunctions solar cells. Preliminary results of these studies will be presented.Acknowledgments: research supported by Project AQUA-SOL - Aqueous processable polymer solar cells: from materials to photovoltaic modules (PRIN 2012A4Z2RY)1 Bundgaard, Krebs, Solar En Mater & Solar Cells 91 (2007) 954.2 Jayakannan, Van Hal, Janssen , J. Pol. Sci. A Pol. Chem 40 (2002) 251.3 Di Mauro, Toscanini, Piovani, Samperi, Curri, Corricelli, Comparelli, Agostiano, Destri, Striccoli, Eur Pol J 72 (2014) 222.4 Zappia, Mendichi, Battiato, Scavia, Mastria, Samperi, Destri, Polymer 80 (2015) 245; Samperi, Montaudo Battiato, Zappia, Destri, paper submitted.5 Zappia, Destri, Striccoli, Curri, Di Mauro, Zoobia, Maruccio, Rizzo, Mastria, Adv. Sci. Technol. 93 (2014) 235; Zappia, Di Mauro, Mastria, Rizzo, Curri, Striccoli,

A simple and cost-effective strategy for mercury ion sensing based on an easy and reliable colorimetric approach is investigated through L-cysteine functionalized gold nanorods (Au NRs). Detection tests are performed on several ions, such as Hg2+, Zn2+, Cd2+, Cu2+, Pb2+, and As2+, and monitored by UV-Vis absorption spectroscopy, transmission electron microscopy (TEM), and infrared spectroscopy (ATR-FTIR). L-cysteine functionalized Au NRs demonstrated a remarkable sensitivity for Hg2+ with limit of detection (LOD) at a few ppt level. A red-shift in the maximum of the typical longitudinal plasmon band of Au NRs is observed and recognized related to aggregation phenomena occurring among functionalized Au NRs and triggered only by the presence of Hg2+ ions in solution. Interestingly, a significantly different response is recorded for the other tested ions. The results highlight that the functionalization of Au NRs with L-cysteine is an excellent route to implement a reliable colorimetric sensing device, able to push further down the LOD recorded for similar strategies based on spherical Au NPs.

A simple and low cost strategy for heavy metal sensing based on an easy and reliable colorimetric detection was investigated by using water soluble gold nanorods (Au NRs), functionalized with L-cysteine. Detection tests have been performed on several heavy metal ions, namely Zn2+, Cd2+, Hg2+, Cu2+, Pb2+ and As3+ ions and monitored by UV-Vis absorption spectroscopy and transmission electron microscopy (TEM). The system has demonstrated a remarkable sensitivity for Hg2+ with limit of detection (LOD) at ppt level. A red-shift in the maximum of the typical longitudinal plasmon band of Au NRs has been observed and recognized related to aggregation phenomena occurring among Au NRs only in presence of Hg2+ ions. Interestingly, a significantly different response is recorded for the other tested heavy metal ions. The results highlight that the functionalization of Au NRs with L-cysteine is an excellent route to implement a reliable colorimetric sensing device, able to push further down the detection limit recorded for similar strategies based on spherical Au NPs.

The unique size-and shape-dependent electronic properties of nanocrystals (NCs) make them extremely attractive as novel structural building blocks for constructing a new generation of innovative materials and solid-state devices. Recent advances in material chemistry has allowed the synthesis of colloidal NCs with a wide range of compositions, with a precise control on size, shape and uniformity as well as specific surface chemistry. By incorporating such nanostructures in polymers, mesoscopic materials can be achieved and their properties engineered by choosing NCs differing in size and/or composition, properly tuning the interaction between NCs and surrounding environment. In this contribution, different approaches will be presented as effective opportunities for conveying colloidal NC properties to nanocomposite materials for micro and nanofabrication. Patterning of such nanocomposites either by conventional lithographic techniques and emerging patterning tools, such as ink jet printing and nanoimprint lithography, will be illustrated, pointing out their technological impact on developing new optoelectronic and sensing devices.

Rod-shaped TiO2 nanocrystals (TiO2 NRs), capped by oleic acid molecules (OLEA), were synthesized with controlled size, shape and surface chemistry by using colloidal routes. They were investigated for application as coating materials for preserving architectural stone of monumental and archaeological interest, in consideration of their self-cleaning and protection properties. For this purpose, two different deposition techniques, namely casting and dipping, were tested for the application of a nanocrystal dispersion on a defined stone type, as a relevant example of porous calcarenites, namely the Pietra Leccese, a building stone widely used in monuments and buildings of cultural and historic interest of the Apulia region (Italy). The physical properties of the stone surface were investigated before and after the treatment with the prepared nanostructured materials. In particular, colour, wettability, water transfer properties and stability of the coating were monitored as a function of time and of the application method. The self-cleaning properties of the TiO2 NRs coated surfaces were tested under simulated and real solar irradiation. The obtained results were discussed in the light of the specific surface chemistry and morphology of TiO2 NRs, demonstrating the effectiveness of TiO2 NRs as an active component in formulations for stone protection.

Room Temperature Ionic Liquids (ILs) have been intensively investigated as promising materials for applications in the field of energy conversion and storage. Furthermore, Polymeric ionic liquids (PILs) are a relatively new class of polyelectrolytes, merging peculiar physical-chemical features of ionic liquids with flexibility, mechanical stability and processability typical of polymers. The combination of ILs or PILs with colloidal semiconducting nanocrystals leads to novel nanocomposite materials with high potential for batteries and solar cells. Here the results of a spectroscopic study focused on the interactions between titanium dioxide nanorods and imidazolium-based ionic liquids are reported. TiO2 nanoparticles are unquestionably the most used material for the fabrication of sensitized solar cells and batteries, in which ILs are being used in order to replace conventional electrolytes. Anatase TiO2 rod-like nanocrystals, synthesized by means of a colloidal synthetic procedure, have been dispersed in a series of alkyl-substituted imidazolium based ILa, in order to investigate the interactions between the organic and inorganic moieties and the effects induced by different anions and alkyl chain lengths. Time-resolved spectroscopic measurements have highlighted significant differences in the recombination decay of ILs in presence of TiO2 nanorods. Such a behaviour can be reasonably ascribed to charge-transfer phenomena from photo-excitedTiO2 nanocrystals to imidazolium-based ILs. Also hybrid nanocomposites made of colloidal luminescent CdSe nanocrystals incorporated in a novel imidazolium-based PIL functionalized with a thiol end-group have been investigated. A capping exchange procedure has been implemented for replacing the pristine organic capping molecules of the colloidal CdSe nanocrystals with inorganic chalcogenide ions, aiming to disperse the nano-objects in the PILs, by using a common polar solvent. Spectroscopic measurements highlight the beneficial effect of the thiol functionality at the termini of PIL chains in completely retaining the optical properties of the CdSe NCs. In addition, the possible coordination of PIL functionalities to the NC surface favors the occurrence of charge transfer processes from SH-PIL to the CdSe NCs emitting states. The obtained results are of considerable interest for designing batteries and solar cells based on nanostructured materials and ionic liquids and can represent the starting point for developing innovative electroactive nanocomposite hybrid materials for the fabrication of electrochemical devices and actuators.

