Colloidal quantum dots (QDs) stand among the most attractive light-harvesting materials to be exploited for solution-processed optoelectronic applications. To this aim, quantitative replacement of the bulky electrically insulating ligands at the QD surface coming from the synthetic procedure is mandatory. Here we present a conceptually novel approach to design light-harvesting nanomaterials demonstrating that QD surface modification with suitable short conjugated organic molecules permits us to drastically enhance light absorption of QDs, while preserving good long-term colloidal stability. Indeed, rational design of the pendant and anchoring moieties, which constitute the replacing ligand framework leads to a broadband increase of the optical absorbance larger than 300% for colloidal PbS QDs also at high energies (>3.1 eV), which could not be predicted by using formalisms derived from effective medium theory. We attribute such a drastic absorbance increase to ground-state ligand/QD orbital mixing, as inferred by density functional theory calculations; in addition, our findings suggest that the optical band gap reduction commonly observed for PbS QD solids treated with thiol-terminating ligands can be prevalently ascribed to 3p orbitals localized on anchoring sulfur atoms, which mix with the highest occupied states of the QDs. More broadly, we provide evidence that organic ligands and inorganic cores are inherently electronically coupled materials thus yielding peculiar chemical species (the colloidal QDs themselves), which display arising (opto)electronic properties that cannot be merely described as the sum of those of the ligand and core components.

Three new metal-free organic dyes with the [1]benzothieno[3,2-b]benzothiophene (BTBT) π-bridge, having the structure donor-π-acceptor (D-π-A) and labeled as 19, 20 and 21, have been designed and synthesized for application in dye-sensitized solar cells (DSSC). Once the design of the π-acceptor block was fixed, containing the BTBT as the π-bridge and the cyanoacrylic group as the electron acceptor and anchoring unit, we selected three donor units with different electron-donor capacity, in order to assemble new chromophores with high molar extinction coefficients (ε), whose absorption features well reflect the good performance of the final DSSC devices. Starting with the 19 dye, which shows a molar extinction coefficient ε of over 14,000 M(-1) cm(-1) and takes into account the absorption maximun at the longer wavelength, the substitution of the BFT donor unit with the BFA yields a great enhancement of absorptivity (molar extinction coefficient ε > 42,000 M(-1) cm(-1)), until reaching the higher value (ε > 69,000 M(-1) cm(-1)) with the BFPhz donor unit. The good general photovoltaic performances obtained with the three dyes highlight the suitable properties of electron-transport of the BTBT as the π-bridge in organic chromophore for DSSC, making this very cheap and easy to synthesize molecule particularly attractive for efficient and low-cost photovoltaic devices.

An explorative dye solar cell architecture based on the implementation of a 3D micropatterned photoelectrode is disclosed here. An array of conical micropillars has been realized by laser micromachining of photosensitive glass which has been advantageously used as a substrate for deposition of a thin transparent conductive layer and a thick mesoporous TiO2 electrode. A significantly higher photocurrent density has been detected as an effect of the extended overall absorbing area of the micropatterned photoelectrode with respect to a conventional 2D reference photoelectrode. This enhancement can also be partially imputable to a not negligible "waveguide effect" occurring within the glass micropillars.

Surface modification of textiles with desired functionalities can be engineered by a considerable number of techniques ranging from traditional treatments to multifunctional approaches. Textiles, in fact, offer a challenging platform for functional modifications in order to meet additional strategic requirements for a large variety of applications. This article reviews recent developments involving modification of cotton textiles using physical methods (corona discharge, plasma) and chemical methods (vapor-phase atomic layer deposition treatment, surface grafting, enzymatic modification, cationic modification with nanoparticles, sol-gel technique, method and treatment with different reagents) and their characterization. The authors will present how the controlled wettability has been integrated into traditional materials to improve their performances and to extend their practical applications by developing new functionalities. The authors give a brief background on applications of cotton-modified surfaces and the development of novel innovative production techniques used to modify the surface materials and to improve the product quality.

An organic based microcavity showing fully reversible colour tunability has been achieved for the first time. The emission output changes according to the modulation from pure photonic to polaritonic resonant modes through UV irradiation of the light-switchable matrix.

A novel free-standing and flexible counter electrode for dye solar cells has been developed by conveniently transferring a vertically aligned carbon nanotube forest onto an oxygen-plasma-treated flexible, free-standing and conductive nanocomposite foil. Vertically aligned carbon nanotubes were first grown onto an aluminium foil by chemical vapour deposition and then transferred to the nanocomposite surface by hot pressing. The most meaningful electrochemical parameters have been quantitatively analyzed by means of electrochemical impedance spectroscopy and cyclic voltammetry in order to elucidate how the implementation of the anisotropic carbon nanotube top layer impacts the ultimate catalytic performances of the plate. Such an engineered counter electrode is able to guarantee a fast and effective reduction of the iodide-based electrolyte as well as to provide a solar conversion efficiency that is comparable with a typical Pt/TCO-coated rigid counter electrode. A photocurrent density higher than 13.36 mA cm(-2) along with a solar conversion efficiency of 7.26% have been reported for the dye solar cell mounting a counter-electrode based on vertically aligned carbon nanotubes implanted onto a conductive nanocomposite plate.

Partial shading is a commonly encountered mismatch problem in a photovoltaic system. In the drawing near perspective of their massive building integration, dye solar cell (DSC) modules may realistically receive different levels of irradiance, a situation similar to partial shading. In these conditions, the electrical characteristics of the DSC module significantly change. Here a general model for the description and the analysis of dye solar generators is proposed. A new equivalent circuit for DSCs has been developed that is characterized by the introduction of a second diode, capable to conveniently take into account the behavior of the reverse-biased cell/s. An experimental demonstration of the proposed two-diode model's validity is provided. A detailed description, based on numerical analysis, of the influence of partial shading on the photovoltaic performances of a DSC module made by four W-connected cells is given. We here demonstrate that the implementation of a two-diode model allows an excellent matching between the experimentally measured I-V characteristics of the partially shaded module and the simulated ones. Copyright (c) 2012 John Wiley & Sons, Ltd.

Functional supramolecular architectures for bottom-up organic nano- and microtechnology are a high priority research topic. We discovered a new recognition algorithm, resulting from the combination of thioalkyl substituents and head-to-head regiochemistry of substitution, to induce the spontaneous self-assembly of sulfur overrich octathiophenes into supramolecular crystalline fibers combining high charge mobility and intense fluorescence. The fibers were grown on various types of surfaces either as superhelices or straight rods depending on molecular structure. Helical fibers directly grown on a field effect transistor displayed efficient charge mobility and intrinsic 'memory effect'. Despite the fact that the oligomers did not have chirality centers, one type of hand-helicity was always predominant in helical fibers, due to the interplay of molecular atropisomerism and sup ramolecular helicity induced by terminal substituents. Finally, we found that the new sulfur overrich oligothiophenes can easily be prepared in high yields through ultrasound and microwave assistance in green conditions.

The manuscript deals with the synthesis and properties of four new all-donor alternating poly(arylene-ethynylene)s DBSA, DBSTA, DTSA, and DTSTA. The polymers have been obtained by a Sonogashira cross-coupling of 9,10-diethynyl-anthracene with the dibromo-derivatives of 9,9-dioctyl-dibenzosilole (DBSA), 2,7-dithienyl-9,9-dioctyl-dibenzosilole (DBSTA), 4,4-dioctyl-dithienosilole (DTSA), or 2,6-dithienyl-9,9-dioctyl-dithienosilole (DTSTA). The polymers exhibited absorption profiles and frontier orbital energies strongly dependent on their primary structure. Density functional theory calculations confirmed experimental observations and provided an insight into the electronic structure of the macromolecules. In particular, the effects exerted by the thiophene units in DBSTA and DTSTA on the optical properties of the corresponding polymers could be rationalized with respect to DBSA and DTSA. Preliminary photovoltaic measurements have established that the performance of DTSA is among the highest reported for an all-donor polymer. Moreover, UV irradiation of DTSA films under air evidenced a remarkable photostability of this material, providing further evidence that ethynylene-containing electron-rich systems are promising donors for organic solar cells applications. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4860-4872

Although photons in vacuum are massless particles that do not appreciably interact with each other, significant interactions appear in suitable nonlinear media, leading to hydrodynamic behaviours typical of quantum fluids(1-6). Here, we show the generation and manipulation of vortex-antivortex pairs in a coherent gas of strongly dressed photons (polaritons) flowing against an artificial potential barrier created and controlled by a light beam in a semiconductor microcavity. The optical control of the polariton flow allows us to reveal new quantum hydrodynamical phenomenologies such as the formation of vortex pairs upstream from the optical barrier, a case of ultra-short time excitation of the quantum flow, and the generation of vortices with counterflow trajectories. Additionally, we demonstrate how to permanently trap and store quantum vortices hydrodynamically generated in the wake of a defect. These observations are supported by time-dependent simulations based on the non-equilibrium Gross-Pitaevskii equation(7).

Although optical technology provides the best solution for the transmission of information, all-optical devices must satisfy several qualitative criteria to be used as logic elements. In particular, cascadability is difficult to obtain in optical systems, and it is assured only if the output of one stage is in the correct form to drive the input of the next stage. Exciton-polaritons, which are composite particles resulting from the strong coupling between excitons and photons, have recently demonstrated huge non-linearities and unique propagation properties. Here we show that polariton fluids moving in the plane of the microcavity can operate as input and output of an all-optical transistor, obtaining up to 19 times amplification and demonstrating the cascadability of the system. Moreover, the operation as an AND/OR gate is shown, validating the connectivity of multiple transistors in the microcavity plane and opening the way to the implementation of polariton integrated circuits.

The manuscript describes the design, preparation and characterization of two structurally isomeric random poly(arylene-vinylene)s, the properties of which have been optimized for their use as donor materials in BHJ solar cells. The structure of the polymers was aimed at broadening as much as possible their absorption profile. Poly[9,9-dioctylfluorene-vinylene-co-4,7-dithiophen-2-yl-benzo[1,2,5]thiadiazole-vinylene] (P1) and poly[2,7-dithiophen-2-yl-9,9-dioctylfluorene-vinylene-co-4,7-benzo[1,2,5]thiadiazole-vinylene] (P2) were prepared using the Suzuki-Heck polymerization. The polymers were characterized by elemental analysis, NMR, UV-vis absorption and photoluminescence, cyclic voltammetry, and GPC. The electrochemical characterization of P1 and P2 revealed similar HOMO/LUMO energy levels, although the UV-vis absorption profile of P2 is markedly broader than the one exhibited by P1. The more panchromatic absorption of P2 was explained by DFT and TDDFT calculations showing that the model systems, contributing together to the description of the random polymeric structure, exhibited different calculated excitation energies, that cover a broader portion of the absorption spectrum. In BHJ solar cells, the broadness of the absorption strongly influences the BHJ solar cell performances of P2 compared to P1 leading to higher short circuit currents and to a 3-fold higher power conversion efficiency. The PCE value (0.6%) obtained with P2 is in line with those obtained for other poly(heteroarylene-vinylene)s donors and is amenable to improvement by optimizing the device construction (PC61BM amount in the blend or use of annealing processes). These results demonstrate how combination of a suitable choice of the sequence of aryl units together with the potentialities offered by random polymers, can be useful tools in the design of new light-harvesting polymers in BHJ.

Almost all Iridium(III) complexes employed both as dopants in PhOLEDs and as pharmaceuticals and fluorescence bioprobes are racemic mixtures. In this study the single enantiomers of the most stable diastereomeric form fac-trans-N-N, bis[2-(4,6-difluorophenyl)pyridinato-C(2),N](picolinato)iridium(III) (FIrpic) were separated and analysed. The data obtained showed that the complex can be separated into stable optically active Λ and Δ isomers employing cellulose based chiral stationary phase both in normal and polar phase mode. Their chirality was confirmed and their absolute configuration assigned employing several methods (DFT and TDDFT calculations, CD and VCD). The CPL spectroscopy of the isolated enantiomers of FIrpic was also recorded due to its possible value in the OLEDs field. The chromatographic method was applied for a semipreparative purpose demonstrating that polar organic solvent chromatography (POSC) could be used to avoid the low-solubility issues associated with these Iridium(III) complexes. Finally, the chemical and stereochemical stability of the single isomers was evaluated under thermal stress by liquid chromatography coupled to high-resolution mass spectrometry (LC-QTOF) on both chiral and achiral columns. No racemization and/or isomerization was observed; however, the dissociation of the ancillary ligand was demonstrated employing LC-QTOF.

This study deals with the synthesis and characterization of two new di-anchoring dyes for applications in dye-sensitized solar cells. The materials were designed with a branched D(-pi-A)(2) structure containing (i) a rigid alkyl-functionalized carbazole core as the donor part, (ii) one (DYE1) or two (DYE2) thiophene units as the pi-bridge and (iii) a cyano-acrylic moiety as acceptor and anchoring part. Electrochemical impedance spectroscopy indicated that the injected electron lifetime is higher in the case of DYE2, probably due to the length of the pi-spacer that, in combination with the alkyl chain on the carbazole unit, hampers the charge recombination with the electrolyte. Stability tests on TiO2-sensitized films revealed that the di-anchoring remarkably slows down the desorption process, which conversely is evident for classic reference dyes. The highest power conversion efficiency reaches 5.01% in the case of DYE2 with a photovoltage of 0.70 V and a photocurrent of 10.52 mA cm(-2), substantially deriving from a broader absorption with respect to DYE1, as also confirmed by IPCE measurements. These results support the efforts aimed at the structural engineering of D(-pi-A)(2) dyes to design new, more efficient and stable organic sensitizers.

Aim of this work was to investigate the automatic echographic detection of an experimental drug delivery agent, halloysite clay nanotubes (HNTs), by employing an innovative method based on advanced spectral analysis of the corresponding "raw" radiofrequency backscatter signals. Different HNT concentrations in a low range (5.5-66 × 10(10) part/mL, equivalent to 0.25-3.00 mg/mL) were dispersed in custom-designed tissue-mimicking phantoms and imaged through a clinically-available echographic device at a conventional ultrasound diagnostic frequency (10 MHz). The most effective response (sensitivity = 60%, specificity = 95%), was found at a concentration of 33 × 10(10) part/mL (1.5 mg/mL), representing a kind of best compromise between the need of enough particles to introduce detectable spectral modifications in the backscattered signal and the necessity to avoid the losses of spectral peculiarity associated to higher HNT concentrations. Based on theoretical considerations and quantitative comparisons with literature-available results, this concentration could also represent an optimal concentration level for the automatic echographic detection of different solid nanoparticles when employing a similar ultrasound frequency. Future dedicated studies will assess the actual clinical usefulness of the proposed approach and the potential of HNTs for effective theranostic applications.

Halloysite clay Nanotubes (HNTs) are nanomaterials composed of double layered aluminosilicate minerals with a hollow tubular structure in the submicron range. They are characterized by a wide range of applications in anticancer therapy as agent delivery. In this work we aim to investigate the automatic detection features of HNTs through advanced quantitative ultrasound imaging employing different concentrations (3-5 mg/mL) at clinical conventional frequency, i.e. 7 MHz. Different tissue mimicking samples of HNT containing agarose gel were imaged through a commercially available echographic system, that was opportunely combined with ultrasound signal analysis research platform for extracting the raw ultrasound radiofrequency (RF) signals. Acquired data were stored and analyzed by means of an in-house developed algorithm based on wavelet decomposition, in order to identify the specific spectrum contribution of the HNTs and generate corresponding image mapping. Sensitivity and specificity of the HNT detection were quantified. Average specificity (94.36%) was very high with reduced dependency on HNT concentration, while sensitivity showed a proportional increase with concentration with an average of 46.78%. However, automatic detection performances are currently under investigation for further improvement taking into account image enhancement and biocompatibility issues

We report on the fabrication of the first bicolor micropixelated OLED from a single molecular material using a single-step bottom up procedure, The implementation of a deposition technique, based on a spatial-switch and con formational-sensitive STD surface-tension-driven lithography, has allowed us to exploit the spontaneous supramolecular properties and the conformational flexibility of a conjugated thiophene-based material, 6-bis-(50-hexyl-[2, 20]bithiophen-5-yl)-3, 5-dimethyl-dithieno[3, 2-b: 20, 30-d]-thiophene (DTT7Me). The existence of two regularly alternating emitting regions on a micrometer scale allows obtaining electroluminescent emission at two different wavelengths from a single material.

