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.

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 present study investigates the effect of a silver (Ag)-containing nanocomposite coating on Staphylococcus epider-midis adhesion and icaA gene expression. Bacterial interactions with organic coatings with and without Ag nanoclusters were assessed through a combination of both conventional phenotypic analysis, using microscopy, and genotypic analy-sis, using the relative reverse transcription Real-Time Polymerase Chain Reaction (RT-PCR). The results suggest that the incorporation of Ag in organic coatings can significantly decrease bacterial adhesion and viability with time, in comparison to the organic coating alone. The initial Ag release though at concentrations lower than the bactericidal, significantly increased icaA gene expression for the bacteria interacting with the Ag containing coating two hours post adhesion, especially under the higher shear rate. Stress-inducing conditions such as sub-bactericidal concentrations of Ag and high shear rate can therefore increase icaA expression, indicating that analysis of gene expression can not only refine our knowledge of bacterial-material interactions, but also yield novel biomarkers for potential use in assessing biomaterials antimicrobial performance.

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.

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.

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.

The behavior of cells in terms of cell-substrate and cell-cell interaction is dramatically affected by topographicalcharacteristics as shape, height, and distance, encountered in their physiological environment. The combinationof chemistry and topography of a biomaterial surface influences in turns, important biological responses asinflammatory events at tissue-implant interface, angiogenesis, and differentiation of cells. By disentangling theeffect of material chemistry from the topographical one, the possibility of controlling the cell behavior can beprovided. In this paper, surfaces with different roughness and morphology were produced by radiofrequency (RF,13.56 MHz) glow discharges, fed with hexafluoropropylene oxide (C3F6O), in a single process. Coatings withdifferent micro/nanopatterns and the same uppermost chemical composition were produced by combining twoplasma deposition processes, with C3F6O and tetrafluoroethylene (C2F4), respectively. The behavior of osteoblastlikecells toward these substrates clearly shows a strict dependence of cell adhesion and proliferation on surfaceroughness and morphology.

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.

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.

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.

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 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

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.