We report a very effective synthetic approach to achieve the in situ growth, directly at the surface of single walled carbon nanotubes, of shape controlled anatase TiO2 nanocrystals, either as nanorods or nanospheres, by simply tuning the ratio between reactants. Remarkably, the obtained SWCNTs/TiO2 heterostructures result dispersible in organic solvents, leading to optically clear dispersions. The photocatalytic activity of the SWCNTs/TiO2 heterostructures, compared with bare TiO2 nanorods or nanospheres demonstrates a significant enhancement. In particular, SWCNTs/TiO2 heterostructures demonstrates an enhancement of reaction rate up to 3 times with respect to the commercially available standard TiO2 powder (TiO2 P25) under UV light and up to 2 times under visible light.

Iron oxide nanocrystals, synthesized by surfactant-assisted thermal decomposition of Fe(CO)(5), were selectively incorporated into the microseparated PS block phase of polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymer to design novel nanostructured inorganic/organic materials with magnetic properties. The colloidal synthesis led to oleic acid- and oleylamine- capped magnetic gamma-Fe2O3 maghemite nanocrystals, which resulted well-dispersible in the block copolymer up to 60 wt % due to the affinity between PS block and organic surfactants. Atomic force and scanning electron microscopy confirmed that nanocomposites with nanocrystal loading lower than 40 wt % maintained cylindrical morphology, even without additional treatment applied to enhance their nanostructuration. Nanocrystals appeared well-dispersed in the nanocomposites at low contents, while nanocrystal clusters, with size depending on their loading, were observed at higher contents. At the highest nanocrystal content, the nanostructured area size decreased and nanocrystals covered the entire surface. Magnetic force microscopy measurements confirmed the magnetic behavior of gamma-Fe2O3 nanocrystals confined in PS block of PS-b-PMMA block copolymer after applying UV treatment to the samples. The results demonstrated that the incorporation of as-synthesized colloidal iron oxide nanocrystals (up to 40%) in self-assembled PS-b-PMMA block copolymer offers a simple and direct approach to successfully design and fabricate novel nanostructured magnetic composites.

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.

Inorganic nanocrystals and nanoparticles have aroused increasing attention in the last years due to their original optoelectronic, thermodynamic, mechanical and catalytic properties, which are extremely attractive for fundamental understanding as well as for their huge potential in applications. The ability to strongly exploit the original potential of such nano-objects and access their properties relies on the ability to bridge the gap between the nanoscopic and mesoscopic scale. Indeed, to integrate nanoparticles in structures, materials and finally devices, their incorporation in processable systems, and their organization in morphologically controlled assembly and/or ordered arrays is crucial. The fabrication of 2/3 D patterned micro- and nanostructure is a promising strategy for integrating the nanoparticles in macroscopic entities in order to properly exploit their unprecedented functionality for biomedical, electronic, catalytic materials and devices. In this paper, different and complementary strategies able to engineer inorganic colloidal nanocrystals due to their organization in original functional materials and structures will be described.

The interaction between plasmons and excitons in photonic crystal structures is demonstrated to benefit the light extraction capabilities of polymer-based light emitting components. An enhancement of up to a factor of 40 is reported in structures fabricated by nanoimprint lithography. © 2011 IEEE.

An optically transparent and UV-light active anode, characterized by high (photo) conductivity, charge mobility and exciton lifetime, based on graphene, grown by CVD, decorated with colloidal TiO2 nanocrystals (NCs), has been fabricated, by a direct and facile solution-based procedure. TiO2 NCs anchor onto graphene by means of p-p stacking interactions occurring between the pyrene-1-butyric acid (PBA) surface coating ligand and the 2-D platform and assemble in a highly interconnected multilayered layout, by means of interligand pi-pi forces, retaining composition and geometry, along with the graphene structure. Remarkably, the PBA-coated TiO2 NCs on the graphene increase its electrical conductivity, electroactivity, and capacitive behavior, as well as photoelectrical response under UV-light, resulting in a 50% enhanced photoelectroactivity and a long exciton recombination lifetime. The photoanodes can be integrated into solar cells as optically transparent electrodes, in photodetectors, FETs and (bio)sensors.

The relaxation dynamics of charge carriers of organic capped TiO2 nanorods dispersed in chloroform was investigated by femtosecond transient absorption in a weak-excitation regime. Anisotropic TiO2 nanocrystals were excited in the UVvis range, using different pump wavelengths, namely above (300 nm), close to (350 nm), and below (430 nm) the direct band gap of anatase TiO2. We show that the ultrafast dynamics strongly depends on excitation wavelength and determine the time constants of all the processes entering the relaxation. Moreover, we demonstrate that two transient absorption bands at 500 and 700 nm, typically attributed to trapped h(+) and e, respectively, are accessible only when TiO2 is photoexcited well above the band gap, while there is no evidence of such bands when TiO2 is photoexcited close to or below its band gap. In such cases the observed dynamics are attributed to trapped excitons.

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.

A facile, cost-effective, and general solution-based "bottom-up" method for nanopatterning dense arrays of colloidal Au nanoparticles (NPs) has been developed. The organization of the NPs has been successfully achieved onto a microphase-separated poly(styrene-block-ethylene oxide) (PS-b-PEO) block copolymer (BCP) thin film which acts as structural template. The NP assembly process occurs by incubating the BCP films in dispersions of the ex situ synthesized Au NPs, not requiring any chemical pre-treatment or activation step of the copolymer surface, and has demonstrated to be distinctively controlled by multiple, cooperative, and selective hydrogen bonding interactions between hydroxyl functionalities of the capping molecules coating the Au NP surface and the hydrophilic PEO block. The effect of incubation time and concentration of NPs on the selectivity of the assembly has been investigated by atomic force and scanning electron microscopy. The results show that the BCP pattern is preserved after decoration with the Au NPs. The fabricated nanopatterns are good candidates for nanostructure integration in sensing and optoelectronic applications, as well as in memory devices and photonic systems. Moreover, the proposed immobilization protocol represents a model system that can be extended to other NPs having different compositions and surface chemistries.