Oil spills at sea are a severe global environmental issue. Smart materials with controllable wettability are of global challenging interest in oil-water related applications. Nature offers a versatile platform of remarkable hierarchical structures with a chemical component, which provides bioinspired solutions for solving many challenges. In this study, an approach to achieve robust superhydrophobic/oleophobic property on flexible polydimethylsiloxane (PDMS) surfaces which mimics the hierarchical morphology of the natural lotus leaf surface is shown. The structure is prepared by hydrothermal assembly of zinc oxide nanorods onto the microstructured surface, which results in an underwater superoleophobic surface with an oil contact angle up to 153 degrees which can effectively prevent the surface from being polluted by oils. Our results are significant in terms of their importance to academic research and industrial applications and may lead to an innovative impact in the science field.

Liquid flow in microchannels is completely laminar and uniaxial, with a very low Reynolds number regime and long mixing lengths. To increase fluid mixing and solubility of reactants, as well as to reduce reaction time, complex three-dimensional networks inducing chaotic advection have to be designed. Alternatively, turbulence in the liquid can be generated by active mixing methods (magnetic, acoustic waves, etc.) or adding small quantities of elastic materials to the working liquid. Here, polyelectrolyte multilayer capsules embodying a catalytic polyoxometalate complex have been suspended in an aqueous solution and used to create elastic turbulence and to propel fluids inside microchannels as an alternative to viscoelastic polymers. The overall effect is enhanced and controlled by feeding the polyoxometalate-modified capsules with hydrogen peroxide, H2O2, thus triggering an on-demand propulsion due to oxygen evolution resulting from H2O2 decomposition. The quantification of the process is done by analysing some structural parameters of motion such as speed, pressure, viscosity, and Reynolds and Weissenberg numbers, directly obtained from the capillary dynamics of the aqueous mixtures with different concentrations of H2O2. The increases in fluid speed as well as the capsule-induced turbulence effects are proportional to the H2O2 added and therefore dependent on the kinetics of H2O2 dismutation.

Multicompartment, spherical microcontainers were engineered through a layer-by-layer polyelectrolyte deposition around a fluorescent core while integrating a ruthenium polyoxometalate (Ru4POM), as molecular motor, vis-a-vis its oxygenic, propeller effect, fuelled upon H2O2 decomposition. The resulting chemomechanical system, with average speeds of up to 25 mu ms(-1), is amenable for integration into a microfluidic set-up for mixing and displacement of liquids, whereby the propulsion force and the resulting velocity regime can be modulated upon H2O2-controlled addition.

The exploitation of cell-instructive scaffolds with uniform physical/chemical surfaces and controlled stiffness will be greatly useful in tissue engineering applications to resemble the extracellular matrix (ECM) or topographical appearance of native tissues. We herein describe a versatile and straightforward method to assemble a polydimethylsiloxane (PDMS)-composite structure in which a uniformly laminin-coated membrane is placed on top of a micropatterned substrate that applies a stiffness gradient. This 'double-sheet' structure provides soft or stiff microdomains that guide the self-patterning of different cell types [e. g. chronic myeloid leukemia (KU812), cervix carcinoma (HeLa), NIH 3T3 and BJ], thereby stimulating their cytoskeletal remodeling. More interestingly, we used these uniform PDMS surfaces with patterned rigidity for obtaining co-cultures of tumor blood cells (KU812) and adherent fibroblasts (NIH 3T3) with spatially-controlled distribution. Thus, beyond single-cell stiffening and mechanosensing, these surfaces should also be used as simple and feasible co-culture systems for mimicking and dissecting the bidirectional interactions between blood cells and specific stromal elements of their in vivo microenvironment.

A thin anatase titanium dioxide compact film was deposited by electron beam evaporation as buffer layer between the conductive transparent electrode and the porous TiO2-based photoelectrode in dye-sensitized solar cells. The effect of such a buffer layer on the back transfer reaction of electrons to tri-iodide ions in liquid electrolyte-based cells has been studied by means of both electrochemical impedance spectroscopy and open circuit photovoltage decay analysis. The influence of the thickness has been also investigated and an increment in overall quantum conversion efficiency eta as high as +31% with respect to the standard cell - fabricated onto an uncoated conductive glass - has been revealed in the case of a 120 nm thick buffer layer. (C) 2010 Elsevier B.V. All rights reserved

Here we investigate charge carrier generation and extraction processes in hybrid polymer/nanocrystal solar cells by means of time-resolved optical and photoelectrical techniques. We addressed the role of both poly(3-hexylthiophene) and colloidal arenethiolate-capped PbS quantum dots, which constitute the hybrid composite nanomaterial, in the photoinduced processes most relevant to device operation by changing the compositional ratio and applying chemical and thermal postdeposition treatments. The carrier generation processes were found to be wavelength-dependent: excitons generated in the polymer domains led to long-lived weakly bound charge pairs upon electron transfer to PbS nanocrystals; whereas charge carrier generation in the nanocrystal domains is highly efficient, although effective separation required the application of external electric field. Overall, charge carrier generation was found efficient and almost independent of the strength of applied electric field; therefore, competition between separation of electron–hole pairs into free carriers and geminate recombination is the major factor limiting the fill factor of nanocomposite-based solar cells. Device efficiency improvements thus require faster interfacial charge transfer processes, which are deeply related to the refinement of nanocrystal surface chemistry.

Suitable postsynthesis surface modification of lead-chalcogenide quantum dots (QDs) is crucial to enable their integration in photovoltaic devices. Here we exploit arenethiolate anions to completely replace pristine oleate ligands on PbS QDs in the solution phase, thus preserving the colloidal stability of QDs and allowing their solution-based processability into photoconductive thin films. Complete QD surface modification relies on the stronger acidic character of arenethiols compared to that of alkanethiols and is demonstrated by FTIR and UVvisNIR absorption spectroscopy analyses, which provide quantitative evaluation of stoichiometry and thermodynamic stability of the resulting system. Arenethiolate ligands induce a noticeable reduction of the optical band gap of PbS QDs, which is described and explained by charge transfer interactions occurring at the organic/inorganic interface that relax exciton confinement, and a large increase of QD molar absorption coefficient, achieved through the conjugated moiety of the replacing ligands. In addition, surface modification in the solution phase promotes switching of the symmetry of PbS QD self-assembled superlattices from hexagonal to cubic close packing, which is accompanied by further reduction of the optical band gap, ascribed to inter-QD exciton delocalization and dielectric effects, together with a drastic improvement of the charge transport properties in PbS QD solids. As a result, smooth dense-packed thin films of arenethiolate-capped PbS QDs can be integrated in heterojunction solar cells via a single solution-processing step. Such single PbS QD layers exhibit abated cracking upon thermal or chemical postdeposition treatment, and the corresponding devices generate remarkable photocurrent densities and overall efficiencies, thus representing an effective strategy toward low-cost processing for QD-based photovoltaics.

We implemented a low-temperature approach to fabricate efficient photoanodes for dye-sensitized solar cells, which combines three different nanoarchitectures, namely, a highly conductive and highly transparent AZO film, a thin TiO2-blocking layer, and a mesoporous TiO2 nanorod-based working electrode. All the components were processed at T 200 degrees C. Both the AZO and the TiO2 blocking layers were deposited by reactive sputtering, whereas the TiO2 nanorods were synthesized by surfactant-assisted wet-chemical routes and processed into photoelectrodes in which the native geometric features assured uniform mesoporous structure with effective nanocrystal interconnectivity suitable to maximize light harvesting and electron diffusion. Because of the optimized structure of the TiO2-blocking/AZO bilayer, and thanks to the good adhesion of the TiO2 nanorods over it, a significant enhancement of the charge recombination resistance was demonstrated, this laying on the basis of the outstanding power conversion efficiency achievable through the use of this photoanode's architecture: a value of 4.6% (N719) was achieved with a 4-mu m-thick electrode processed at T = 200 degrees C. This value noticeably overcomes the current literature limit got on AZO-based cells (N719), which instead use Nb-doped and thicker blocking layers, and thicker nanostructured photoanodes, which have been even sintered at higher temperatures (450-500 degrees C).

In this study we evaluated an efficient microwave-solvothermal method to synthesize effective visible-light photocatalists based on the use of anatase TiO2 nanorods. The nanocrystals were obtained by hydrolysis of titanium tetraisopropoxide (TTIP) in the presence of benzyl alcohol at 210 °C. The method was effective and produced TiO2 nanocrystals in the anatase phase with a rapid kinetics of crystallization. A significant size control was obtained tuning the TTIP to oleic acid molar ratio. High volumetric yield and reduced energy costs were achieved. All synthesized TiO2 nanocrystals showed a high photoactivity in comparison with commercial P25 titania, as they could degrade faster and completely Rhodamine B dye in solution under visible-light irradiation. The nanocrystals were characterized in detail by X-ray diffraction, low- and high-resolution transmission electron microscopy, microRaman and FT-IR spectroscopy. A distorted anatase structure due to oxygen vacancies was identified as being at the origin of the introduction of new energy levels into the anatase band gap, which probably promoted the visible-light photoactivity.

Three fluorenone-derived two-photon fluorescent probes (TK) targeting the lysosomes (TK-Lyso) and mitochondria (TK-Mito1 and TK-Mito2) were synthesized by introducing different diphenylamine moieties into the fluorenone core. The TK dyes showed high biocompatibility and long-term retention, low cytotoxicity, large Stokes shift and good fluorescence quantum yield. The results of the present work disclose a class of organic dyes with potential wide applications as specific and efficient probes for lysosomes and mitochondria in the study of various biological processes.

We present a spectroscopic investigation on a new hyperbranched cadmium selenide nanocrystals (CdSe NC)/poly(3-hexylthiophene) (P3HT) blend, a potentially good active component in hybrid photovoltaics. Combined ultrafast transient absorption spectroscopy and morphological investigations by means of an ultrafast confocal microscope reveal a strong influence of the complex local structure on the photogenerated carrier dynamics. In particular, we map the electron-transfer process across the hybrid NC/polymer interface, and we reveal that charge separation occurs through a preferential pathway from the CdSe nanobranches to the P3HT chains. Efficient charge generation at the distributed heterojunction is also confirmed by scanning kelvin probe force microscopy measurements.

To evaluate the diagnostic performance of gold nanorod (GNR)-enhanced optoacoustic imaging employing a conventional echographic device and to determine the most effective operative configuration in order to assure optoacoustic effectiveness, nanoparticle stability, and imaging procedure safety. The most suitable laser parameters were experimentally determined in order to assure nanoparticle stability during the optoacoustic imaging procedures. The selected configuration was then applied to a novel tissue-mimicking phantom, in which GNR solutions covering a wide range of low concentrations (25-200 pM) and different sample volumes (50-200 μL) were exposed to pulsed laser irradiation. GNR-emitted optoacoustic signals were acquired either by a couple of single-element ultrasound probes or by an echographic transducer. Off-line analysis included: (a) quantitative evaluation of the relationships between GNR concentration, sample volume, phantom geometry, and amplitude of optoacoustic signals propagating along different directions; (b) echographic detection of "optoacoustic spots," analyzing their intensity, spatial distribution, and clinical exploitability. MTT measurements performed on two different cell lines were also used to quantify biocompatibility of the synthesized GNRs in the adopted doses. Laser irradiation at 30 mJ/cm(2) for 20 seconds resulted in the best compromise among the requirements of effectiveness, safety, and nanoparticle stability. Amplitude of GNR-emitted optoacoustic pulses was proportional to both sample volume and concentration along each considered propagation direction for all the tested boundary conditions, providing an experimental confirmation of isotropic optoacoustic emission. Average intensity of echographically detected spots showed similar behavior, emphasizing the presence of an "ideal" GNR concentration (100 pM) that optimized optoacoustic effectiveness. The tested GNRs also exhibited high biocompatibility over the entire considered concentration range. An optimal configuration for GNR-enhanced optoacoustic imaging was experimentally determined, demonstrating in particular its feasibility with a conventional echographic device. The proposed approach can be easily extended to quantitative performance evaluation of different contrast agents for optoacoustic imaging.

In the last few years, a new class of smart multifunctional photoelectrochemical devices has been attracting the interest of several academic institutions and industrial companies: photovoltachromic cells, combining the features of photoelectrochromic cells with those of dye-sensitized solar cells. Here, we report the results of a detailed electrochemical analysis aiming at investigating the electrochemical behavior of these complex photoelectrochemical devices. In particular, we have been focused on the effect of Li+ ions displacement during the coloration of the electrochromic tungsten oxide on the performances of the photovoltaic unit. As we had previously observed striking differences between the performances of the barely photovoltaic mode (with the tungsten oxide in the bleached state) and the photovoltachromic mode (with the tungsten oxide in the colored state), we thus attempted to provide a reasonable physical interpretation to the observed phenomena. © 2013 John Wiley & Sons, Ltd.

High-yield, rapid and facile synthesis of elongated pure anatase titania nanoparticles has been achieved through a nonaqueous microwave-based approach. The residual organics onto nanoparticles surfaces were completely removed through a new treatment under ozone flow, at room temperature in air. Such an ozone cleaning method revealed an effective inexpensive dry process of removing organic contaminants from nanoparticles surfaces. The TiO2 elongated nanoparticles having a length of 13.8 ± 5.5 nm and a diameter of 9.0 ±1.2 nm were characterized by powder X-Ray diffraction, transmission electron microscopy, selected area diffraction, BET surface area analyzer and FT‑IR spectroscopy. Photocatalytic evaluation demonstrated that the as-synthesized ozone-cleaned TiO2 nanoparticles and TiO2 nanoparticles loaded with platinum possess excellent Rhodamine B performance with respect to both commercial spherical nanotitania P25 and P25 loaded with platinum. This could be attributed to the anatase phase purity, small size, large specific surface area and clean surfaces of the prepared nanoparticles.

Three families of linear shaped TiO2 anatase nanocrystals with variable aspect ratio (4, 8, 16) and two sets of branched TiO2 anatase nanocrystals (in the form of open-framework sheaf-like nanorods and compact braid-like nanorod bundles, respectively) were employed to fabricate high-quality mesoporous photoelectrodes and then implemented into dye-sensitized solar cells to elucidate the intrinsic correlation holding between the photovoltaic performances and the structure of the nanocrystal building blocks. To this aim, the chemical capacitance and the charge-transfer resistance of the photoelectrodes were extrapolated from electrochemical impedance spectroscopy measurements and used to draw a quantitative energy diagram of the dye-sensitized solar cells realized, on the basis of which their photovoltaic performances have been discussed. It has thus been revealed that photoanodes made from braid-like branched-nanorod bundles exhibited the most favorable conditions to minimize recombination at the interface with the electrolyte due to their deep distribution of trap states, whereas linear-shaped nanorods with higher aspect-ratios result in more remarkable downshift of the conduction band edge.

High-yield, rapid and facile synthesis of elongated pure anatase titania nanoparticles has been achieved through a nonaqueous microwave-based approach. The residual organics onto nanoparticles surfaces were completely removed through a new treatment under ozone flow, at room temperature in air. Such an ozone cleaning method revealed an effective inexpensive dry process of removing organic contaminants from nanoparticles surfaces. The TiO2 elongated nanoparticles having a length of 13.8 +/- 5.5 nm and a diameter of 9.0 +/- 1.2 nm were characterized by powder X-Ray diffraction, transmission electron microscopy, selected area diffraction, BET surface area analyzer and FT-IR spectroscopy. Photocatalytic evaluation demonstrated that the as-synthesized ozone-cleaned TiO2 nanoparticles and TiO2 nanoparticles loaded with platinum possess excellent Rhodamine B performance with respect to both commercial spherical nanotitania P25 and P25 loaded with platinum. This could be attributed to the anatase phase purity, small size, large specific surface area and clean surfaces of the prepared nanoparticles.