Because of the growing potential of nanoparticles in biological and medical applications, tuning and directing their properties toward a high compatibility with the aqueous biological milieu is of remarkable relevance. Moreover, the capability to combine nanocrystals (NCs) with biomolecules, such as proteins, offers great opportunities to design hybrid systems for both nanobiotechnology and biomedical technology. Here we report on the application of the micelle-to-vesicle transition (MVT) method for incorporation of hydrophobic, red-emitting CdSe@ZnS NCs into the bilayer of liposomes. This method enabled the construction of a novel hybrid proteo-NC-liposome containing, as model membrane protein, the photosynthetic reaction center (RC) of Rhodobacter sphaeroides. Electron microscopy confirmed the insertion of NCs within the lipid bilayer without significantly altering the structure of the unilamellar vesicles. The resulting aqueous NC-liposome suspensions showed low turbidity and kept unaltered the wavelengths of absorbance and emission peaks of the native NCs. A relative NC fluorescence quantum yield up to 8% was preserved after their incorporation in liposomes. Interestingly, in proteo-NC-liposomes, RC is not denatured by Cd-based NCs, retaining its structural and functional integrity as shown by absorption spectra and flash-induced charge recombination kinetics. The outlined strategy can be extended in principle to any suitably sized hydrophobic NC with similar surface chemistry and to any integral protein complex. Furthermore, the proposed approach could be used in nanomedicine for the realization of theranostic systems and provides new, interesting perspectives for understanding the interactions between integral membrane proteins and nanoparticles, i.e., in nanotoxicology studies.

Semiconductor nanocrystals and room-temperature ionic liquids have been extensively investigated as promising materials for applications in the field of energy conversion and storage. Titanium dioxide nanoparticles are unquestionably the most used material for the fabrication of sensitized solar cells and batteries, in which room-temperature ionic liquids have been used to replace conventional electrolytes. The study of their interactions is, therefore, undoubtedly of large scientific and technological interest for their implementation in innovative energy devices. Here, a spectroscopic study focused on the interactions, in terms of charge and/or energy transfer, between titanium dioxide nanorods and imidazolium-based ionic liquids is reported. Anatase TiO2 rodlike nanocrystals, synthesized by means of a colloidal synthetic procedure, have been dispersed at increasing loading in a series of dialkyl-substituted imidazolium-based ionic liquids, characterized by different anions and alkyl chain lengths. Time-resolved spectroscopic measurements have highlighted a significant increase of the photoluminescence decay times in the presence of TiO2 nanorods. This increase has been shown to directly depend on TiO2 load and has been ascribed to charge-transfer phenomena from photoexcited TiO2 nanorods to imidazolium rings of ionic liquids. The obtained results are of considerable interest for designing batteries and solar cells based on nanostructured materials and ionic liquids.

We investigated the excitation density dependence of the photoluminescence spectra of hybrid poly(9,9-dioctylfluorene)-CdSe/ZnS nanocrystals (PF8-NCs) thin films. We demonstrate that this experiment allows the determination of the efficiency of all the CdSe/ZnS NCs excitation processes and that the presence of amplified spontaneous emission (ASE) from the PF8 leads to a strong dependence of the NC excitation processes from the laser excitation density. Below the PF8 ASE threshold only about 6% of the excitons in the NCs are due to pump laser absorption, while about 94% of the NC excitation is due to the interaction with the PF8, and it is due for about 58% to PF8 -> NC Forster resonant energy transfer (FRET) and for about 37% to reabsorption by the NCs of the PF8 luminescence. ne presence of PF8 ASE significantly modifies this scenario by strongly decreasing the FRET importance and strongly increasing the reabsorption one. The interplay between reduced FRET and increased reabsorption overall decreases the NC excitation due to PF8 indicating that ASE from the donors should be avoided if efficient NCs excitation under strong pumping is wished.

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.

In recent years the use of nanocrystals (NCs) as inorganic semiconductors in conjugated polymer-based hybrid solar cells (HSCs) results as a challenging target for researchers because of their high electron mobility and good mechanical robustness compared to fullerene derivatives, as well as their capability of harvesting photons in the visible to near-infrared region of the solar spectrum.Unfortunately HSCs still suffer from a major drawback, that is a poor control over the organic donor and inorganic acceptor domain size distributions. The domain size of the donor and acceptor materials should be comparable to the exciton diffusion length in order to increase the probability of exciton dissociation, and to improve charge carrier transport and collection at the device electrodes. The readiness of inorganic NCs to macrophase separate from non-polar conjugated polymers at higher loading concentrations, prevents the building of a controllable interpenetrating percolation network.A suitable nanostructuring compatibilizer can induce selective intermolecular interactions, leading to morphological order associated to an improvement in the interface processes, which consequently drive a strong rising in the performances of the device by decreasing recombination losses. For this purpose, block copolymers are particularly significant because they can self-assemble through phase separation by rationally tailoring the blocks using functional moieties with different physical-chemical behaviours.We report on the synthesis of a rod-coil diblock copolymer based on poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b']dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] (PCPDTBT), a low band gap copolymer, and a coil block of poly(4-vinylpyridine) able to interact with semiconducting CdSe NCs with the aim of using it as coordinating material in the preparation of PCPDTBT/CdSe NCs-based hybrid solar cells.

Hepatocellular carcinoma (HCC) is the sixth most common malignancy and is the leading cause of mortality in patients with cirrhosis. When the tumor is in an advanced stage and a radical surgery is, in most cases, no longer feasible, medical management is the only possible treatment option. Sorafenib is currently the first and sole biological agent clinically approved for patients with advanced HCC. As well as significant activity, sorafenib is characterized by severe toxic side effects and poor solubility in aqueous environment, limiting the possible therapeutic response and its application for local treatment [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 concomitant reduced toxicity of normal tissue. 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. Here, lipid based nanoformulations containing sorafenib and SPIONs have been prepared and thoroughly investigated by means of complementary techniques, thus finally resulting effective drug delivery magnetic nanovectors with good stability in aqueous medium and high drug encapsulation efficiency [2]. In addition, the relaxometric characterization has proven that the magnetic nanocarriers loaded with sorafenib are also very efficient contrast agents, with a great potential in magnetic resonance imaging technique. The proposed magnetic nanovectors loaded with sorafenib represent promising candidates for image guided and magnetic targeting of sorafenib to liver towards an efficacious treatment of HCC.

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.

Nanocrystal superlattices are attracting significant interest due to novel and peculiar collective properties arising from the interactions of the nanocrystals forming the superlattice. A large variety of superlattice structures can be obtained, involving one or more types of nanocrystals, with different sizes and concentrations. Engineering of the superlattice properties relies on accurate structural and morphological characterization, able to provide not only a fundamental feedback for synthesis procedures, but also relevant insight into their structural properties for possible applications. Electron microscopy and X-ray based techniques are complementary approaches for nanoscale structural imaging, which however become challenging in the presence of building blocks only a few nanometers in size. Here, a structure solution for a three-dimensional (3D) self-assembly of PbS nanocrystals with bimodal size distribution is obtained, by exploiting small-angle X-ray diffraction, transmission electron microscopy, crystallographic procedures, and geometric constraints. In particular, analysis of small-angle X-ray diffraction data, based on the Patterson function and on the single crystal model, is shown to provide relevant information on the 3D superlattice structure as well as on particle size, the scattering signal being sensitive to particles as small as 1.5 nm. The combined approach here proposed is thus demonstrated to effectively overcome important resolution limitations in the imaging of superlattices including small nanocrystals.

We report on a method to enhance the light-emission efficiency of printable thin films of a polymer doped with luminescent (CdSe)ZnS nanocrystals via metallic nanoparticles and nanoimprinted photonic crystals. We experimentally show a strong fluorescence enhancement of nanocrystals by coupling exciton-plasmon with the localized surface plasmon of metallic nanoparticles. The emitted light is efficiently diffracted by photonic crystals structures directly imprinted in the nanocomposite polymer. By combining the field susceptibility technique with optical Bloch equations, we examine the interaction of the quantum and plasmonic entities at small distances.

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.

The photocatalytic degradation of pollutants is a key technological application for nanomaterials. Ourwork aims at developing a multifunctional nanocrystalline heterostructure based on TiO2nanorods,FexOyand Ag nanoparticles (NPs), TiO2NRs/FexOy/Ag, integrating in one nanostructure a visible lightphotoactive moiety (TiO2NRs/Ag) and a magnetic domain (FexOy), in order to address the photoactivityunder visible light and the possibility of recovery and reuse the photocatalyst. The synthesis was carriedby preparing first the TiO2NRs/FexOybased heterostructure and then growing Ag NPs with control on size.The resulting multidomain structures were characterized by FTIR and absorption spectroscopy, TEM andSEM microscopy, EDS and XRD analysis. The influence of the Ag NP domain and of its size on the photoac-tivity of the TiO2NRs/FexOy/Ag nanostructures under visible light were investigated in the photocatalyticdegradation of the Nalidixic Acid, an antibiotic used as a model compound representative of recalci-trant pollutants. In the presence of the Ag domain a significant increase of the photoactivity with respectto TiO2NRs/FexOyheterostructures and to the commercially available TiO2P25 was observed. Such anenhanced photocatalytic efficiency was found dependent on the size of the Ag domain and explainedtaking into account the plasmonic properties and the different possible photoactivation mechanisms.

Photo-oxidation processes assisted by nanosized semiconductors are receiving increasing attention due to their potential application in environmental field. The ability to exploit the strong potential of photoactive nanomaterials and access their properties relies on the ability to integrate them in photo-reactors and to effectively deposit them on large surfaces. Such a strategy can bridge the gap between the nanoscopic and mesoscopic scale and avoiding nanoparticle release in the environment. In order to integrate nanopartides in functional structures and, finally, devices, their incorporation in suitable host matrices is crucial to achieve processable nanocomposite materials. Here, a comprehensive overview on the preparation of photocatalytic nanocomposite materials and their application for pollutants degradation will be provided. In particular, we will focus on modern synthetic approaches to synthetize UV and visible light active nanocatalysts, on their post-synthesis surface functionalization and on their incorporation in suitable host matrices toward nanocomposite preparation. Finally, some examples from recent literature on their application in environmental remediation and as bactericidal and self-cleaning coatings will be reported. (C) 2016 Elsevier B.V. All rights reserved.

Polymeric ionic liquids (PILs) are an interesting class of polyelectrolytes, merging peculiar physical-chemical features of ionic liquids with the flexibility, mechanical stability and processability typical of polymers. The combination of PILs with colloidal semiconducting nanocrystals leads to novel nanocomposite materials with high potential for batteries and solar cells. We report the synthesis and properties of a hybrid nanocomposite made of colloidal luminescent CdSe nanocrystals incorporated in a novel ex situ synthesized imidazolium-based PIL, namely, either a poly(N-vinyl-3-butylimidazolium hexafluorophosphate) or a homologous PIL functionalized with a thiol end-group exhibiting a chemical affinity with the nanocrystal surface. A capping exchange procedure has been implemented for replacing the pristine organic capping molecules of the colloidal CdSe nanocrystals with inorganic chalcogenide ions, aiming to disperse the nano-objects in the PILs, by using a common polar solvent. The as-prepared nanocomposites have been studied by TEM investigation, UV-Vis, steady-state and time resolved photoluminescence spectroscopy for elucidating the effects of the PIL functionalization on the morphological and optical properties of the nanocomposites.

PbS colloidal nanocrystal (NC) assemblies with monomodal and bimodal size distribution have been fabricated by slow evaporation of solvent on silicon substrates. The interparticle distances of the assembled structures have been carefully defined, both in the plane and in the z direction, perpendicular to the substrate, thanks to the combination of small and wide-angle X-ray diffraction and TEM measurements. The spectroscopic characteristics of PbS NCs, both in solution and organized in a superlattice, have been investigated by steady-state and time-resolved photoluminescence measurements. The optical results reveal the occurrence of a Forster resonant energy transfer (FRET) mechanism between closed-packed neighboring PbS NCs. The occurrence of FRET is dependent on NC assembly geometry, and thus on their interparticle distance, suggesting that only when NCs are close enough, as in the close-packed arrangement of the monomodal assembly, the energy transfer can be promoted. In bimodal assemblies, the energy transfer between large and small NCs is negligible, due to the low spectral overlap between the emission and absorption bands of the different sized nanoparticles and to the large interparticle distance. Moreover, recombination lifetimes on the microsecond time scale have been observed and explained in terms of dielectric screening effect, in agreement with previous findings on lead chalcogenide NC optical properties.

Controlling light interactions with matter on the nanometer scale provides for compelling opportunities for modern technology and stretches our understanding and exploitation of applied physics, electronics, and fabrication science. The smallest size to which light can be confined using standard optical elements such as lenses and mirrors is limited by diffraction. Plasmonic nanostructures have the extraordinary capability to control light beyond the diffraction limit through an unique phenomenon called the localized plasmon resonance. This remarkable capability enables unique prospects for the design, fabrication and characterization of highly integrated photonic signal-processing systems, nanoresolution optical imaging techniques and nanoscale electronic circuits. This paper summarizes the basic principles and the main achievements in the practical utilization of plasmonic effects in nanoparticles. Specifically, the paper aims at highlighting the major contributions of nanoparticles to nanoscale temperature monitoring, modern "drug free" medicine and the application of nanomaterials to a new generation of opto-electronics integrated circuits.

Here, silica-coated PbS quantum dots (QDs) with photoluminescence emission properties in the near-infrared (NIR) region are proposed as potential effective single particle optical nanoprobes for future in vivo imaging of tumors.. The dispersibility in aqueous medium of hydrophobic PbS QDs was accomplished by growing a silica shell on their surface by exploiting a base assisted water-in-oil microemulsion method. The silica-coated PbS QDs were then conjugated with a specifically designed cyclic arginine-glycine-aspartic acid (cRGD) peptide that is able to specifically recognize alpha nu beta 3 integrins, which are overexpressed in angiogenic tumor-induced vasculatures and on some solid tumors, to achieve tumor-specific targeting. The cRGD peptide PbS silica-coated QDs were systematically characterized, at each step of their preparation, by means of complementary optical and structural techniques, demonstrating appropriate colloidal stability and the maintenance of their optical futures in aqueous solutions. The cellular uptake of cRGD peptide functionalized luminescent nanostructures in human melanoma cells, where overexpression of alpha nu beta 3 was observed, was assessed by means of confocal microscopy analysis and cytometric study. The selectivity of the cRGD peptide PbS silica-coated QDs for the alpha nu beta 3 integrin was established, consequently highlighting the significant potential of the developed NIR emitting nanostructures as optically traceable nanoprobes for future alpha nu beta 3 integrin receptor in vivo targeting in the NIR region.