This study deals with the synthesis and characterization of two p-extended organic sensitizers (G1 and G2) for applications in dye-sensitized solar cells. The materials are designed with a D-A-pi-A structure constituted by i) a triarylamine group as the donor part, ii) a dithienyl-benzothiadiazole chromophore followed by iii) a further ethynylene-thiophene (G1) or ethynylene-benzene (G2) pi-spacer and iv) a cyano-acrylic moiety as acceptor and anchoring part. An unusual structural extension of the p-bridge characterizes these structures. The so-configured sensitizers exhibit a broad absorption profile, the origin of which is supported by density functional theory. The absence of hypsochromic shifts as a consequence of deprotonation as well as notable optical and electrochemical stabilities are also observed. Concerning the performances in devices, electrochemical impedance spectroscopy indicates that the structural modification of the pi-spacer mainly increases the electron lifetime of G2 with respect to G1. In devices, this feature translates into a superior power conversion efficiency of G2, reaching 8.1%. These results are comparable to those recorded for N719 and are higher with respect to literature congeners, supporting further structural engineering of the pi-bridge extension in the search for better performing pi-extended organic sensitizers.

The current trend in the development of biomaterials is towards bioactive and biodegradable systems. In particular, enzyme-responsive structures are useful tools to realize biodegradable surfaces for the controlled delivery of biomolecules/drugs through a triggered surface erosion process. Up to now, enzyme-responsive structures have been designed by covalent linkage between synthetic polymers and biodegradable functionalities that are responsive to chemical and biological cues (i.e. proteases or pH) [1], [2], [3] and [4]. Here, we present a novel approach to achieve enzyme-responsive surface-attached networks by exploiting the non-covalent interaction between streptavidin and biotin. The functional component of this three-dimensional (3D) structure is a layer of biotinylated peptides that are degraded by the action of specific proteases. The system was stable under typical physiological conditions; however, it was efficiently degraded upon enzyme exposure. Further, the controlled release of biomolecules and drugs – previously entrapped into the surface-attached network – was demonstrated to occur as a consequence of the enzymatic cleavage. This versatile approach does not require complex chemical procedures. Interestingly, it can be easily adapted to different enzyme-peptide partners and therefore is very attractive for tissue replacement, drug delivery and biosensing.

In this paper, we report on the effect of metal oxidation on strong coupling interactions between silver nanostructures and a J-aggregated cyanine dye. We show that metal oxidation can sensibly affect the plexcitonic system, inducing a change in the coupling strength. In particular, we demonstrate that the presence of oxide prevents the appearance of Rabi splitting in the extinction spectra for thick spacers. In contrast, below a threshold percentage, the oxide layer results in an higher coupling strength between the plasmon and the Frenkel exciton. Contrary to common belief, a thin oxide layer seems thus to act, under certain conditions, as a coupling mediator between an emitter and a localized surface plasmon excited in a metallic nanostructure. This suggests that metal oxidation can be exploited as a means to enhance light-matter interactions in strong coupling applications.

There is a strong demand of implantable devices for diverse applications. Most of them are dedicated and are used for therapy activators, and others for monitoring physiological parameters. The aforementioned demand must be correlated to the utilization of new materials and their reliability during use. This research proposes a design of a complete implantable packaging for encompassing neuro-recording electroencephalogram signals. The content of all system is also illustrated in terms of inner devices and simulated in terms of thermal behavior. Finally the neuro-packaging has been built in polylactic acid and tested in appropriate experimental setup for a specific characterization by measuring temperature, humidity and deformation. However, since PLA is a bioadsorbable polymer, a further design has been performed covering the neuro-packaging with another biocompatible nanomaterial called ultra-high-molecular-weight polyethylene in order to avoid the bioabsorption.

Spin-glass theory is one of the leading paradigms of complex physics and describes condensed matter, neural networks and biological systems, ultracold atoms, random photonics and many other research fields. According to this theory, identical systems under identical conditions may reach different states. This effect is known as replica symmetry breaking and is revealed by the shape of the probability distribution function of an order parameter named the Parisi overlap. However, a direct experimental evidence in any field of research is still missing. Here we investigate pulse-to-pulse fluctuations in random lasers, we introduce and measure the analogue of the Parisi overlap in independent experimental realizations of the same disordered sample, and we find that the distribution function yields evidence of a transition to a glassy light phase compatible with a replica symmetry breaking.

In this work, we investigate the optical and structural properties of the well-known triplet emitter bis(4',6'-difluorophenylpyridinato)-iridium(III) picolinate (FIrpic), showing that its ability to pack in two different ordered crystal structures promotes attractive photophysical properties that are useful for solid-state lighting applications. This approach allows the detrimental effects of the nonradiative pathways on the luminescence performance in highly concentrated organic active materials to be weakened. The remarkable electro-optical behavior of sky-blue phosphorescent organic light-emitting diodes incorporating crystal domains of FIrpic, dispersed into an appropriate matrix as an active layer, has also been reported as well as the X-ray diffraction, nuclear magnetic resonance, electro-ionization mass spectrometry, and scanning electron microscopy analyses of the crystalline samples. We consider this result as a crucial starting point for further research aimed at the use of a crystal triplet emitter in optoelectronic devices to overcome the long-standing issue of luminescence self-quenching.

Exciton-polaritons are bosonic quasiparticles that arise from the normal mode splitting of photons in a microcavity and excitons in a semiconductor material. One of the most intriguing extensions of such a lightmatter interaction is the so-called ultrastrong coupling regime. It is achieved when the Rabi frequency (Omega(R), the energy exchange rate between the emitter and the resonant photonic mode) reaches a considerable fraction of the emitter transition frequency, omega(0). Here, we report a Rabi energy splitting (2h Omega(R)) of 1.12 eV and record values of the coupling ratio (2 Omega(R)/omega(0)) up to 0.6-fold the material band gap in organic semiconductor microcavities and up to 0.5-fold in monolithic heterostructure organic light-emitting diodes working at room temperature. Furthermore, we show that with such a large coupling strength it is possible to undress the exciton homogeneous linewidth from its inhomogeneous broadening, which allows for an unprecedented narrow emission line (below the cavity finesse) for such organic LEDs. The latter can be exploited for the realization of novel monochromatic sources and near-IR organic emitting devices

We demonstrate the fabrication of all-inorganic heterostructured n–p junction devices made of colloidal PbS quantum dots (QDs) and TiO2 nanorods (NRs). The entire device fabrication procedure relies on room-temperature processing, which is compatible with flexible plastic substrates and low-cost production. Through Kelvin Probe Force Microscopy and femtosecond pump and probe spectroscopy we decipher the electron transfer process occurring at the interface between the colloidal PbS QDs and TiO2 anatase NRs. Overall we demonstrate a high power conversion efficiency of [similar]3.6% on glass and [similar]1.8% on flexible substrates, which is among the highest reported for entirely inorganic-nanocrystal based solar cells on plastic supports.

Abstract Hybrid inorganic/organic core/shell nanoparticles were prepared through a two step synthesis procedure. In the first step, pure anatase TiO2 nanoparticles were synthesized though a rapid microwave assisted non-aqueous route. Then, the obtained titania nanoparticles were coated with polyvinyl alcohol (PVA) using a simple solution method followed by relatively low temperature treatment. The PVA-coated titania nanoparticles samples were prepared at different TiO2-PVA weight ratio and they were characterized using X-Ray diffraction, transmission electron microscopy, infrared spectroscopy and Brunauer-Emmett-Teller (BET) analysis. Photocatalytic performance was also evaluated for all samples and the results indicated that TiO2:PVA weight ratio was a key factor to obtain an improvement of the photocatalytic activity with respect to bare TiO2 nanoparticles, since {PVA} concentration influenced the surface area and the aggregation of nanoparticles and the thickness of the coating layer. This inexpensive system provides a simple, quick and effective approach which allows to obtain core/shell hybrid nanostructures.

Electrospinning is a versatile method for preparing functional three-dimensional scaffolds. Synthetic and natural polymers have been used to produce micro- and nanofibers that mimic extracellular matrices. Here, we describe the use of emulsion electrospinning to prepare blended fibers capable of hosting aqueous species and releasing them in solution. The existence of an aqueous and a non-aqueous phase allows water-soluble molecules to be introduced without altering the structure and the degradation of the fibers, and means that their release properties under physiological conditions can be controlled. To demonstrate the loading capability and flexibility of the blend, various species were introduced, from magnetic nanoparticles and quantum rods to biological molecules. Cellular studies showed the spontaneous adhesion and alignment of cells along the fibers. Finally, in vivo experiments demonstrated the high biocompatibility and safety of the scaffolds up to 21 days post-implantation.

This study reports oil the first monodispersed molecular materials embodying the dibenzothiophene-5,5-dioxide core for the achievement of blue electroluminescence. The core has been functionalised in its 2.8- or 3,7-positions with dimethyl-fluorene (2,8-DBTOF and 3,7-DBTOF) or methyl-carbazole (2,8-DBTOC and 3,7-DBTOC) groups. The obtained compounds were characterised by H-1 and C-13 NMR, APCI-MS, thermal analysis (TGA and DSQ and cyclic voltammetry. Their optical and photophysical properties were investigated by UV and PL measurements as well as by time-dependent density-functional theory calculations. The materials were successfully employed as active layers ill blue to purplish blue p-i-n OLED devices. that reached, in the case of 3,7-DBTOC, performances as high as 11 422 cd m(-2) and 3.25 cd A(-1).

We demonstrate a general approach to fabricate a novel low-cost, lightweight and flexible nanocomposite foil that can be effectively implemented as a monolithic counter-electrode in dye solar cells. The pivotal aim of this work was to replace not only the platinum catalyzer film, but even the underlying transparent conductive oxide-coated substrate, by means of a monolithic counter electrode based on carbonaceous materials. According to our approach, a proper dispersion of multiwalled carbon nanotubes (MWCNTs) has been added to a dilute polypropylene solution in toluene. The composite solution has been then adequately mixed and subsequently dried by means of a controlled solvent evaporation process; the resulting powder has been modeled by compression molding into thin plates. Four different series of plates have been realized by tuning the carbon nanotubes concentration from 5 wt % to 20 wt %. Finally, a specifically setup reactive ion etching treatment with oxygen plasma has been carried out onto the plate surface to remove the residual polymeric capping layer and allow the embedded CNTs to protrude on top of the surface. A fine-tuning of the morphological features has been made possible by adjusting the plasma etching conditions. For all the treated surfaces, the most meaningful electrochemical parameters have been quantitatively analyzed by means of both electrochemical impedance spectroscopy and cyclic voltammetry measurements. An as high as 13.8 mA/cm(2) photocurrent density, along with a solar conversion efficiency of 6.67%, has been measured for a dye solar cell mounting a counter-electrode based on a 20 wt % CNT nanocomposite.

Novel triphenylamine (TPA)-based organic dyes were synthesized and assessed for their performance in dye-sensitized solar cells (DSSCs). In the dyes considered the TPA group and the cyanoacetic acid have the role of electron-donor and -acceptor, respectively, whereas a thienyl-fluoro-phenyl-substituted was introduced as p-linker to improve the dye performance in DSSCs. Experimental characterizations empasize that the presence of electron withdrawing substituents in the linker close to the electron-acceptor moiety leads to a more efficient intramolecular photoinduced charge transfer. In fact, photovoltaic experiments reveal that the DSSCs based on the thienyl-o-fluoro-phenyl substituted dyes yield a better solar-energy-to-electricity conversion efficiency.

We report on a multilayer structure hybrid light-emitting device (HLED) using a water/alcohol-soluble polymer poly(9,9-bis{30-[(N,N-dimethyl)-N-ethylammonium}-propyl]-2,7-fluorene dibromide) as an electron-transporting layer and a close-packed quantum dot-layer (QD-layer) as an emitting layer. The device was realized by full spin-coating technology without thermal evaporation process for the deposition of organic layers. The QD-layer was a mixture of QDs with two different sizes, in which large size QD-emitters were dispersed in small size QDs to weaken the concentration quenching. The device achieved a maximum power efficiency of 0.58 lm/W, which nearly quadrupled that of the HLED with a plain large size QD-EML. (C) 2010 American Institute of Physics.[doi: 10.1063/1.3484145]

In this work glucose (G), α-cyclodextrin (α-CD) and sodium salt of carboxymethyl cellulose (CMCNa) are used as dispersing agents for graphene oxide (GO), exploring the influence of both saccharide units and geometric/steric hindrance on the rheological, thermal, wettability and electrochemical properties of a GO/poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) nanocomposite. By acting on the saccharide-based additives, we can modulate the rheological, thermal, and wettability properties of the GO/PEDOT:PSS nanocomposite. Firstly, the influence of all the additives on the rheological behaviour of GO and PEDOT:PSS was investigated separately in order to understand the effect of the dispersing agent on both the components of the ternary nanocomposite, individually. Subsequently, steady shear and dynamic frequency tests were conducted on all the nanocomposite solutions, characterized by thermal, wettability and morphological analysis. Finally, the electrochemical properties of the GO/ PEDOT composites with different dispersing agents for supercapacitors were investigated using cyclic voltammetry (CV). The CV results revealed that GO/PEDOT with glucose exhibited the highest specific capacitance among the systems investigated.

The donor/acceptor inter-mixing in bulk heterojunction (BHJ) solar cells is a critical parameter, often leading to irreproducible performance of the finished device. An alternative solution-processed device fabrication strategy towards a better control of the micro/nano-structured morphology consists of a sequential coating of the donor (e.g., poly-(3-hexylthiophene), P3HT) and the acceptor (e.g., [6,6]-phenyl-C61-butyric acid methyl ester, PCBM) from orthogonal solvents. We demonstrate that, in spite of the solvent orthogonality, this technique does not lead to a well-defined bilayer with a sharp interface, but it rather results in a graded vertical phase-separated junction, resulting from the diffusion of the PCBM in the P3HT bottom layer. We are able to control the diffusion of PCBM, which occurs preferentially in the amorphous P3HT domains, by easily varying the ratio between crystalline/amorphous domains in the P3HT. Such a ratio can be simply modified by changing the solvent for P3HT. We show that the donor–acceptor diffused bilayer (DB) junction is an intermediate structure which combines both advantages of the well-defined bilayer and conventional BHJ configurations. Indeed, the DB device geometry ensures the good reproducibility and charge percolation, like the well-defined bilayer, while preserving the interpenetration of the donor and acceptor species, resulting in an efficient charge separation, characteristic of the BHJ. Overall the annealed DB device geometry can be assimilated to a graded BHJ with an improved reproducibility and mean power conversion efficiency (PCE) of 3.45%, higher than that of the standard BHJ devices of 3.07%. Furthermore, we demonstrate the highest performance for the as-cast DB device with a PCE of 2.58%. It is worthy to note that our DB device exhibits improved open circuit voltage, fill factor, series and shunt resistances, which denote that the vertically phase separated DB junction ensures improved charge percolation.

Here we conceive an innovative nanocomposite to endow hybrid perovskites with the easy processability of polymers, providing a tool to control film quality and material crystallinity. We verify that the employed semiconducting polymer, poly[2-methoxy-5-(2-ethylhexyloxy)-1,4-phenylenevinylene] (MEH-PPV), controls the self-assembly of CH₃NH₃PbI₃ (MAPbI₃) crystalline domains and favors the deposition of a very smooth and homogenous layer in one straightforward step. This idea offers a new paradigm for the implementation of polymer/perovskite nanocomposites towards versatile optoelectronic devices combined with the feasibility of mass production. As a proof-of-concept we propose the application of such nanocomposite in polymer solar cell architecture, demonstrating a power conversion efficiency up to 3%, to date the highest reported for MEH-PPV. On-purpose designed polymers are expected to suit the nanocomposite properties for the integration in diverse optoelectronic devices via facile processing condition.

The technology of white organic light-emitting diodes (WOLEDs) is attracting growing interest due to their potential application in indoor lighting. Nevertheless the simultaneous achievement of high luminous efficacy (LE), high color rendering index (CRI), very low manufacturing costs and compatibility with flexible thin substrates is still a great challenge. Indeed, very high efficiency devices show usually low values of CRI, not suitable for lighting applications, and use expensive indium tin oxide (ITO) electrodes which are not compatible with low cost and/or flexible products. Here we show a novel low cost ITO-free WOLED structure based on a multi-cavity architecture with increased photonic mode density and still broad white emission spectrum, which allows for simultaneous optimization of all device characteristics. Without using out-coupling optics or high refractive index substrates, CRI of 85 and LE as high as 33 lm W-1 and 14 lm W-1 have been demonstrated on ITO-free glass and flexible substrates, respectively. (C) 2013 Elsevier Ltd. All rights reserved.