As-synthesized organic-capped TiO2 nanorods were incorporated into polystyrene-block-poly(methyl methacrylate) (PS-b-PMMA) diblock copolymer to achieve TiO2/PS-b-PMMA nanocomposites with enhanced optical and conductive properties. The specific surface chemistry of TiO2 nanorods derived from the colloidal synthetic approach allowed their prompt incorporation in the PS-b-PMMA block copolymer template up to SO wt %, which resulted in films with an extended coverage of highly dispersed nanoparticles for contents higher than 30 wt %. At such high nanorod contents, the films fabricated by the prepared nanocomposites demonstrated enhanced optical properties. Atomic force microscopy investigation of the nanocomposite films showed a cylindrical morphology for low nanorod contents. Conversely, higher nanorod contents resulted upon removal of the organic component in the nanocomposites with UV treatment in overall nanorod coverage of the film surface with the concomitant formation of charge percolation paths, which led to noticeable conductivity values. EFM and PF-TUNA measurements confirmed the conductive properties of the composites at nanoscale, whereas semiconductor analyzer measurements provided their macroscale characterization. In addition, an increase in the UV-vis absorption was observed with the increase in the nanorod content along with a remarkable conductivity of the overall film.

We report on the synthesis, characterization and application of a novel nanocomposite made of a negative tone epoxy based photoresist modified with organic-capped Fe(2)O(3) nanocrystals (NCs). The mechanical properties of the nanocomposite drastically improve upon incorporation of a suitable concentration of NCs in the polymer, without deteriorating its photolithography performance. High aspect ratio 3D microstructures made of the nanocomposite have been fabricated with a uniform surface morphology and with a resolution down to few micrometres. The embedded organic-capped Fe(2)O(3) NCs drastically increase the stiffness and hardness of the epoxy based photoresist matrix, making the final material extremely interesting for manufacturing miniaturized polymer based mechanical devices and systems. In particular, the nanocomposite has been used as structural material for fabricating photoplastic Atomic Force Microscopy (AFM) probes with integrated tips showing outstanding mechanical response and high resolution imaging performance. The fabricated probes consist of straight cantilevers with low stress-gradient and high quality factors, incorporating sharp polymeric tips. They present considerably improved performance compared to pure epoxy based photoresist AFM probes, and to commercial silicon AFM probes.

A simple fabrication approach for achieving nanoparticle patterns based on a room temperature chemically driven strategy is reported. Suitably engineered colloidal luminescent nanocrystals (NCs) (4 and 6 nm in diameter), namely organic capped and silica-coated negatively charged CdSe@ZnS NCs, have been selectively assembled onto defined domains in a binary hydrophobic/hydrophilic chemical pattern, purposely fabricated by combining microcontact printing and wet chemistry procedures. The goal of the work has been to investigate the experimental parameters governing the assembly process at molecular level, in order to elucidate factors regulating interactions at the interfaces. For this purpose, specific sets of conditions, namely substrate patterns and NCs with distinct surface functionalization, have been prepared and tested using different NC dispersing solvents. The NC assembly has been demonstrated driven by non-covalent forces, namely Van der Waals or electrostatic interactions occurring at the NC/substrate interface. The overall study has provided a comprehensive understanding of the role of solvent and molecular chemistry at interfaces in NC assembling. The obtained results can be valuable to set up reliable procedures for developing reproducible patterning protocols potentially useful for the fabrication of NC-based devices.

Anatase TiO2 nanorocls (NRs), with an average diameter of 3-4 nm and an average length of 25-30 nm were investigated as Li-insertion material. The NRs, capped with oleic acid, were synthesized by a low temperature colloidal route based on thermal decomposition of the precursors in presence of coordinating agents. A highly porous and connective network of NRs and carbon was prepared by taking advantage of this organic capping to inhibit the nanoparticle agglomeration and to act as a precursor for the formation of a carbonaceous percolating network. Composite electrodes, made of such material, were able to deliver reversible capacities of about 250 mAh g(-1) (corresponding to 0.75 equiv. of Li per TiO2 unit). Reversible capacities of 210 mAh g(-1) (0.63 Li per TiO2), 194 mAh g(-1) (0.58 Li per TiO2), 165 mAh g(-1) (0.49 Li per TiO2). and 130 mAh g(-1) (0.39 Li per TiO2) were observed during cycle tests at 1C, 2C, 5C, and 10C, respectively, confirming the excellent high rate performance of the well-dispersed NRs. Finally, the electrodes showed excellent cycle life performance. (C) 2011 Elsevier B.V. All rights reserved.

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.

Colloidal chemistry allows the fabrication of metal, semiconductor, oxide, and magnetic nanocrystals (NCs) with well-controlled sizes and shapes, as well as of heterostructures with exotic shapes and composition (1). Such NCs are promising materials in several technological fields. For example, the high-purity emission color of semiconductor NCs has been applied in optical displays (2), and their broadband absorption has been exploited in innovative solar cells (3). Other applications include field-effect transistors, light-emitting diodes, and sensors (4). However, for the fabrication of advanced electronic devices in a parallel and scalable fashion for industrial production, NCs must be integrated into structures to bridge the gap between the nano- and mesoscopic regimes (5). Thus, the organization of NCs in morphologically controlled patterns and processable systems is of paramount importance. On page 385 of this issue, Wang et al. (6) present a pioneering and straightforward approach for the patterning of functional inorganic NCs on substrates with optical lithography. This advance could add--literally--a multilayer dimension to the development of NC-based devices.

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.

Nanocomposite materials have been obtained by dispersing organic capped TiO(2) nanocrystals (NCs) with different shape and surface chemistry in poly(methyl methacrylate) (PMMA) as a host medium. Films of the prepared nanocomposites based on TiO(2) NCs have been fabricated by spin coating and morphologically characterized as a function of the preparative conditions. The organic vapor absorption ability of the PMMA/TiO(2) NC based nanocomposites has been then investigated both for spherical and rod-like NCs, and the chemical nature of the coordinating organic molecules has been also varied. The results of the investigation have demonstrated that NC geometry and surface chemistry can modulate the specific absorption characteristics of the modified PMMA in order to absorb different solvent molecules (i.e. acetone, ethanol, propan-2-ol and water). Such features, due to specific interactions between the potential analyte vapors and the functionalized surface of NCs, can effectively be addressed in a controlled and reproducible way, thus offering original opportunities for designing innovative chemical sensors.

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.