In this Letter, we demonstrate a way to control the charge carrier transport mechanisms in phosphorescent organic light-emitting devices based on the mixing of two p and n host materials in the emissive layer (EML). The matrices have been selected in order to fulfill the requirements of the energy level mismatch with the transporting and emitting materials. By using the mixed-host approach in combination with a phosphorescent red emitter, namely (1-phenylisoquinoline) iridium (III) [Ir(piq)(3)], maximum external and power efficiencies of 14.3% and 10 lm/W, respectively, have been achieved, with an average external efficiency value of 12% in the luminance range 100-10,000 cd/m(2). (C) 2010 Optical Society of America

We demonstrate a general approach by which colloidal anatase TiO2 nanocrystals with anisotropically tailored linear and branched shapes can safely be processed into high-quality mesoporous photoelectrodes for dye-sensitized solar cells (DSSCs). A detailed study has been carried out to elucidate how the nanoscale architecture underlying the photoelectrodes impacts their ultimate performances. From the analysis of the most relevant electrochemical parameters,an intrinsic correlation between the photovoltaic performances and the structure of the nanocrystal building blocks has been deduced and explained on the basis of relative contributions of the electron transport and light-harvesting properties of the photoelectrodes. Depending on the nanocrystals incorporated,these devices can exhibit an energy conversion efficiency of 5.2% to 7.8%,which ranks 38% to 53% higher than that achievable with corresponding cells based on reference spherical nanoparticles. It has been ascertained that DSSCs based on high aspect-ratio linear nanorods allow for a remarkable improvement in the charge-collection efficiency due to minimization of detrimental charge-recombination processes at the photoelectrode/electrolyte interface. On the other hand,DSSCs fabricated from branched nanocrystals with a peculiar bundle-like configuration are characterized by a drastic reduction of undesired charge-trapping phenomena. These findings can be useful in the design and fabrication of future generations of high-performing DSSCs based on colloidal nanocrystals with properly engineered size and shape parameters.

The strong coupling of an excitonic transition with an electromagnetic mode results in composite quasi-particles called exciton polaritons, which have been shown to combine the best properties of their individual components in semiconductor microcavities. However, the physics and applications of polariton flows in organic materials and at room temperature are still unexplored because of the poor photon confinement in such structures. Here, we demonstrate that polaritons formed by the hybridization of organic excitons with a Bloch surface wave are able to propagate for hundreds of microns showing remarkable third-order nonlinear interactions upon high injection density. These findings pave the way for the study of organic nonlinear light-matter fluxes and for a technologically promising route of the realization of dissipation-less on-chip polariton devices operating at room temperature.

An engineered bi-layered photoelectrode for dye solar cells has been developed which profitably employs two synergistic meso-ordered components, namely a thin meso-ordered TiO2 film and a main microparticles-based photoelectrode. The former has been deposited as an interfacial layer at the FTO-coated substrate and suppresses the back-transport reaction by blocking direct contact between the electrolyte and conductive oxide. The latter is made of hierarchical micro- and nano-structured building blocks prepared by template synthesis, which permits efficient light scattering without sacrificing the internal surface area. The optimization of light harvesting and charge recombination dynamics allowed us to achieve as high energy conversion efficiency as 9.7%.

Driven by the tremendous opportunities offered by dye solar cells technology in terms of building integration, a new generation of smart multifunctional photoelectrochemical cells has the potential to attract the interest of a rapidly growing number of research institutions and industrial companies. Photovoltachromic devices are capable to produce a smart modulation of the optical transmittance and, at the same time, to generate electrical power by means of solar energy conversion. In this work, a specifically designed bifunctional counterelectrode has been realized by depositing a C-shaped platinum frame which bounds a square region occupied by a tungsten oxide (WO3) film onto a transparent conductive substrate. These two regions have been electrically separated to make possible distinct operations on one or both of the available circuits. Such an unconventional counterelectrode makes it possible to achieve a twofold outcome: a smart and fast-responsive control of the optical transmittance and a relatively high photovoltaic conversion efficiency. In particular we investigated the effect of the electrolyte composition on both photoelectrochromic and photovoltaic performances of such devices by systematically tuning the iodide content in the electrolyte. The best result was obtained by filling the cell with an iodine concentration of 0.005 M: a coloration efficiency of 61.10 cm(2) C-1 at a wavelength of 780 nm and, at the same time, a photovoltaic conversion efficiency of 6.55% have been reported.

Four different species of ionically conductive polymers were synthesized and successfully implemented to formulate novel quasi-solid electrolytes for dye solar cells. A power conversion efficiency superior to 85% of the correspondent liquid electrolyte as well as an excellent cell's stability was demonstrated after 500 days of storage.

Silica nanoparticles (SiNPs) are widely studied nanomaterials for their potential employment in advanced biomedical applications, such as selective molecular imaging and targeted drug delivery. SiNPs are generally low cost and highly biocompatible, can be easily functionalized with a wide variety of functional ligands, and have been demonstrated to be effective in enhancing ultrasound contrast at clinical diagnostic frequencies. Therefore, SiNPs might be used as contrast agents in echographic imaging. In this work, we have developed a SiNPs-based system for the in vitro molecular imaging of hepatocellular carcinoma cells that express high levels of glypican-3 protein (GPC-3) on their surface. In this regard, a novel GPC-3 targeting peptide was designed and conjugated to fluorescent silica nanoparticles. The physicochemical properties, acoustic behavior, and biocompatibility profile of the functionalized SiNPs were characterized; then binding and uptake of both naked and functionalized SiNPs were analyzed by laser scanning confocal microscopy and transmission electron microscopy in GPC-3 positive HepG2 cells, a human hepatocarcinoma cell line. The results obtained showed that GPC-3-functionalized fluorescent SiNPs significantly enhanced the ultrasound contrast and were effectively bound and taken up by HepG2 cells without affecting their viability.

A colloidal crystal-splitting growth regime has been accessed, in which TiO2 nanocrystals, selectively trapped in the metastable anatase phase, can evolve to anisotropic shapes with tunable hyperbranched topologies over a broad size interval. The synthetic strategy relies on a nonaqueous sol–gel route involving programmed activation of aminolysis and pyrolysis of titanium carboxylate complexes in hot surfactant media via a simple multi-injection reactant delivery technique. Detailed investigations indicate that the branched objects initially formed upon the aminolysis reaction possess a strained monocrystalline skeleton, while their corresponding larger derivatives grown in the subsequent pyrolysis stage accommodate additional arms crystallographically decoupled from the lattice underneath. The complex evolution of the nanoarchitectures is rationalized within the frame of complementary mechanistic arguments. Thermodynamic pathways, determined by the shape-directing effect of the anatase structure and free-energy changes accompanying branching and anisotropic development, are considered to interplay with kinetic processes, related to diffusion-limited, spatially inhomogeneous monomer fluxes, lattice symmetry breaking at transient Ti5O5 domains, and surfactant-induced stabilization. Finally, as a proof of functionality, the fabrication of dye-sensitized solar cells based on thin-film photoelectrodes that incorporate networked branched nanocrystals with intact crystal structure and geometric features is demonstrated. An energy conversion efficiency of 6.2% has been achieved with standard device configuration, which significantly overcomes the best performance ever approached with previously documented prototypes of split TiO2 nanostructures. Analysis of the relevant photovoltaic parameters reveals that the utilized branched building blocks indeed offer light-harvesting and charge-collecting properties that can overwhelm detrimental electron losses due to recombination and trapping events.

Manganese blue is a synthetic barium manganate(VI) sulphate compound that was produced from 1935 to the 1990s and was used both as a blue pigment in works of art and by conservators in the restoration of paintings. The photophysical properties of the compound are described as well as the setup needed to record the spatial distribution of the pigment in works of art.

AIM: The lack of sensitivity of chronic myeloid leukemia (CML) stem cells to imatinib mesylate (IM) commonly leads to drug dose escalation or early disease relapses when therapy is stopped. Here, we report that packaging of IM into a biodegradable carrier based on polyelectrolyte microcapsules increases drug retention and antitumor activity in CML stem cells, also improving the ex vivo purging of malignant progenitors from patient autografts. MATERIALS & METHODS: Microparticles/capsules were obtained by layer-by-layer (LbL) self-assembly of oppositely charged polyelectrolyte multilayers on removable calcium carbonate (CaCO(3)) templates and loaded with or without IM. A leukemic cell line (KU812) and CD34(+) cells freshly isolated from healthy donors or CML patients were tested. RESULTS & DISCUSSION: Polyelectrolyte microcapsules (PMCs) with an average diameter of 3 microm, fluorescently labelled multilayers sensitive to the action of intracellular proteases and 95-99% encapsulation efficiency of IM, were prepared. Cell uptake efficiency of such biodegradable carriers was quantified in KU812, leukemic and normal CD34(+) stem cells (range: 70-85%), and empty PMCs did not impact cell viability. IM-loaded PMCs selectively targeted CML cells, by promoting apoptosis at doses that exert only cytostatic effects by IM alone. More importantly, residual CML cells from patient leukapheresis products were reduced or eliminated more efficiently by using IM-loaded PMCs compared with freely soluble IM, with a purging efficiency of several logs. No adverse effects on normal CD34(+) stem-cell survival and their clonogenic potential was noticed in long-term cultures of hematopoietic progenitors in vitro. CONCLUSION: This pilot study provides the proof-of-principle for the clinical application of biodegradable IM-loaded PMC as feasible, safe and effective ex vivo purging agents to target CML stem cells, in order to improve transplant outcome of resistant/relapsed patients or reduce IM dose escalation.

Seizure detection and monitoring are generally carried out by electroencephalogram (EEG) instrumentation with electrodes located on the scalp. For 24 h monitoring, it is possible to use an EEG recorder brought by the patient positioned on a bed or normally moving in the hospital and doing everything. This paper presents findings in the design of a neurocase for hosting a neurorecording system and its conformity to IEEE 24451 limited to wireless aspects related to data transmission. The recording system also provides for suppressing spikes and surges in EEG signals since these signals can be considered as a series of voltages with a relationship with space and time. Nanotechnology solutions relative to materials have been illustrated. Moreover, a stress simulation has been also performed in order to verify the sustainability of the design. The studied system considers the implementation of the neurorecording system including, design of circuital electronic components and thermoelectric power board supply, and 3-D package.

We exploit TiO2 surface functionalization as a tool to induce the crystallization process of CH3NH3PbI3−xClx perovskite thin films resulting in a reduction of the degree of orientation of the (110) crystallographic planes. Notably, the variation of the film crystalline orientational order does not affect the photovoltaic performances of the perovskite-based devices, whose efficiency remains mostly unchanged. Our findings suggest that other factors are more significant in determining the device efficiency, such as the non-homogenous coverage of the TiO2 surface causing charge recombination at the organic/TiO2 interface, defect distribution on the perovskite bulk and at the interfaces, and transport in the organic or TiO2 layer. This observation represents a step towards the comprehension of the perovskite film peculiarities influencing the photovoltaic efficiency for high performance devices.

The ligand exchange reaction with pyridine is the standard procedure for the integration of colloidal semiconductor nanocrystals (NCs) in photovoltaic devices; however, for large sized and irregularly shaped branched NCs, such as CdSe@CdTe tetrapods, this procedure can lead to a considerable waste of materials and the aggregation of NCs in the colloidal solution, therefore resulting in the formation of an inhomogeneous film and low device performances. Here, we report on alternative post-deposition treatments with carboxylic acids on films of CdSe@CdTe tetrapod shaped NCs. This approach guarantees the removal of the insulating surfactant, necessary to obtain good charge transport among NCs, while preserving the film integrity. We perform a complete characterization of the nanocrystalline films treated with different carboxylic acids and demonstrate the successful integration of such films in photovoltaic devices, showing a doubled efficiency with respect to the standard ligand exchange procedure. Our approach represents a general route towards the development of NC based devices with improved performances and minimized waste of material.

Understanding the mechanism of cell migration and interaction with the microenvironment is not only of critical significance to the function and biology of cells, but also has extreme relevance and impact on physiological processes and diseases such as morphogenesis, wound healing, neuron guidance, and cancer metastasis. External guidance factors such as topography and physical cues of the microenvironment promote directional migration and can target specific changes in cell motility and signalling mechanisms. Recent studies have shown that cells can directionally respond to applied electric fields (EFs), in both in vitro and in vivo settings, a phenomenon called electrotaxis. However, the exact cellular mechanisms for sensing electrical signals are still not fully well understood, and it is thus far unknown how cells recognize and respond to electric fields, although some studies have suggested that electromigration of some cell surface receptors and ion channels in cells could be involved. Applied electric fields may have a potential clinical role in guiding cell migration and present a more precise manageability to change the magnitude and direction of the electric field than most other guidance cues such as chemical cues. Here we present a review of recent studies used for studying electrotaxis to point out similarities, identify points of disagreement, and stimulate new directions for investigation. Insights into the mechanisms by which applied EFs direct cell migration, morphological change and development will enable current and future therapeutic applications to be optimized.

In this report, we evaluate the impact of a systematic change to the extracellular environment on cell morphology and functionality by combining the inherent properties of biocompatible polymers such as polydimethylsiloxane and polycaprolactone with a specific surface response. By microstructuring pillars and pits on the substrates, varying spacing and height of the structures, we investigate the role of topography in fibroblast cell adhesion and viability. The change of wetting behaviour was tailored and evaluated in terms of contact angle measurements. It was shown that the range of micro-scale physical cues at the interface between the cells and the surrounding environment affects cell shape and migrations, indicating a tendency to respond differently to higher features of the micro-scale. We found that surface topography seems dominant over material wettability, fibroblasts responded to variations in topography by altering morphology and migrating along the direction of spacing among the features biased by the height of structures and not by the material. It is therefore possible to selectively influence either cell adhesion or morphology by choosing adequate topography of the surface. This work can impact in the design of biomaterials and can be applied to implanted biomedical devices, tissue engineering scaffolds and lab on chip devices.

Charge generation and transport in (CH3NH3) Pbl(3-x)Cl(x) sensitized mesostructured solar cells are investigated. A highly efficient charge generation is directly proven by time correlated single photon counting analysis. Photoinduced absorption and transient photo-voltage investigations depict double charge recombination dynamics. To explain the high device performances according to those spectroscopic observations, we suggest the existence of two complementary paths for electron transport, involving either TiO2 or perovskite matrixes.

We propose a new approach for converting light energy into electrical energy, based on the photogeneration of nano-dipoles at donor-acceptor interfaces. The nano-dipoles are oriented in space so as to contribute to a collective polarization that induces a potential difference across the material, sandwiched between electrodes. A current is detected in the external circuit upon illumination. Such a device would exploit many advantages of organic semiconductors and get rid of the main limitation, namely transport. We provide a proof of concept and we discuss the ideal limit of the device based on numerical simulations. This provides design guidelines to the achievement of best performances. Simulations show that the proposed device can be an appealing opportunity with giant conversion efficiency provided some technological issues are overcome.

The integration of a plasmonic lamellar grating in a heterostructure organic solar cell as a light trapping mechanism is investigated with numerical Finite Elements simulations. A global optimization of all the geometric parameters has been performed. The obtained wide-band enhancement in optical absorption is correlated with both the propagating and the localized plasmonic modes of the structure, which have been identified and characterized in detail.

A structurally correlated series of cell-permeant thiophene fluorophores, characterized by intense green or red fluorescence inside live mouse embryonic fibroblasts, was developed. The fluorophores displayed rapid internalization, excellent retention inside the cells, and high optical stability in the cytosolic environment and did not alter cell viability and reproducibility. Depending on the molecular structure, they experienced distinct fate inside the cells: from bright and lasting staining of the cytoplasm to selective tagging of a small set of globular proteins.

In our search for thiophene fluorophores that can overcome the limits of currently available organic dyes in live-cell staining, we synthesized biocompatible dithienothiophene-S,S-dioxide derivatives' (DTTOs). that were spontaneously taken up by live mouse embryonic fibroblasts and HeLa cells. Upon treatment with DTTOs, the cells secreted nanostructured fluorescent fibrils, while cell viability remained unaltered. Comparison with the behavior of Other cell-permeant, newly synthesized thiophene fluorophores showed that the formation of fluorescent fibrils was peculiar to DTTO dyes. Laser scanning confocal microscopy of the fluorescent fibrils showed that most of them were characterized by helical supramolecular organization. Electrophoretic analysis and theoretical calculations suggested that the DTTOs were selectively recognized by the HyPro component of procollagen polypeptide chains and incorporated through the formation of multiple H-bondings.