Two colloidal methods, namely one pot and two steps approaches, have been exploited to synthesize light emitting CdSe/ZnS core-shell nanocrystals, differing in growth process of the inorganic ZnS shell and, therefore in the resulting surface chemistry of the two types of nanocrystals. The synthesized nanocrystals have been incorporated, by using an "ex situ" procedure, in different thermoplastic PMMA-based polymers, including PMMA co-polymer specifically functionalized by means of groups having high chemical affinity to nanocrystal surface, and the resulting nanocomposites have been processed in thin films. Spectroscopic steady state and time-resolved investigations, carried out both on nanocomposite solution and thin film samples, indicate as a change in the optical properties of the two steps nanocrystals is observed upon incorporation in polymers, especially in PMMA homopolymer, where significant aggregation of inorganic nanostructures occurs. On the contrary, the one pot CdSe/ZnS nanocrystals preserve in all investigated samples their long-lived radiative emission. Such nanocrystals result homogeneously dispersed in the polymers, providing high quality films and thus representing ideal candidates for future optical applications.

This study reports for the first time the use of a red-emitting AIEgen, i.e. TPE-AC, for the realization of efficient luminescent solar concentrators (LSCs) based on poly(methyl methacrylate) (PMMA) and polycarbonate (PC) thin films (25 +/- 5 mu m). TPE-AC is an AIEgen with D-A features that absorbs visible light in the range between 400 and 550 nm and emits fluorescence peaked at 600-620 nm, with a maximum quantum yield (QY) of 50% when dispersed (0.1-1.5 wt%) in PMMA and PC matrices. QY and lifetime investigations demonstrated that fluorescence quenching occurred with varying the TPE-AC concentration, even if the optical features were still significant even at the highest fluorophore content. Study of the LSCs' performances yielded worthy optical efficiencies of 6.7% for the TPE-AC/PC systems due to their superior light harvesting features and the compatibility of the AIEgen within the PC matrix.

In this work the performance improvement of hybrid solar cells (HSCs), constituted by polycyclopentadithiophene-benzothiadiazole (PCPDTBT) and CdSe nanocrystals (NCs), achieved thanks to the use as additive of an on-purpose designed rod-coil block copolymer (BCP), is evaluated. The rod-coil BCP, namely polycyclopentadithiophene-benzothiadiazole-b/ock-poly(4-vinylpyridine) (PCPDTBT-b-P4VP), is synthesized with a chain growth-like procedure starting from a PCPDTBT macroinitiator suitably tailored in order to achieve molecular similarity with the commercial PCPDTBT homopolymer here used in the HSCs, in order to optimize the interactions between the two materials in the device. Nitroxide-mediated radical polymerization (NMRP) of 4-vinylpyridine generates the rod-coil flexible chain which is maintained short to limit the insertion of insulating moieties in the additive structure. The employment of the rod-coil BCP as additive is demonstrated to be an effective alternative to the standard post-deposition thermal treatment. The device with 1% of additive performs better than the thermal annealed one and shows an improvement of 60% in power conversion efficiency (PCE) if compared to the pristine CdSe NCs/PCPDTBT cell. The optical and morphological analysis of the CdSe NCs/PCPDTBT films with and without additive elucidates the relation between the device performance and the active layer microstructure and clearly highlights how the improvement of the miscibility between the polymer and the inorganic NC species can be associated to the increased efficiency in HSCs. A future development of this room-temperature processing approach of the active layer, not requiring any additional post-fabrication annealing steps, could implement HSCs fabrication by common printing technologies for a cost-effective fabrication of devices onto large-area and flexible substrates. (C) 2016 Elsevier Ltd. All rights reserved.

Nanocomposites based on colloidal CdSe nanocrystals (NCs) and a poly(styrene-co-4-vinylpyridine), able to specifically coordinate the NC surface, have been designed and prepared. For first time, the polymer synthesis has been performed by using 2,2,5-tri-methyl-4-phenyl-3-azahexane-3-nitroxide as a mediator, increasing the percentage of 4-vinylpyridine monomeric unit, thus obtaining a random copolymer. The nanocomposite properties have been investigated as a function of NC surface chemistry and copolymer composition, by means of spectroscopic, morphological and structural characterization techniques. An improved uniformity of NC dispersion in the nanocomposite has been found at increased percentage of 4-vinylpyridine in the copolymer. The improved NC dispersion in the nanocomposite films has been discussed in terms of the ability of the copolymer to act as a multivalent ligand. The reported results offer a valuable contribution toward the design and the fabrication of innovative nanocomposite material, formed of copolymers and colloidal NCs, specifically suited for energy conversion 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.

Here the synthesis of distinct monomodal and bimodal PbS nanocrystal (NC) populations, with narrow size-distribution, is reported. The ability to achieve careful control of NC size and size distribution allowed the preparation, in one single synthetic step, of two distinct populations of PbS NCs, with tuneable size ratio. The NC growth was carefully studied in order to gain insight into the mechanism underlying the formation of the mono and bimodal PbS NC families. The synthesized PbS NCs were structurally and chemically characterized, and subsequently used as building blocks for fabricating solid crystal assemblies by solvent evaporation. In particular the role played by different parameters, namely NC size and concentration, dispersing solvent and substrate, on crystallinity, geometry and structure of the obtained solids was systematically investigated. Interestingly the assembly of bimodal PbS NC samples leads to the formation of diverse superlattice structures, with a final geometry dependent on the NC size and the size ratio in the bimodal population. The synthetic procedure was then ultimately responsible of the superlattice structures, through the control of the PbS NC size and size ratio in the bimodal population.

A growing interest is devoted to the study of imidazolium-based ionic liquids as innovative materials to combine with functional elements for advanced technological applications. Materials based on semiconductor and oxide nanocrystals in ionic liquids can be promising for their integration in lithium batteries, as well as in innovative solar cells. Although the physical chemical properties and the solvation dynamics of bare ionic liquids have been extensively studied, their combination with colloidal nanocrystals still remains almost unexplored. Here, the optical properties of organic-capped luminescent cadmium selenide nanocrystals coated by a shell of zinc sulfide (CdSe(ZnS)) dispersed in 1,3-dialkyl imidazolium ionic liquids have been investigated, also in dependence of the alkyl chain length on the imidazolium ring and of the anion nature, by using both time-integrated and time-resolved optical spectroscopy. The observed variations in decay profiles of the ionic liquid in presence of colloidal nanocrystals suggest that the dispersion of the nanostructures induces modifications in the ionic liquid structural order. Finally, atomic force microscopy analysis has provided insight into the topography of the investigated dispersions deposited as film, confirming the organization of the ionic liquids in super-structures, also upon nanocrystal incorporation.