We describe the synthesis of two novel poly(1,4-arylene-2,5-thienylene)s P1 and P2 containing benzo[c][2,1,3]thiadiazole monomeric units via Suzuki-Miyaura polymerization of a thiophene diboronic ester with aryl diiodides. The use of a catalyst complex consisting of Pd(OAc)(2) in combination with the electron-rich biaryl phosphine S-Phos resulted in efficient polymerization reactions. The polymers synthesized, P1 and P2, were characterized by UV-vis spectroscopy and cyclic voltammetry. Theoretical calculations and electrochemical measurements on P1 suggested a favorable position of the molecular orbitals for employment in polymer solar cells in combination with PCBM. Devices containing P1:PCBM 1:2 in the active layer showed an efficiency of 1.2% by simple spin casting from chloroform. (C) 2011 Elsevier B.V. All rights reserved.

A simple and efficient method for synthesizing a range of hybrid nanocomposites based on a core of silica nanospheres (160, 330, and 660 nm in diameter) covered by an outer shell of superparamagnetic nanoparticles, either iron oxide or heterodimeric FePt-iron oxide nanocrystals, is presented. The magnetic and ultrasound characterization of the resulting nanocomposites shows that they have great potential as contrast agents for dual-mode imaging purposes, combining magnetic resonance imaging (MRI) and ultrasonography (US).

Hybrid halide perovskites represent one of the most promising solutions toward the fabrication of all solid nanostructured solar cells, with improved efficiency and long-term stability. This article aims at investigating the structural properties of iodide/ chloride mixed-halide perovskites and correlating them with their photovoltaic performances. We found out that, independent of the components ratio in the precursor solution, Cl incorporation in an iodide-based structure, is possible only at relatively low concentration levels (below 3-4%). However, even if the material band gap remains substantially unchanged, the Cl doping dramatically improves the charge transport within the perovskite layer, explaining the outstanding performances of meso-superstructured solar cells based on this material.

Alignment of skeletal myoblasts is considered a critical step during myotube formation. The C2C12 cell line is frequently used as a model of skeletal muscle differentiation that can be induced by lowering the serum concentration in standard culture flasks. In order to mimic the striated architectures of skeletal muscles in vitro, micro-patterning techniques and surface engineering have been proven as useful approaches for promoting elongation and alignment of C2C12 myoblasts, thereby enhancing the outgrowth of multi-nucleated myotubes upon switching from growth media (GM) to differentiative media (DM). Herein, a layer-by-layer (LbL) polyelectrolyte multilayer deposition was combined with a micro-molding in capillaries (MIMIC) method to simultaneously provide biochemical and geometrical instructive cues that induced the formation of tightly apposed and parallel arrays of differentiating myotubes from C2C12 cells maintained in GM media for 15 days. This study focuses on two different types of patterned/self-assembled nanofilms based on alternated layers of poly (allylamine hydrochloride) (PAH)/poly(sodium 4-styrene-sulfonate) (PSS) as biocompatible but not biodegradable polymeric structures, or poly-L-arginine sulfate salt (pARG)/dextran sulfate sodium salt (DXS) as both biocompatible and biodegradable surfaces. The influence of these microstructures as well as of the nanofilm composition on C2C12 skeletal muscle cells' differentiation and viability was evaluated and quantified, pointing to give a reference for skeletal muscle regenerative potential in culture conditions that do not promote it. At this regard, our results validate PEM microstructured devices, to a greater extent for (PAH/PSS)5-coated microgrooves, as biocompatible and innovative tools for tissue engineering applications and molecular dissection of events controlling C2C12 skeletal muscle regeneration without switching to their optimal differentiative culture media in vitro. Biotechnol. Bioeng. 2013; 110: 586596. (c) 2012 Wiley Periodicals, Inc.

Microfluidics based on the capillarity-induced filling of elastomeric channels by a suitable liquid or solution represents a useful route for realizing portable diagnostic devices designed without additional mechanical or electrical micropumps. In this study, an elastomeric mold made of poly(dimethylsiloxane) (PDMS), containing relief patterns placed in intimate contact with a silicon substrate, is utilized to create a continuous network of rectangular micro-channels for the motion of water fluid. The immobilization on activated PDMS surface of suitable functional molecules such as hydrophilic and hydrophobic fluorine-containing aminonaphthols, obtained through a straightforward and versatile synthetic procedure, allowed us to modulate PDMS surface properties depending on the structural characteristics of the employed derivative. In this context, the incorporation of fluorine groups is important for improving biocompatibility of the resulting device, providing surfaces that could be chemically and biologically inert as well as resistant to surface adhesion phenomena. The functionalization from liquid phase of PDMS replicas, involving a covalent derivatization via silanization reaction of the above mentioned compounds to an oxidized PDMS surface, resulted in a successful modification of microfluidic motion of water in rectangular capillaries, moreover contact angle values evidence also how wettability of PDMS films could be modulated, with the fluorinated aminonaphthols fuctionalized PDMS exhibiting higher contact angles. (C) 2009 Elsevier B.V. All rights reserved.

Hybrid composites obtained upon blending conjugated polymers and colloidal semiconductor nanocrystals are regarded as attractive photo­active materials for optoelectronic applications. Here it is demonstrated that tailoring nanocrystal surface chemistry permits to control non-covalent and electronic interactions between organic and inorganic components. The pending moieties of organic ligands at the nanocrystal surface are shown to not merely confer colloidal stability while hindering charge separation and transport, but drastically impact morphology of hybrid composites during formation from blend solutions. The relevance of this approach to photovoltaic applications is demonstrated for composites based on poly(3-hexylthiophene) and lead sulfide nanocrystals, considered as inadequate until this report, which enable the fabrication of hybrid solar cells displaying a power conversion efficiency that reaches 3%. By investigating (quasi)steady-state and time-resolved photo-induced processes in the nanocomposites and their constituents, it is ascertained that electron transfer occurs at the hybrid interface yielding long-lived separated charge carriers, whereas interfacial hole transfer appears hindered. Here a reliable alternative aiming to gain control over macroscopic optoelectronic properties of polymer/nanocrystal composites by mediating their non-covalent interactions via ligands' pending moieties is provided, thus opening new possibilities towards efficient solution-processed hybrid solar cells.

The relations between the chemical-physical properties of novel designed monodispersed donors and their photovoltaic performances are discussed. The importance of intermolecular interactions is emphasized to figure out the achievement of high performing bulk hetero-junction solar cells which are solution processed.

Although several multinational companies have recently released products incorporating bioinspired functional coatings, their practical integration in building envelopes is still an open issue. High production costs associated to the existing vacuum deposition technologies, as well as the difficulties in extending the number of functions achievable by a single coating, represent to date the main limitations to their diffusion on a large scale. This review summarizes the key topics in the field of functional coatings for architectural glasses, focusing in particular on the potential applications of sol-gel based antireflective and self-cleaning coatings, that have received a tremendous attention in the last years. It provides an overview of the recent research efforts aimed to improve their properties and to extend their range of applicability. The bioinspired principles, upon which such coatings are based, are also described and are related to the chemical and morphological properties of such surfaces. (C) 2009 Elsevier Ltd. All rights reserved.

Hybrid halide perovskites have emerged as promising active constituents of next generation solution processable optoelectronic devices. During their assembling process, perovskite components undergo very complex dynamic equilibria starting in solution and progressing throughout film formation. Finding a methodology to control and affect these equilibria, responsible for the unique morphological diversity observed in perovskite films, constitutes a fundamental step towards a reproducible material processability. Here we propose the exploitation of polymer matrices as cooperative assembling components of novel perovskite CH3NH3PbI3 : polymer composites, in which the control of the chemical interactions in solution allows a predictable tuning of the final film morphology. We reveal that the nature of the interactions between perovskite precursors and polymer functional groups, probed by Nuclear Magnetic Resonance (NMR) spectroscopy and Dynamic Light Scattering (DLS) techniques, allows the control of aggregates in solution whose characteristics are strictly maintained in the solid film, and permits the formation of nanostructures that are inaccessible to conventional perovskite depositions. These results demonstrate how the fundamental chemistry of perovskite precursors in solution has a paramount influence on controlling and monitoring the final morphology of CH3NH3PbI3 (MAPbI3) thin films, foreseeing the possibility of designing perovskite : polymer composites targeting diverse optoelectronic applications.

Nanometer-sized poly(acrylic acid) (PAA) hydrogels were synthesized by emulsion polymerization of methyl acrylate and subsequent acidic hydrolysis. The nanohydrogel was characterized by spectroscopic methods (FTIR and H-1-NMR) and scanning probe techniques, and their pH-dependent swelling behavior was studied by dynamic light scattering. To determine the suitability of PAA nanogels as pH-sensitive carriers for biomedical applications, uptake and release of an oligothiophene fluorophore and its albumin conjugated from PAA nanogels were investigated as a function of pH by absorption and photoluminescence measurements. It was observed that uptake and release processes of both the oligothiophene and its conjugate could be controlled by changing the pH of the external solution. (C) 2010 Wiley Periodicals, Inc. J Appl Polym Sci 116: 2808-2815, 2010

Herein we describe the realization of nanowalled polymeric microtubes through a novel and versatile approach combining the layer-by-layer (LbL) deposition technique, the self-rolling of hybrid polymer/semiconductor microtubes and the subsequent removal of the semiconductor template. The realized channels were characterized in detail using scanning electron and atomic force microscopes. Additionally, we report on the incorporation of a dye molecule within the nanowalls of such microtubes, demonstrating a distribution of the fluorescence signal throughout the whole channel volume. This approach offers the possibility to tailor the properties of micro/nanotubes in terms of size, wall thickness and composition, thus enabling their employment for several applications.

Three novel organic dyes, coded TK1, TK2 and TK3, incorporating two donor moieties, cyanoacrylic acid as an acceptor/anchoring group, the dibenzofulvene core and an oligothiophene spacer in a 2D-π-A system, were designed, synthesized, and successfully utilized in dye-sensitized solar cells. The dye TK3, containing two thiophene rings as spacers, shows an IPCE action spectrum with a high plateau from 390 nm to 600 nm, increased open-circuit photovoltage by 40 mV and short-circuit photocurrent by 7.03 mA cm-1, with respect to TK1. Using CDCA as the co-adsorbent material, the Jsc of TK3 was increased to 14.98 mA cm-1 and a strong enhancement in the overall conversion efficiency (7.45%) was realized by TK3 compared to TK1 (1.08%), in liquid electrolyte-based DSSCs.

A spectroscopic investigation focusing on the charge generation and transport in inverted p-type perovskite-based mesoscopic (Ms) solar cells is provided in this report. Nanocrystalline nickel oxide and PCBM are employed respectively as hole transporting scaffold and hole blocking layer to sandwich a perovskite light harvester. An efficient hole transfer process from perovskite to nickel oxide is assessed, through time-resolved photoluminescence and photoinduced absorption analyses, for both the employed absorbing species, namely MAPbI3-xClx and MAPbI3. A striking relevant difference between p-type and n-type perovskite-based solar cells emerges from the study.

The products of ligation reaction of a 24 nucleotides long PolyA RNA adsorbed on mica were observed by atomic force microscopy. The occurrence of oligonudeotides at different degrees of polymerization has been quantitatively studied before and after ligation reaction. The microscopy images at the nanoscale show that nonenzymatic ligation of pristine RNA monomers results in the formation of supramolecular aggregates, with prevalence of dimers and tetramers. Analytical conditions were defined allowing the identification, the quantitative evaluation, and their distribution after ligation reaction, also providing an estimate of the degree of hydration of the objects. Such investigation is of particular biological relevance and provides the simplest yet model system for direct investigation of RNA reactions by advanced microscopy.

A simple synthesis was applied and tested for the preparation of boron-doped titanium dioxide [TiO2(B)] nanocrystals using titanium tetraisopropoxide (TTIP) together with boric acid (H3BO3) and benzyl alcohol as reaction solvent. Changes in the TTIP/H3BO3 molar ratio allowed a scalable synthetic protocol with a significant B-dopant control. In particular, this approach does not need surfactants or a final calcination step. X-ray diffractometry (XRD), low- and high-resolution transmission electron microscopy (TEM and HRTEM), and micro Raman spectroscopy revealed that the TiO2 nanocrystals produced have diameters up to about 10 nm and are mainly of the anatase phase but that a brookite phase was progressively formed with increased dopant level. The amount of boron was measured by inductively coupled plasma atomic emission spectroscopy (ICP-AES), and the presence of boron inside the crystals was determined by 11B cross-polarized magic-angle spinning nuclear magnetic resonance (11B CP-MAS NMR) spectroscopy. X-ray photoelectron spectroscopy (XPS) revealed the presence of boron on the nanocrystal surfaces, confirming the trend in the dopant concentration already observed with ICP-AES elemental analysis. Microphotoluminescence studies indicated the formation of three different typical luminescent defect states in correlation with the amount of added boron in the titania. UV/Vis absorption spectra showed a boron-dependent redshift of the absorption edge.

We present a novel, facile, and cost-effective method to prepare highly transparent mesoporous films made by anatase TiO2 nanorods that have been synthesized by a single-step solvothermal process. Such nanorods have been conveniently used as prepared-without completely removing the residual organics-to obtain suitable screen-printable paste by means of the use of proper polymeric binders. This method has been successfully implemented to fabricate highly efficient nanorod-based photoelectrodes for dye-sensitized solar cells. They showed an increment of the overall quantum conversion efficiency comprised between 34% and 58% with respect to cells based oil commercial P25 titanium dioxide nanoparticles. In particular, a maximum photocurrent density and solar conversion efficiency of 16.9 mA/cm(2) and 7.9% have been obtained, respectively.

Synthetic carriers that mimic "natural lipid-based vesicles" (such as micro/nanovesicles, exosomes) have found broad applications in biomedicine for the delivery of biomolecules and drugs. Remarkable advantages of using synthetic carriers include control over the lipid composition, structure and size, together with the possibility to add tracer molecules to monitor their in situ distribution via fluorescence microscopy. Over the past few years, new methods of vesicles production have been developed and optimized, such as those based on microfluidic techniques. These innovative approaches allow us to overcome the limitations faced in conventional methods of liposome preparation, such as size distribution and polydispersity. Herein, a Microfluidic Hydrodynamic Focusing (MHF) device has been used for the production of lipid-based vesicles with different lipid combinations that resemble natural exosomes, such as phosphatidylcholines (PC), cholesterol (Chol), dicetyl phosphate (DCP) and ceramide (Cer). Thanks to a fine control on fluid manipulation, the MHF device allows preparation of vesicles with controlled size, a relevant feature in the emerging field of carrier-assisted cell-delivery. Interestingly, PC/Chol/Cer vesicles exhibit low polydispersity and high stability up to 45 days. Later, quantum dots (QDs) were successfully embedded in these vesicles through the same preparation process. The development of QD-embedded lipid nanovesicles by MHF devices has never been described previously.

To experimentally investigate the acoustical behavior of silica nanoparticles within conventional diagnostic ultrasound fields and to determine a suitable configuration, in terms of particle size and concentration, for their employment as targetable contrast agents. We also assessed the effectiveness of a novel method for automatic detection of targeted silica nanoparticles for future tissue typing applications.

Novel Donor-pi-Acceptor triphenylamine-based dyes were synthesized and characterized with regard to their photophysical and photoelectrochemical properties by introducing the ethynyl-2-thienyl moiety as spacer (YS-1). The modification of the donor triphenylamine, performed by intodroducing two p-methoxy groups gave the YS-2 dye. Experimental results showed that the UV-Vis absorption spectra changed exhibiting the increasing of the molar extinction coefficient as well as the red-shift in dichloromethane solution. The maximum power conversion efficiency under standard global AM 1.5 illumination for YS-1 was 4.1% rising to 5.3% when the cell was sensitized with YS-2. The interpretation of the improvement and the discussion of the experimental results were corroborated by Time-Dependent Density-Functional Theory calculations, carried out for the photosensitizers in vacuo and in solution. In particular, the effects on the spectroscopic properties of the dyes due to the presence of the solvent and to the common deprotonation of the carboxylic unit in polar solvents have been investigated.

Low-molecular-weight organic gelators are widely used to influence the solidification of polymers, with applications ranging from packaging items, food containers to organic electronic devices, including organic photovoltaics. Here, this concept is extended to hybrid halide perovskite-based materials. In situ time-resolved grazing incidence wide-angle X-ray scattering measurements performed during spin coating reveal that organic gelators beneficially influence the nucleation and growth of the perovskite precursor phase. This can be exploited for the fabrication of planar n-i-p heterojunction devices with MAPbI3 (MA = CH3NH3 +) that display a performance that not only is enhanced by ≈25% compared to solar cells where the active layer is produced without the use of a gelator but that also features a higher stability to moisture and a reduced hysteresis. Most importantly, the presented approach is straightforward and simple, and it provides a general method to render the film formation of hybrid perovskites more reliable and robust, analogous to the control that is afforded by these additives in the processing of commodity “plastics.”

A bottom contact/top gate ambipolar "p-i-n" layered light emitting field effect transistor with the active medium inserted between two doped transport layers, is reported. The doping profile results crucial to the capability of emitting light, as well as to the electrical characteristics of the device. In this sense, high output current at relative low applied gate/drain voltage and light emission along the whole large area transistor channel are observed, putting the basis to full integration of organic light emitting field effect transistors in planar complex devices.

We report on a novel approach to integrate colloidal anatase TiO2 nanorods as key functional components into polymer bulk heterojunction (BHJ) photovoltaic devices by means of mild, all-solution-based processing techniques. The successful integration of colloidal nanoparticles in organic solar cells relies on the ability to remove the long chain insulating ligands, which indeed severely reduces the charge transport. To this aim we have exploited the concomitant mechanisms of UV-light-driven photocatalytic removal of adsorbed capping ligands and hydrophilicization of TiO2 surfaces in both solid-state and liquid-phase conditions. We have demonstrated the successful integration of the UV-irradiated films and colloidal solutions of TiO2 nanorods in inverted and conventional solar cell geometries, respectively. The inverted devices show a power conversion efficiency of 2.3% that is a ca. three times improvement over their corresponding cell counterparts incorporating untreated TiO2, demonstrating the excellent electron-collecting property of the UV-irradiated TiO2 films. The integration of UV-treated TiO2 solutions in conventional devices results in doubled power conversion efficiency for the thinner active layer and in maximum power conversion efficiency of 2.8% for 110 nm thick devices. In addition, we have demonstrated, with the support of device characterizations and optical simulations, that the TiO2 nanocrystal buffer layer acts both as electron-transporting/hole-blocking material and optical spacer.

Photovoltachromic devices combine photovoltaic and electrochromic behaviours to enable adjustable transparency glazing, where the photovoltaic component supplies the power to drive the coloration. Such stand-alone, self-powered devices are of commercial interest for integration into windows and surfaces of buildings and vehicles. Here, we report for the first time a perovskite-based photovoltachromic device with self-adaptive transparency. This multifunctional device is capable of producing electrical power by solar energy conversion as well as undergoing a chromic transition from neutral-color semi-transparent to dark blue-tinted when irradiated with solar light, without any additional external bias. The combination of semi-transparent perovskite photovoltaic and solid-state electrochromic cells enables fully solid-state photovoltachromic devices with 26% (or 16%) average visible transmittance and 3.7% (or 5.5%) maximum light power conversion efficiency. Upon activating the self-tinting, the average visible transmittance drops to 8.4% (or 5.5%). These results represent a significant step towards the commercialization of photovoltachromic building envelopes.

A photovoltachromic window can potentially act as a smart glass skin which generates electric energy as a common dye-sensitized solar cell and, at the same time, control the incoming energy flux by reacting to even small modifications in the solar radiation intensity. We report here the successful implementation of a novel architecture of a photovoltachromic cell based on an engineered bifunctional counter electrode consisting of two physically separated platinum and tungsten oxide regions, which are arranged to form complementary comb-like patterns. Solar light is partially harvested by a dye-sensitized photoelectrode made on the front glass of the cell which fully overlaps a bifunctional counter electrode made on the back glass. When the cell is illuminated, the photovoltage drives electrons into the electrochromic stripes through the photoelectrochromic circuit and promotes the Li+ diffusion towards the WO3 film, which thus turns into its colored state: a photocoloration efficiency of 17 cm(2) min(-1) W-1 at a wavelength of 650 nm under 1.0 sun was reported along with fast response (coloration time <2 s and bleaching time <5 s). A fairly efficient photovoltaic functionality was also retained due to the copresence of the independently switchable micropatterned platinum electrode.

Tetrapod-shaped CdSe(core)/CdTe(arms) colloidal nanocrystals, capped with alkylphosphonic acids or pyridine, were reacted with various small molecules (acetic acid, hydrazine and chlorosilane) which induced their tip-to-tip assembly into soluble networks. These networks were subsequently processed into films by drop casting and their photoconductive properties were studied. We observed that films prepared from tetrapods coated with phosphonic acids were not photoconductive, but tip-to-tip networks of the same tetrapods exhibited appreciable photocurrents. On the other hand, films prepared from tetrapods coated with pyridine instead of phosphonic acids were already highly photoconductive even if the nanocrystals were not joined tip-to-tip. Based on the current-voltage behavior under light we infer that the tunneling between tetrapods is the dominant charge transport mechanism. In all the samples, chemically-induced assembly into networks tended to reduce the average tunneling barrier. Additionally, pyridine-coated tetrapods and the tip-to-tip networks made out of them were tested as active materials in hybrid photovoltaic devices. Overall, we introduce an approach to chemically-induced tip-to-tip assembly of tetrapods into solution processable networks and demonstrate the enhancement of electronic coupling of tetrapods by various ligand exchange procedures.

We have recently reported initial results concerning an original approach to introduce additional properties into fibrillar proteins produced by live fibroblasts and extruded into the ECM. The key to such an approach was biocompatible, fluorescent and semiconducting synthetic molecules which penetrated spontaneously the cells and were progressively encompassed via non-bonding interactions during the self-assembly process of the proteins, without altering cell viability and reproducibility. In this paper we demonstrate that the intracellular secretion of fluorescent microfibers can be generalized to living primary and immortalized human/mouse fibroblasts. By means of real-time single-cell confocal microscopy we show that the fluorescent microfibers, most of which display helical morphology, are generated by intracellular coding of the synthetic molecules. We also describe co-localization experiments on the fluorescent microfibers isolated from the cell milieu demonstrating that they are mainly made of type-I collagen. Finally, we report experimental data indicating that the embedded synthetic molecules cause the proteins not only to be fluorescent but also capable of electrical conductivity.

Exciton-polaritons in semiconductors are quasi-particles which have recently shown the capability to undergo phase transition into a coherent hybrid state of light and matter. The observation of such quasi-particles in organic microcavities has attracted increasing attention for their characteristic of reaching condensation at room temperature. In this work, the emission properties of organic polaritons are demonstrated not to depend on the overlap between the absorption and emission states of the molecule and that the emission dynamics are modified in the strong coupling regime, showing a significant enhancement of the photoluminescence intensity as compared to the bare dye. This paves the way to the investigation of molecules with large absorption coefficients but poor emission efficiencies for the realization of polariton condensates and organic electrically injected lasers by exploiting strong exciton-photon coupling regimes.

A poly-(3-hexylthiophene) (P3HT)/[6,6]-phenyl-C-61-butyric-acid-methyl-ester (PCBM) bilayer structure has been realized by single step matrix-assisted pulsed laser evaporation (ss-MAPLE) technique using the same solvent for both the polymers under vacuum conditions. Our ss-MAPLE procedure allows the fabrication of polymeric multilayer device stacks, which are very difficult to realize with the conventional solvent assisted deposition methods. A proof of concept bilayer P3HT/PCBM solar cell based on ss-MAPLE deposition has been realized and characterized. This demonstration qualifies ss-MAPLE as a general and alternative technique for the implementation of polymeric materials in hetero-structure device technology.

Polymorphic crystalline microfibers from an achiral octithiophene with one S-hexyl substituent per ring are separately and reproducibly grown with the same characteristics on various solid surfaces, including the interdigitated electrodes/SiO2 surface of a bottomcontact field-effect transistor. The arrangement of the same molecule in two diverse supramolecular structures leads to markedly different electronic, optical, and charge mobility properties. The microfibers-straight and yellow emitting or helical and red emitting-exhibit p-type charge transport characteristics, with the yellow ones showing a charge mobility and on/off current ratio of one and three orders of magnitude, respectively, greater than the red ones. Both forms show circular dichroism signals with significant differences from one form to the other. DFT calculations show that the octithiophene exists in two different quasi-equienergetic conformations aggregating with diverse orientations of the substituents. This result suggests that the observed polymorphism is conformational in nature. The self-assembly, driven by sulfur-sulfur non-bonding interactions, amplifies the small property differences between conformers, leading to quite different bulk properties.

In this paper it is reported a novel approach for the fabrication of polymeric microtubes based on the combination of semiconductor strain released thin films and Layer-by-Layer (LbL) deposition technique. The structure consisting of a LbL self-assembled polylectrolytes (PEs) film deposited onto a strained GaAs/InGaAs bilayer, was properly patterned and structured to enable the self rolling of an array of channels of different lengths. Then, the semiconductor film, acting as a sacrificial template, was selectively etched to obtain polymer microtubes. The so-realized polymeric channels were characterized in detail using Scanning Electron Microscopy (SEM) and Atomic Force Microscopy (AFM). Additionally, such microtubes were analyzed by confocal microscopy to prove the successful incorporation of a dye molecule within the polymeric nanowalls.

We report optical writing at the nanometer scale of spin coated PMMA-spiropyran films. By using a near-field optical microscope, pure optical nano-writing with a resolution of 160 nm and writing speed of 0.4 mu m/s was achieved. Simultaneous topographic and optical writing was also obtained by simply coupling to the near-field few more mW of laser power. Due to the fast optical response of the spiropyran molecule, nanolithography on PMMA-spyropyran thin films appears to be very attractive for future photonics applications. (C)2014 Optical Society of America

The realization of white-light sources with a combination of high color rendering index ( CRI), which is the average of the first eight rendering indices, and the deep-red color rendering R9 is an important challenge in the field of solid-state lighting. Herein, we report on a pure white hybrid light-emitting device combining a deep-blue emission from a polymer with blue, green, and red emissions from ternary CdSe/ZnS quantum dots. By carefully designing the device structure and tuning the ratio of QDs with different sizes, high CRI of 94 and R9 of 92 at 525 cd/m(2) were achieved. (C) 2010 Optical Society of America

A highly dense and uniform layer of Au nanoparticles (NPs) on poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) film has been produced by the pulsed laser deposition (PLD) technique toward the production of an improved efficiency photovoltaic device. The advantage of PLD over other techniques is the easy and precise control of the Au NPs size and spatial distribution, without needing of further NP surface functionalization. The efficiency enhancement factor related to Au NPs doping has been evaluated in a solar cell based on poly-(3-hexylthiophene):[6,6]-phenyl-C61-butyric acid methyl ester (P3HT:PCBM) diffused bilayer. The short-circuit current density, J SC, increases by 18 % and the power conversion efficiency by 22 %, respectively, in comparison with an equivalent device without Au NPs. The optical and morphological properties of the Au NPs layer have been selected in order to evaluate the contribution of the surface plasmon resonance as enhancement factor of the solar cell efficiency, in a range size where light scattering is negligible.

Nowadays it is well-accepted to attribute bulk-like optical absorption properties to colloidal PbS quantum dots (QDs) at wavelengths above 400 nm. This assumption permits to describe PbS QD light absorption by using bulk optical constants and to determine QD concentration in colloidal solutions from simple spectrophotometric measurements. Here we demonstrate that PbS QDs experience the quantum confinement regime across the entire near UV–vis–NIR spectral range, therefore also between 350 and 400 nm already proposed to be sufficiently far above the band gap to suppress quantum confinement. This effect is particularly relevant for small PbS QDs (with diameter of ≤4 nm) leading to absorption coefficients that largely differ from bulk values (up to ∼40% less). As a result of the broadband quantum confinement and of the high surface-to-volume ratio peculiar of nanocrystals, suitable surface chemical modification of PbS QDs is exploited to achieve a marked, size-dependent enhancement of the absorption coefficients compared to bulk values (up to ∼250%). We provide empirical relations to determine the absorption coefficients at 400 nm of as-synthesized and ligand-exchanged PbS QDs, accounting for the broadband quantum confinement and suggesting a heuristic approach to qualitatively predict the ligand effects on the optical absorption properties of PbS QDs. Our findings go beyond formalisms derived from Maxwell Garnett effective medium theory to describe QD optical properties and permit to spectrophotometrically calculate the concentration of PbS QD solutions avoiding underestimation due to deviations from the bulk. In perspective, we envisage the use of extended π-conjugated ligands bearing electronically active substituents to enhance light-harvesting in QD solids and suggest the inadequacy of the representation of ligands at the QD surface as mere electric dipoles.

Microfluidic technologies are gaining increasing importance due to their capability of manipulating fluids at the microscale that should allow to synthesize many products with surprisingly high yields and short reaction times. In the lab-on-chip field researchers have developed microfluidic apparatuses to provide special equipments for producing positron emission tomography (PET) radiopharmaceuticals in a quicker, safer, and more reliable way compared to traditional vessel-based approaches. In this paper, we have selected a number of polymeric materials, such as polydimethylsiloxane (PDMS), SU-8, and Teflon-like coatings deposited on PDMS or hard substrates, to be used for the fabrication of micro apparatuses for radiosynthesis. Their radioactivity resistance was investigated employing different setups and the results analyzed by atomic force microscopy (AFM), optical microscopy, and Fourier transform infrared spectroscopy (FT-IR). To evaluate undesired absorption effects in the investigated materials, the fluoride radioactive trapping inside microchannel was measured through autoradiography. We found out that polymeric materials such as SU-8 and Teflon coated on hard materials seem very appealing for fabricating microreactors for radiochemistry.

Random laser emission is obtained from a fluidic paper-based device realized by conventional soft-lithography techniques on common, flexible, renewable and biocompatible commercial paper. The device is realized exclusively on paper by creating microfluidic porous channels on the cellulose fibres, in which a laser dye (Rhodamine B) can flow by capillarity. The modulation of the random lasing characteristics, in terms of threshold and spectral position, can be tailored by acting on the confinement induced by the lithographic process as well as on the shape and functionalization at the interface of the emitting regions.

The random laser emission from the functionalized thienyl-S,S-dioxide quinquethiophene (T5OCx) in confined patterns with different shapes is demonstrated. Functional patterning of the light emitter organic material in well defined features is obtained by spontaneous molecular self-assembly guided by surface tension driven (STD) lithography. Such controlled supramolecular nano-aggregates act as scattering centers allowing the fabrication of one-component organic lasers with no external resonator and with desired shape and efficiency. Atomic force microscopy shows that different geometric pattern with different supramolecular organization obtained by the lithographic process tailors the coherent emission properties by controlling the distribution and the size of the random scatterers.

Microcavity polaritons are two-dimensional bosonic fluids with strong nonlinearities, composed of coupled photonic and electronic excitations. In their condensed form, they display quantum hydrodynamic features similar to atomic Bose-Einstein condensates, such as long-range coherence, superfluidity and quantized vorticity. Here we report the unique phenomenology that is observed when a pulse of light impacts the polariton vacuum: the fluid which is suddenly created does not splash but instead coheres into a very bright spot. The real-space collapse into a sharp peak is at odd with the repulsive interactions of polaritons and their positive mass, suggesting that an unconventional mechanism is at play. Our modelling devises a possible explanation in the self-trapping due to a local heating of the crystal lattice, that can be described as a collective polaron formed by a polariton condensate. These observations hint at the polariton fluid dynamics in conditions of extreme intensities and ultrafast times.