The amplification of Raman signals of the heteroaromatic cation 1-(N-methylpyrid-4-yl)-2-(N-methylpyrrol-2-yl)ethylene (PEP+)) bound to Au nanorods (NRs) was investigated at different excitation wavelengths to study the effect of the laser resonance with the absorption band of the PEP+ moiety and with the two plasmon oscillation modes of the NR. Two different PEP+ derivatives, differing in the length of the alkyl chain bearing the anchoring group, were used as target molecules. Raman spectra obtained exciting at 514 or at 785 nm (i.e., exciting the transverse or the longitudinal plasmon band) present a higher intensity than that at 488 nm suggesting a higher Raman amplification when the laser excitation wavelength is resonant with one of the two plasmon modes. Moreover, considering results of Discrete Dipole Approximation (DDA) calculations of the local field generated at the NR surface when either the transverse or the longitudinal plasmon modes are excited, we deduced that the resonance condition of the 514-nm laser excitation with the absorption band of the dye strongly contributes to the amplification of the Raman signal.

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.

Currently, sorafenib is the only systemic therapy capable of increasing overall survival of hepatocellular carcinoma patients. Unfortunately, its side effects, particularly its overall toxicity, limit the therapeutic response that can be achieved. Superparamagnetic iron oxide nanoparticles (SPIONs) are very attractive for drug delivery because they can be targeted to specific sites in the body through application of a magnetic field, thus improving intratumoral accumulation and reducing adverse effects. Here, nanoformulations based on polyethylene glycol modified phospholipid micelles, loaded with both SPIONs and sorafenib, were successfully prepared and thoroughly investigated by complementary techniques. This nanovector system provided effective drug delivery, had an average hydrodynamic diameter of about 125 nm, had good stability in aqueous medium, and allowed controlled drug loading. Magnetic analysis allowed accurate determination of the amount of SPIONs embedded in each micelle. An in vitro system was designed to test whether the SPION micelles can be efficiently held using a magnetic field under typical flow conditions found in the human liver. Human hepatocellular carcinoma (HepG2) cells were selected as an in vitro system to evaluate tumor cell targeting efficacy of the superparamagnetic micelles loaded with sorafenib. These experiments demonstrated that this delivery platform is able to enhance sorafenib's antitumor effectiveness by magnetic targeting. The magnetic nanovectors described here represent promising candidates for targeting specific hepatic tumor sites, where selective release of sorafenib can improve its efficacy and safety profile.

Room temperature ionic liquids are currently used as functional materials in several application and their optical investigation can provide a better understanding of their physical and chemical behavior. Absorption and emission properties of imidazolium-based ILs have been attributed to the imidazolium moiety and related to the presence of energetically different aggregates. Here, time-integrated and time-resolved investigation has been carried out on 1-alkyl-3-methylimidazolium tetrafluoroborate and hexafluorophosphate ionic liquids with different chain lengths in order to probe the occurrence of energy transfer processes, and hence to disclose the presence of various states with different energy. Such a study contributes to provide relevant insight on the effect of alkyl chain and anion type on the emission characteristics, and, hence, on the presence of associated structures.

In this Letter, a solution-based approach has been used for chemically immobilising oleic acid (OLEA)-capped TiO2 nanocrystals (NCs) on the surface of microcantilevers formed of SU-8, a negative tone epoxy photoresist. The immobilisation has been carried out at room temperature, under visible light, in ambient atmosphere and without applying any external driving force or chemical activation of the epoxy photoresist surface. Atomic force microscopy, scanning electron microscopy and X-ray photoelectron spectroscopy investigation demonstrate the spontaneous chemical anchoring of the organic-coated TiO2 NCs on the microcantilevers, which resulted in a highly interconnected nanoporous multilayer structure. The chemical and morphological characterisation shows that the immobilised NCs do not change either their pristine morphology or the chemical structure after binding. Spectroscopic investigation infers that the TiO2 NCs chemically bind through the free and highly reactive epoxy groups located on the epoxy photoresist surface by means of the OLEA capping molecules. Finally, the results show that the fabrication procedure of the microcantilevers has not been affected by the immobilisation protocol. The capability of the immobilised TiO2 NCs to generate surface-reactive hydroxyl radicals under UV-light irradiation has a good potential for detecting families of organic compounds when integrating the modified microcantilevers in electronic noses.

In this work, single walled carbon nanotubes (SWNTs) have been chemically functionalized at their walls with a membrane protein, namely the mutated bacteriorhodopsin D96N, integrated in its native archaeal lipid membrane. The modification of the SWNT walls with the mutant has been carried out in different buffer solutions, at pH 5, 7.5 and 9, to investigate the anchoring process, the typical chemical and physical properties of the component materials being dependent on the pH. The SWNTs modified by interactions with bacteriorhodopsin membrane patches have been characterized by UV-vis steady state, Raman and attenuated total reflection Fourier transform infrared spectroscopy and by atomic force and transmission electron microscopy. The investigation shows that the membrane protein patches wrap the carbon walls by tight chemical interactions undergoing a conformational change; such chemical interactions increase the mechanical strength of the SWNTs and promote charge transfers which p-dope the nano-objects. The functionalization, as well as the SWNT doping, is favoured in acid and basic buffer conditions; such buffers make the nanotube walls more reactive, thus catalysing the anchoring of the membrane protein. The direct electron communication among the materials can be exploited for effectively interfacing the transport properties of carbon nanotubes with both molecular recognition capability and photoactivity of the cell membrane for sensing and photoconversion applications upon integration of the achieved hybrid materials in sensors or photovoltaic devices.

In the last decades, the enormous interest in 2/3D nanocrystal (NC) architectures boosted the development of many and diverse techniques which allowed to precisely positioning the nanoparticles on substrates. The tremendous importance of such NC organizations is due to the novel collective properties arising from inter-particle interactions that emerge in these artificial materials, with promising application in opto-electronics, photonics and biomedicines.

Conjugated polymers are characterized by the delocalization of ?-electrons responsible of their electrical properties and structural rigidity. The manipulation of the chemical structures through the introduction of flexible chains allows to influence the morphology controlling the nanosegregation of the material.The use of nanocrystals (NCs) of inorganic semiconductors in "hybrid solar cells" offers high electron mobility enhancing the performance of the devices. The control of the active layer morphology at the nanoscale level ensures the further improve of the efficiency of the cells.The goal of this work is the evaluation of two approaches for the synthesis of a rod-coil copolymer based on poly[2,6-(4,4-bis-(2-ethylhexyl)-4H-cyclopenta[2,1-b:3,4-b']dithiophene)-alt-4,7-(2,1,3-benzothiadiazole)] rod-like block (electrondonor) and a coil block of poly(4-vinylpyridine) able to interact with semiconducting CdSe NCs (electronacceptor) with the aim of using it as both active and coordinating material for nanocomposites preparation with over 90% of NCs.