We report observation of oscillations in the dynamics of a microcavity polariton condensate formed under pulsed nonresonant excitation. While oscillations in a condensate have always been attributed to Josephson mechanisms due to a chemical potential unbalance, here we show that under some localization conditions of the condensate, they may arise from relaxation oscillations, a pervasive classical dynamics that repeatedly provokes the sudden decay of a reservoir, shutting off relaxation as the reservoir is replenished. Using nonresonant excitation, it is thus possible to obtain condensate injection pulses with a record frequency of 0.1 THz

Hybrid nanocomposites (HCs) obtained by blend solutions of conjugated polymers and colloidal semiconductor nanocrystals are among the most promising materials to be exploited in solution-processed photovoltaic applications. The comprehension of the operating principles of solar cells based on HCs thus represents a crucial step toward the rational engineering of high performing photovoltaic devices. Here we investigate the effect of conjugated polymers on hybrid solar cell performances by taking advantage from an optimized morphology of the HCs comprising lead sulfide quantum dots (PbS QDs). Uncommonly, we find that larger photocurrent densities are achieved by HCs incorporating wide-bandgap polymers. A combination of spectroscopic and electro-optical measurements suggests that wide-bandgap polymers promote efficient charge/exciton transfer processes and hinder the population of midgap states on PbS QDs. Our findings underline the key role of the polymer in HC-based solar cells in the activation/deactivation of charge transfer/loss pathways.

Polaritons are hybrid light-matter quasi-particles that have gathered a significant attention for their capability of showing room temperature and out-of-equilibrium Bose-Einstein condensation. More recently, a novel class of ultrafast optical devices have been realized by using flows of polariton fluids, such as switches, interferometers, and logical gates. However, polariton lifetimes and propagation distances are strongly limited by photon losses and accessible in-plane momenta in normal microcavity samples. In this work, we show experimental evidence of the formation of room temperature propagating polariton states arising from the strong coupling between organic excitons and a Bloch surface wave. This result, which was only recently predicted, paves the way for the realization of polariton devices that could allow lossless propagation up to macroscopic distances. (C) 2014 Optical Society of America

We have developed a room-temperature solution processing approach to integrate colloidal anatase titanium dioxide nanorods (TiO2 NRs) and lead sulfide quantum dots (PbS QDs) into a heterostructured p-n junction device. To this aim we have exploited a post-deposition treatment to remove surface-adsorbed ligands by means of UV-light-irradiation of TiO2 NRs and a dilute acid treatment of PbS QDs. Here we report a systematic study on the optimization of the post-deposition treatments and device fabrication. Our approach is fully compatible with plastic device technology and is potentially useful for the integration of crystalline TiO2 as active component into disparate solar cell architectures and organic optoelectronic devices.

In this paper, a method to synthesize anatase TiO2 nanorods by hydrolysis of titanium(IV) isopropoxide (TTIP) in the presence of benzyl alcohol and acetic acid at 210 degrees C was tested. The novelty of the present approach relies on the evaluation of the shape-controlled synthesis of anatase TiO2 nanocrystals via a microwave-solvothermal method in 45 min. The different TiO2 nanocrystals were obtained by tuning the TTIP/acetic acid ratio under optimized synthetic conditions and were characterized in detail by X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution TEM (HRTEM), micro Raman (together with microphotoluminescence) and FT-IR spectroscopies. The acetic acid coordinated on the nanocrystal surface was removed by the reduction of its carboxyl group via a "super-hydride reaction", and the photocatalytic activity of bare TiO2 nanocrystals, under visible light irradiation, was also evaluated: the best performing TiO2 anatase nanocrystals exhibited a discrete photoactivity, completely degrading Rhodamine B solution in five hours.

We carry out an accurate computational analysis on the nature and distribution of electronic trap states in shape-tailored anatase TiO2 structures, investigating the effect of the morphology on the electronic structure. Linear nanocrystal models up to 6.nm in length with various morphologies, reproducing both flattened and elongated rod-shaped TiO2 nanocrystals, have been investigated by DFT calculations, to clarify the effect of the crystal facet percentage on the nanocrystal electronic structure, with particular reference to the energetics and distribution of trap states. The calculated densities of states below the conduction band edge have been very well fitted assuming an exponential distribution of energies and have been correlated with experimental capacitance data. In good agreement with the experimental phenomenology our calculations show that elongated rod-shaped nanocrystals with higher values of the ratio between (100) and (101) facets exhibit a relatively deeper distribution of trap states. Our results point at the crucial role of the nanocrystal morphology on the trap state density, highlighting the importance of a balance between the low-energy (101) and high-energy (100)/(001) surface facets in individual TiO2 nanocrystals.

An engineered photoelectrode for dye solar cells has been developed through the combination of three mesoporous stacks made of shape-tailored TiO2 anatase nanocrystals, which have been ad hoc synthesized by suitable colloidal routes. Optimization of light harvesting and charge collection efficiency allowed us to obtain a high power conversion efficiency of 10.26%.

A new approach to generate and manage white light from an organic light emitting diode is shown. It consists in the coupling of two microcavity resonators made of only metallic and organic layers, whose operation principle is analogous to that of two mechanical harmonic oscillators coupled by a spring . This approach allows the solution of key open points in the field of plastic white light sources

A new architecture for multifunctional photoelectrochemical devices, namely photovoltachromic devices, is disclosed here, capable of producing electric energy by solar conversion also modulating the devices' optical transmittance in a smart and aesthetically sounding fashion. These devices generally consist of a titanium dioxide photoelectrode and of a bifunctional patterned counter electrode made of platinum and amorphous tungsten oxide. The innovative configuration described hereafter proposes to split the single patterned counter electrode into two distinct electrodes, physically overlapped: the central one is suitably drilled in order to allow the electrolyte to fill both communicating chambers. These three electrode devices allow three independent operating modes: photovoltaic, photoelectrochromic, and photovoltachromic. In this paper, we report the optical, electrical, and electrochemical characterization of this innovative device, varying both available catalytic surface area and the type of sensitizing dye. We eventually obtained the following conversion efficiencies, 2.75%, 2.35%, and 1.91%, in samples having different catalytic areas (397, 360, and 320 mm(2), respectively). We inferred that the higher the platinum area on the interposed platinum-poly(ethylene naphthalate)-indium tin oxide counter electrode, the higher the photovoltaic conversion efficiency. On the other hand, a decrease of the intercommunication openings generates a slowdown of bleaching processes.

We have investigated the spectroscopic behavior of three different sensitizers adsorbed onto titania thin films in order to gain information both on the electron transfer process from dye to titania and on the anchorage of the chromophore onto the semiconductor. We have examined by UV-Vis and fluorescence spectroscopy the widely used ruthenium complex cis-di(thiocyanato) bis(2,2'-bipyridyl-4,4'-dicarboxylato) ruthenium(II) (N719), the more recently developed organic molecular 3-(5-(4-(diphenylamino)styryl)thiophen-2-yl)-2-cyanoacrylic acid (D5), and a push-pull zinc phthalocyanine sensitizer (ZnPc). Three type of titania films with different morphology, characterized by SEM and FT-IR measurement, were considered: a mesoporous transparent film deposited by spin-coating (TiMS), a semiopaque film deposited by doctor-blade from mesoporous titania (TiMS DB) anda semiopaque film deposited by doctor-blade form commercial P25 titania (P25_DB). The use of TiMS is responsible for the adsorption of a higher amount of dye since the mesoporous structure allows increasing the interfacial area between dye and titania. Moreover, the fluorescence emission peak is weaker when the sensitizers are adsorbed onto TiMS. These findings suggest that mesostructured films could be considered the most promising substrates to realize photoanodes with a fast electron transfer process.

The development of alternative deposition techniques is an important step towards the realization of low cost multilayered organic solar cells. While spin-coating needs orthogonal solvents to avoid an intermixing of stacked layers, thermal evaporation is expensive and not applicable to polymers. We show here how an innovative deposition technique called dry spray-coating may represent a promising way to manufacture bulk-hetero-junction (BHJ) and multilayered solar cells. Using standard materials such as poly(3-hexylthiophene-2,5-diyl) and [6,6]-phenyl-C61-butyric acid methyl ester, we achieved efficiency of 2.6% for the BHJ device, while a value of 1.5% was obtained for a bilayer structure using the same solvent for both materials. (C) 2013 AIP Publishing LLC.

To unveil the mechanisms controlling photovoltaic conversion in high-performing perovskite-based meso-structured solar cells, we focus on the key role played by the mesoporous oxide/perovskite interface. We employ several spectroscopic techniques to design a complete scenario and corroborate our results with first principle density functional theory calculations. In particular Stark spectroscopy, a powerful tool allowing interface-sensitive analysis is employed to prove the existence of oriented permanent dipoles, consistent with the hypothesis of an ordered perovskite layer, close to the oxide surface. The existence of a structural order, promoted by specific local interactions, could be one of the decisive reasons for highly efficient carriers transport within perovskite films.

The recent oil spill in the Gulf of Mexico has already caused, and is continuing to cause, significant global environmental issues and has severely impacted people's lives and natural resources. The ramifications of oil spill accidents highlight the difficulty of achieving effective oil-water separation, and the consequences of these accidents are harsh and long-term. In this work, we describe a convenient approach to fabricate cotton textiles with a hydrophilic coating, showing both superhydrophobic and superoleophilic properties. The surfaces are successfully prepared by one-step growth of a diamond-like carbon film onto the textiles via plasma-enhanced chemical vapour deposition and exhibit highly controllable, energy-efficient oil-water separation with high separation efficiency. The results have important implications for oil-absorption dynamics while repelling water completely. The present work suggests encouraging applications to marine spilt oil cleanup and other water-oil separation systems.

Suitable post-synthesis surface modification of lead-chalcogenide quantum dots (QDs) is crucial to enable their integration in photovoltaic devices. We have developed a solution-phase ligand exchange strategy that exploits arenethiolate anions to replace the pristine oleate ligands on PbS QDs, while preserving the long-term colloidal stability of QDs and allowing their solution-based processability into photoconductive thin-films. Complete QD surface modification is demonstrated by IR spectroscopy analysis, whereas UV-Vis-NIR Absorption Spectroscopy provides quantitative evaluation of stoichiometry and thermodynamic stability of the resulting system. Arenethiolate ligands permit to reduce the inter-particle distance in PbS QD solids, leading to a drastic improvement of the photoinduced charge transport properties. Therefore, smooth dense-packed thin-films of arenethiolate-capped PbS QDs obtained via a single solution-processing step are integrated in heterojunction solar cells: such devices generate remarkable photocurrent densities (14 mA cm(-2)) and overall efficiencies (1.85%), which are outstanding for a single PbS QD layer. Solution-phase surface modification of QDs thus represents an effective intermediate step towards low-cost processing for all-inorganic and hybrid organic/inorganic QD-based photovoltaics. (c) 2013 Elsevier B.V. All rights reserved.

A non-aqueous, solvothermal method was applied to the synthesis of TiO(2) nanorods in pure anatase crystal phase using Ti(IV)-isopropoxide. The use of benzyl alcohol as both solvent and reactant was investigated in combination with the addition of acetic acid to the reaction mixture. Various values of the AcOH : Ti(OiPr)(4) molar ratio were realized in the synthesis and tested in order to obtain a significant dimensional and morphological control over the resulting TiO(2) nanostructures, as well as to devise a simple and scalable synthetic protocol. On the basis of the experimental results, a substantially modified version of the well-established "benzyl alcohol route'' was then designed and developed. X-ray diffractometry and transmission electron microscopy revealed that monodisperse anatase nanorods having a length of about 13-17 nm and a diameter of 5 nm can be obtained when AcOH and Ti(OiPr)(4) are reacted in comparable proportions. Investigation of the characteristic parameters of dye-sensitized solar cells fabricated using the synthesized nanorods as photoanode revealed a power conversion efficiency of about 7.5% corresponding to an improvement of 28% with respect to a commercial spheroidal nanotitania (P25) based reference device.

Three new 2D-pi-A dyes (TK4, TK5 and TK6), composed of diarylamine donor groups, a dibenzofulvenethiophene core as the pi-bridge, and a cyanoacrylic acid anchoring group as the acceptor, have been successfully designed, synthesized, and characterized both experimentally and computationally. The performance in DSSC solar cells has been also studied. Octyloxy chains were introduced on the backbone of the dye, in order to increase donor capability, avoid aggregation side effects and increase physical insulation between electrolyte system and the TiO2 layer. The dye containing the octyloxy chains on the donor group and two thiophene ring as an extension of pi-bridge showed the best photovoltaic performance with a maximum of solar energy-to-electricity conversion yield of 7.8% under AM 1.5 irradiation (100 mW/cm(2)). (C) 2016 Elsevier Ltd. All rights reserved.

We have developed a novel and straightforward approach for the green synthesis of reduced graphite oxide (rGO). First, graphite oxide (GO) was prepared by the Hummers' oxidation method, starting from high-surface-area graphite. Then, rGO was generated from GO in aqueous suspension through a UV-irradiation treatment. The influence of different process parameters (including type of UV source, irradiation time and atmosphere) on the GO reduction efficiency was explored and evaluated on the basis of the data acquired by several experimental techniques, such as infrared spectroscopy in attenuated total reflectance mode, X-ray diffraction, UV-vis absorption spectrophotometry, X-ray photoelectron spectroscopy and thermogravimetry. The acquired results allowed identifying appropriate sets of reaction conditions under which GO reduction yield could be maximized. In particular, the highest reduction degree was obtained by exposing GO to UV light in a UV oven for 48 h under inert atmosphere. The reduction strategy developed by us represents an innovative low-cost and easy route to graphene-based nanomaterials, which does not require any stabilizer, photocatalyst or reducing agent. For this reason, our method represents an attractive environmentally friendly alternative approach for the preparation of stable rGO dispersions in large-scale amounts, to be utilizable in disparate engineering applications.

The present investigation reported the synthesis of ultrafine anatase titanium dioxide (TiO2) nanocrystals using titanium isopropoxide (TTIP) as precursor in presence of benzyl alcohol as solvent and glucose as capping agent via a microwave-solvothermal method. The samples were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), nitrogen adsorption, micro Raman and Fourier transform infrared spectroscopies (FT-IR). From this preparation method it was demonstrated that the obtainable TiO2 nanocrystals were less than 10 nm in mean size, mainly in anatase phase, presenting also a mesoporous structure. The use of glucose as capping agent added in the reaction system played a role in the anisotropic growth of the TiO2 nanocrystals, as evidenced by XRD domain size analysis and promoted an increase of the specific surface area.

In this paper, we use X-ray diffraction, X-ray photoelectron spectroscopy, and atomic force microscopy to investigate the structural and morphological properties of methylammonium lead iodide (MAPbI3) thin films deposited on flat TiO2 substrates, as obtained with and without the use of chlorine precursors. We demonstrate that the presence of Cl precursors assists the growth of oriented MAPbI3 domains along a specific growth direction. Such features are attributed to the proximity of the Cl species to the interface with the TiO2 substrate.

The Hanbury Brown-Twiss effect is one of the celebrated phenomenologies of modern physics that accommodates equally well classical (interferences of waves) and quantum (correlations between indistinguishable particles) interpretations. The effect was discovered in the late thirties with a basic observation of Hanbury Brown that radio-pulses from two distinct antennas generate signals on the oscilloscope that wiggle similarly to the naked eye. When Hanbury Brown and his mathematician colleague Twiss took the obvious step to propose bringing the effect in the optical range, they met with considerable opposition as single-photon interferences were deemed impossible. The Hanbury Brown-Twiss effect is nowadays universally accepted and, being so fundamental, embodies many subtleties of our understanding of the wave/particle dual nature of light. Thanks to a novel experimental technique, we report here a generalized version of the Hanbury Brown-Twiss effect to include the frequency of the detected light, or, from the particle point of view, the energy of the detected photons. Our source of light is a polariton condensate, that allows high-resolution filtering of a spectrally broad source with a high degree of coherence. In addition to the known tendencies of indistinguishable photons to arrive together on the detector, we find that photons of different colors present the opposite characteristic of avoiding each others. We postulate that fermions can be similarly brought to exhibit positive (boson-like) correlations by frequency filtering.

Colloidal quantum dots are composed of nanometer-sized crystallites of inorganic semiconductor materials bearing organic molecules at their surface. The organic/inorganic interface markedly affects forms and functions of the quantum dots, therefore its description and control are important for effective application. Herein we demonstrate that archetypal colloidal PbS quantum dots adapt their interface to the surroundings, thus existing in solution phase as equilibrium mixtures with their (metal-)organic ligand and inorganic core components. The interfacial equilibria are dictated by solvent polarity and concentration, show striking size dependence (leading to more stable ligand/core adducts for larger quantum dots), and selectively involve nanocrystal facets. This notion of ligand/core dynamic equilibrium may open novel synthetic paths and refined nanocrystal surface-chemistry strategies.