In this work, we report on similar to 4% power conversion efficiency (PCE) depleted bulk heterojunction (DBH) solar cells based on a high-quality electrode with a three-dimensional nanoscale architecture purposely designed so as to maximize light absorption and charge collection. The newly conceived architecture comprises a mesoporous electron-collecting film made of networked anisotropic metal-oxide nanostructures, which accommodates visible-to-infrared light harvesting quantum dots within the recessed regions of its volume. The three-dimensional electrodes were self-assembled by spin-coating a solution of colloidal branched anatase TiO2 NCs (BNC), followed by photocatalytic removal of the native organic capping from their surface by a mild UV-light treatment and filling with small PbS NCs via infiltration. The PCE similar to 4% of our TiO2 BNC/PbS QD DBH solar cell features an enhancement of 84% over the performance obtained for a planar device fabricated under the same conditions. Overall, the DBH device fabrication procedure is entirely carried out under mild processing conditions at room temperature, thus holding promise for low-cost and large-scale manufacturing.

In this work, the manufacturing andcharacterization of an optically transparent and UV-Iightphotoactive anode, formed of monolayer graphene grown bychemical vapor deposition (CVD) and decorated with a closepacked multHayered nanostructured layout of colloidal TiOznanocrystals (NCs), are reported. The hybrid material has beenprepared by a facHe solution-based procedure, which relays onsoaking the CVD graphene in a solution of I-pyrene butyric acid(PBA) surface coated Ti02 NCs, achieved upon implementationof a capping exchange process for displacing the pristine organicligand deriving from the colloidal synthesis. Pyrene undergoes 'It-'It stacking interactions, anchoring the NCs to the platform withretention of the NC geometry and composition. The NCsimmobilize onto the graphene platform with preservation of itsaromatic structure and the resulting hybrid has been foundoptically transparent in the visible spectral range.(Photo)electrochemical investigation shows that the compositematerial has a promising sensitivity for selectively detectingdopamine and norepinephrine and, concomitantly, exhibits a(photo)electric activity higher than that of bare graphene. Thus,the achieved hybrid material results interesting for themanufacturing of photo-active components to integrate in photorenewable sensor elements along with photodetectors and solarcells

While the primary reason for nanostructuring lithium-ion active materials is commonly the realization of shorter diffusion pathways for ions and electrons, there are also other, less-expected phenomena occurring when leaving the microscale to enter the nanoscale. Herein, we will present one of these phenomena - the thermally induced fragmentation (i.e., "chopping") of oleic acid-capped anatase TiO<inf>2</inf> nanorods perpendicular to the [001] direction. This fragmentation results in the formation of ultrafine TiO<inf>2</inf> nanoparticles with increased (001) facets. Due to this modified surface facets ratio and the advantageous utilization of carboxymethyl cellulose as binder, these ultrafine nanoparticles present an excellent rate performance and cycling stability - even for cathodic cut-off potentials as low as 0.1 V.

Colloidal semiconductor nanocrystals, with intense and sharp-line emission between red andnear-infrared spectral regions, are of great interest for optoelectronic and bio-imagingapplications. The growth of an inorganic passivation layer on nanocrystal surfaces is a commonstrategy to improve their chemical and optical stability and their photoluminescence quantumyield. In particular, cation exchange is a suitable approach for shell growth at the expense of thenanocrystal core size. Here, the cation exchange process is used to promote the formation of aCdS passivation layer on the surface of very small PbS nanocrystals (2.3 nm in diameter), blueshifting their optical spectra and yielding luminescent and stable nanostructures emitting in therange of 700-850 nm. Structural, morphological and compositional investigation confirms thenanocrystal size contraction after the cation-exchange process, while the PbS rock-salt crystallinephase is retained. Absorption and photoluminescence spectroscopy demonstrate the growth of apassivation layer with a decrease of the PbS core size, as inferred by the blue-shift of theexcitonic peaks. The surface passivation strongly increases the photoluminescence intensity andthe excited state lifetime. In addition, the nanocrystals reveal increased stability against oxidationover time. Thanks to their absorption and emission spectral range and the slow recombinationdynamics, such highly luminescent nano-objects can find interesting applications in sensitizedphotovoltaic cells and light-emitting devices.

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. © 2014 American Chemical Society.

A novel UV-light-curable nanocomposite material formed of a methacrylic-siloxane resin loaded with 1 wt % oleic acid and 3-(trimethoxysilyl)propyl methacrylate silane (OLEA/MEMO)-coated TiO2 nanorods (NRs) has been manufactured as a potential self-curing Structural coating material for protection of monuments and artworks, optical elements, and dental components. OLEA-coated TiO2 NRs, presynthesized by a colloidal chemistry route, have been surface-modified by a treatment with the methacrylic-based silane coupling agent MEMO. The resulting OLEA/MEMO-capped TiO2 NRs have been dispersed in MEMO; that is a monomer precursor of the organic formulation; used as a "common solvent" for transferring the NRs in prepolymer components of the formulation. Differential scanning calorimetry and Fourier transform infrared spectroscopy have allowed investigation of the effects of the incorporation of the OLEA/MEMO-capped TiO2 NRs on reactivity and photopolymerization kinetics of the nanocomposite, demonstrating that the embedded NRS significantly increase curing reactivity of the neat organic formulation both in air and inert atmosphere. Such a result has-been explained on the basis of the photoactivity of the nanocrystalline TiO2 which behaves as a free-radical donor photocatalyst in the curing reaction, finally turning out more effective than the commonly used commercial photoinitiator. Namely, the NRs have been found to accelerate the cure rate and increase cross-linking density; promoting Multiple covalent bonds between the resin prepolymers and the NR ligand molecules, and, moreover, they limit inhibition effect of oxygen on photopolymerization. The NRs distribute uniformly in the photocurable matrix, as assessed by transmission electron microscopy analysis, and increase glass transition temperature and water contact angle of the nanocomposite with respect to the neat resin.

Photocatalytic nanomaterials such as TiO2 are receiving a great deal of attention owing to their potential applications in environmental remediation. Nonetheless, the low efficiency of this class of materials in the visible range has, so far, hampered their large-scale application. The increasing demand for highly efficient, visible-light-active photocatalysts can be addressed by hybrid nanostructured materials in which two or more units, each characterised by peculiar physical properties, surface chemistry and morphology, are combined together into a single nano-object with unprecedented chemical-physical properties. The present review intends to focus on hybrid nanomaterials, based on TiO2 nanoparticles able to perform visible-light-driven photocatalytic processes for environmental applications. We give a brief overview of the synthetic approaches recently proposed in the literature to synthesise hybrid nanocrystals and discuss the potential applications of such nanostructures in water remediation, abatement of atmospheric pollutants (including NOx and volatile organic compounds (VOCs)) and their use in self-cleaning surfaces

The present invention relates to a method for manufacturing electrode material particularly for lithium and lithium ion batteries comprising the following steps: a) providing nanoparticles of titanium dioxide, lithium titanate, silicon, silicon oxide or a transition metal oxide, coated with a monocarboxylic acid having a chain length of 7 to 26 carbon atoms; b) heat-treatment of the monocarboxylic acid coated nanoparticles of step a) for carbonization of the monocarboxylic acid coating.