The dissociation energy of the intermetallic molecule NaAu, for which two largely at variance experimental values are available in the literature, has been redetermined by the Knudsen effusion mass spectrometry method. The molecule has been produced in the vapor phase by a specially designed experimental setting inspired by the double oven technique. The equilibrium of dissociation to atoms as well as the exchange equilibrium with the gold dimer were monitored mass-spectrometrically over about a 600 K temperature range. The third-law analysis of the equilibrium data provides the dissociation energy D-0(o) (NaAu, g) = 245.3 +/- 6.8 kJ/mol, corresponding to a formation enthalpy at 298 K of 228.3 +/- 7.5 kJ/mol. The NaAu species was also studied computationally at the CCSD(T) level with basis sets of increasing zeta quality thus allowing to evaluate the molecular parameters and the dissociation energy at the complete basis set limit.

The synthesis of thiophene fluorophores (TFs) and the engineering of molecular structure to achieve bright and stable blue to red and white fluorescence are described. Examples of application of TFs in cellular studies are reported.

AbstractBackground Selective imaging of lysosomes by fluorescence microscopy using specific fluorescent probes allows the study of biological processes and it is potentially useful also for diagnosis. Lysosomes are involved in numerous physiological processes, such as bone and tissue remodeling, plasma membrane repair, and cholesterol homeostasis, along with cell death and cell signaling. Despite the great number of dyes available today on the market, the search for new fluorescent dyes easily up-taken by cells, biocompatible and bearing bright and long-lasting fluorescence is still a priority. Methods Two thiophene-based fluorescent dyes, {TC1} and TC2, were synthetized as lysosome-specific probes. Results The new dyes showed high selectivity for fluorescent staining and imaging of lysosomes and disclosed high photostability, low toxicity and pH insensitivity in the range 2–10. Conclusions The {TC} dyes exhibited high co-localization coefficients (> 95%) and moderate quantum yields. They showed high biocompatibility and long-term retention, important features for biological applications. General significance The results of the present work disclose a new class of organic dyes with potential wide applications as specific and efficient lysosome probes in the study of various biological processes.

In this work, we report on 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 = 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.

The ability to create photoanodes in which the structural and morphological features of the underlying TiO2 nanocrystalline constituents provide a tailored nanotexture with a higher degree of functionality still represents an indispensible step toward boosting the ultimate light-to electricity conversion of photoelectrochemical devices. This is especially evident for dye solar cells. In this paper we have systematically analyzed the impact of several different TiO2 nanorod morphologies on the most meaningful electrochemical features of the mesoporous photoelectrode of a dye solar cell. The most relevant findings have been then adopted as design criteria to realize an optimized multilayered photoelectrode with a properly engineered architecture which embodies three different breeds of nanocrystal with synergistic peculiarities. It exhibited superior power conversion efficiencies with respect to conventional nanoparticle-based reference film.

The Berezinskii-Kosterlitz-Thouless phase transition from a disordered to a quasi-ordered state, mediated by the proliferation of topological defects in two dimensions, governs seemingly remote physical systems ranging from liquid helium, ultracold atoms and superconducting thin films to ensembles of spins. Here we observe such a transition in a short-lived gas of exciton-polaritons, bosonic light-matter particles in semiconductor microcavities. The observed quasi-ordered phase, characteristic for an equilibrium two-dimensional bosonic gas, with a decay of coherence in both spatial and temporal domains with the same algebraic exponent, is reproduced with numerical solutions of stochastic dynamics, proving that the mechanism of pairing of the topological defects (vortices) is responsible for the transition to the algebraic order. This is made possible thanks to long polariton lifetimes in high-quality samples and in a reservoir-free region. Our results show that the joint measurement of coherence both in space and time is required to characterize driven-dissipative phase transitions and enable the investigation of topological ordering in open systems.

Combining localized surface plasmons (LSPs) and diffractive surface waves (DSWs) in metallic nanoparticle gratings leads to the emergence of collective hybrid plasmonic-photonic modes known as surface lattice resonances (SLRs). These show reduced losses and therefore a higher Q factor with respect to pure LSPs, at the price of larger volumes. Thus, they can constitute a flexible and efficient platform for light-matter interaction. However, it remains an open question if there is, in terms of the Q/V ratio, a sizable gain with respect to the uncoupled LSPs or DSWs. This is a fundamental point to shed light upon if such modes want to be exploited, for instance, for cavity quantum electrodynamic effects. Here, using aluminum nanoparticle square gratings with unit cells consisting of narrow-gap disk dimers-a geometry featuring a very small modal volume-we demonstrate that an enhancement of the Q/V ratio with respect to the pure LSP and DSW is obtained for SLRs with a well-defined degree of plasmon hybridization. Simultaneously, we report a 5× increase of the Q/V ratio for the gap-coupled LSP with respect to that of the single nanoparticle. These outcomes are experimentally probed against the Rabi splitting, resulting from the coupling between the SLR and a J-aggregated molecular dye, showing an increase of 80% with respect to the DSW-like SLR sustained by the disk LSP of the dimer. The results of this work open the way toward more efficient applications for the exploitation of excitonic nonlinearities in hybrid plasmonic platforms.

We report on a transition in random lasers that is induced by the geometrical confinement of the emitting material. Different dye doped paper devices with controlled geometry are fabricated by soft lithography and show two distinguished behaviors in the stimulated emission: in the absence of boundary constraints, the energy threshold decreases for larger laser volumes showing the typical trend of diffusive nonresonant random lasers, while when the same material is lithographed into channels, the walls act as cavity and the resonant behavior typical of standard lasers is observed. The experimental results are consistent with the general theories of random and standard lasers and a clear phase diagram of the transition is reported. (C) 2013 Optical Society of America

We study the spin vortices and skyrmions coherently imprinted into an exciton-polariton condensate on a planar semiconductor microcavity. We demonstrate that the presence of a polarization anisotropy can induce a complex dynamics of these structured topologies, leading to the twist of their circuitation on the Poincaré sphere of polarizations. The theoretical description of the results carries the concept of generalized quantum vortices in two-component superfluids, which are conformal with polarization loops around an arbitrary axis in the pseudospin space.

A stable and improved control of the wettability of textiles was obtained by using a coating of diamond like carbon (DLC) films on cotton by PECVD. By controlling different plasma pretreatments of argon, oxygen, and hydrogen on the cotton fibers' surface, we have shown that the pretreatments had a significant impact on wettability behavior resulting from an induced nanoscale roughness combined with an incorporation of selected functional groups. Upon subsequent deposition of diamond like carbon (DLC) films, the cotton fibers yield to a highly controlled chemical stability and hydrophobic state and could be used for self-cleaning applications. By controlling the nature of the plasma pretreatment we have shown that the oxygen plasma pretreatment was more effective than the argon and hydrogen for the superhydrophilic/ultra hydrophobic properties. The chemical and morphological changes of the cotton fibers under different treatments were characterized using X-ray photoelectron and Raman spectroscopy, AFM, and water contact angle measurements. The mechanism underlying the water-repellent properties of the cotton fibers provides a new and innovative pathway into the development of a range of advanced self-cleaning textiles.

We report the experimental observation and control of space and time-resolved light-matter Rabi oscillations in a microcavity. Our setup precision and the system coherence are so high that coherent control can be implemented with amplification or switching off of the oscillations and even erasing of the polariton density by optical pulses. The data are reproduced by a quantum optical model with excellent accuracy, providing new insights on the key components that rule the polariton dynamics.

Extremely lightweight plates made of an engineered PMMA-based composite material loaded with hollow glass micro-sized spheres, nano-sized silica particles and aluminum hydroxide prismatic micro-flakes were realized by cast molding. Their interesting bulk mechanical properties were combined to properly tailored surface topography compatible with the achievement of a superhydrophobic behavior after the deposition of a specifically designed hydrophobic coating. With this aim, we synthesized two different species of fluoromethacrylic polymers functionalized with methoxysilane anchoring groups to be covalently grafted onto the surface protruding inorganic fillers. By modulating the feed composition of the reacting monomers, it was possible to combine the hydrophobic character of the polymer with an high adhesion strength to the substrate and hence to maximize both the water contact angle (up to 157 degrees) and the durability of the easy-to-clean effect (up to 2000 h long outdoor exposure). (C) 2011 Elsevier Inc. All rights reserved.

The coupling of the electromagnetic field with an electronic transition gives rise, for strong enough light-matter interactions, to hybrid states called exciton-polaritons. When the energy exchanged between light and matter becomes a significant fraction of the material transition energy an extreme optical regime called ultrastrong coupling (USC) is achieved. We report a microcavity embedded p-i-n monolithic organic light emitting diode working in USC, employing a thin film of squaraine dye as active layer. A normalized coupling ratio of 30% has been achieved at room temperature. These USC devices exhibit a dispersion-less angle-resolved electroluminescence that can be exploited for the realization of innovative optoelectronic devices. Our results may open the way towards electrically pumped polariton lasers. (C) 2014 AIP Publishing LLC.

The peculiar architecture of a novel class of anisotropic TiO 2(B) nanocrystals, which were synthesized by an surfactant-assisted nonaqueous sol-gel route, was profitably exploited to fabricate highly efficient mesoporous electrodes for Li storage. These electrodes are composed of a continuous spongy network of interconnected nanoscale units with a rod-shaped profile that terminates into one or two bulgelike or branch-shaped apexes spanning areas of about 5 × 10 nm2. This architecture transcribes into a superior cycling performance (a charge capacitance of 222 mAh g-1 was achieved by a carbon-free TiO2(B)-nanorods-based electrode vs 110 mAh g-1 exhibited by a comparable TiO 2-anatase electrode) and good chemical stability (more than 90% of the initial capacity remains after 100 charging/discharging cycles). Their outstanding lithiation/delithiation capabilities were also exploited to fabricate electrochromic devices that revealed an excellent coloration efficiency (130 cm2 C-1 at 800 nm) upon the application of 1.5 V as well as an extremely fast electrochromic switching (coloration time ∼5 s)

Rationale & aim: Imatinib mesylate (IM), a selective tyrosine kinase inhibitor of the oncoprotein BCR-ABL, is the 'gold standard' for patients with chronic myeloid leukemia (CML) but the drug does not eliminate CML stem cells, leading to disease relapse on drug discontinuation. At present, much effort is focused on delivery carriers that can increase the intracellular retention and antileukemic impact of IM. We previously validated IM-loaded polyelectrolyte microcapsules as effective purging agents to eradicate BCR-ABL(+) cells from CML patient autografts. The aim is to develop controlled release carriers that can increase the intracellular retention and functionality of IM in leukemia cells. Materials & methods: Herein, novel polyelectrolyte complexes were used as model carriers for IM in a CML cell line (KU812) and CD34(+) cells freshly isolated from patients. Results & discussion: Polyelectrolyte complexes promoted a long-acting BCR-ABL kinase inactivation that was necessary to promote apoptosis at approximately twofold lower intracellular IM dose compared with the microscale formulation polyelectrolyte microcapsules. Conclusion: IM-loaded polyelectrolyte complexes can be used as more efficient delivery devices for overcoming drug resistance of BCR-ABL(+) leukemic cells.

We investigated the uptake and release of labeled antibodies from pH-sensitive hydrogel microparticles (i.e. microgels) by means of fluorescence analysis of labeled biological samples. The poly(methacrylic acid) (PMAA) hydrogel is a carbon-based network having carboxylic groups on the surface that dissociate according to their acid-base equilibrium. The ability of the PMAA microgel to encapsulate and release anti-CD4 and anti-CD8 monoclonal antibodies (MAbs), differing for the isotype and labeled with highly photostable fluorophore, was studied in solution by photoluminescence spectroscopy. The experimental results indicated that the uptake and release of the tested antibodies were controlled by pH. Furthermore, confocal microscopy analysis in the solid state revealed that the distribution of the labeled antibodies either on the surface or in the core of the microgel matrix was related to the specific properties of these MAbs.

Rationale & aim: Imatinib mesylate (IM), a selective tyrosine kinase inhibitor of the oncoprotein BCR-ABL, is the 'gold standard' for patients with chronic myeloid leukemia (CML) but the drug does not eliminate CML stem cells, leading to disease relapse on drug discontinuation. At present, much effort is focused on delivery carriers that can increase the intracellular retention and antileukemic impact of IM. We previously validated IM-loaded polyelectrolyte microcapsules as effective purging agents to eradicate BCR-ABL(+) cells from CML patient autografts. The aim is to develop controlled release carriers that can increase the intracellular retention and functionality of IM in leukemia cells. Materials & methods: Herein, novel polyelectrolyte complexes were used as model carriers for IM in a CML cell line (KU812) and CD34(+) cells freshly isolated from patients. Results & discussion: Polyelectrolyte complexes promoted a long-acting BCR-ABL kinase inactivation that was necessary to promote apoptosis at approximately twofold lower intracellular IM dose compared with the microscale formulation polyelectrolyte microcapsules. Conclusion: IM-loaded polyelectrolyte complexes can be used as more efficient delivery devices for overcoming drug resistance of BCR-ABL(+) leukemic cells. Original submitted 26 September 2012; Revised submitted 17 July 2013.

Inthis paper, we have investigated the possibility to realize a nanocomposite buffer layer for perovskite solar cells, based on polyelectrolyte poly(3,4-ethylenedioxythiophene): poly(styrene sulfonate) PEDOT:PSS and graphene oxide (GO). To this aim, GO, prepared by a modified Hummers method, was mixed with PEDOT: PSS by solvent swelling method and reduced in situ into the polymer matrix through a green and simple method, by using UV radiation. Thin nanocomposite layers were spin coated on different substrates and characterized by several techniques. GO reduction was first analyzed by XPS analyses, monitoring the decrease of the intensity of the peak of the oxygen groups linked to carbon. The grade of the dispersion of GO into PEDOT: PSS was also analyzed by scanning electron microscopy. Sheet resistance measurements of the films with and without GO before and after UV treatment was performed. The thermal stability of the nanocomposites was then evaluated by thermogravimetric analyses. The nanocomposite layer was finally employed in a perovskite solar cell to evaluate the effect of GO reduction on power conversion efficiency. The interface interaction between the nanocomposite and the perovskite precursors was analyzed by contact angle measurements.

The matrix assisted pulsed laser evaporation (MAPLE) technique is emerging as an alternative route to conventional deposition methods of organic materials (solution-phase and thermal evaporation approaches). However, the high surface roughness of the films deposited by MAPLE makes this technique not compatible with applications in electronics and photonics. In this paper we report the deposition of MAPLE-films of a green light emitting polymer, commercially named ADS125GE, with remarkable low roughness values, down to about 10 nm at the thickness conventionally used in photonic devices (similar to 40 nm). This issue is discussed as a function of polymer concentration, target-substrate distance and substrate rotation based on AFM topography images, roughness estimation and optical (absorption and luminescent) measurements. In addition we have fabricated an organic light emitting diode with this technique using the best deposition parameters which guarantee the lowest roughness. These results open the way to MAPLE applications in organic photonics and opto-electronics.

A collection of more than 1800 carbonized papyri, discovered in the Roman 'Villa dei Papiri' at Herculaneum is the unique classical library survived from antiquity. These papyri were charred during 79 A.D. Vesuvius eruption, a circumstance which providentially preserved them until now. This magnificent collection contains an impressive amount of treatises by Greek philosophers and, especially, Philodemus of Gadara, an Epicurean thinker of 1st century BC. We read many portions of text hidden inside carbonized Herculaneum papyri using enhanced X-ray phase-contrast tomography non-destructive technique and a new set of numerical algorithms for 'virtual-unrolling'. Our success lies in revealing the largest portion of Greek text ever detected so far inside unopened scrolls, with unprecedented spatial resolution and contrast, all without damaging these precious historical manuscripts. Parts of text have been decoded and the 'voice' of the Epicurean philosopher Philodemus is brought back again after 2000 years from Herculaneum papyri.

An experimental study of photovoltachromic (PVCC) devices for dynamic solar control in buildings is presented. The fabricated devices underwent a complete opto-eletctrical characterization and the results obtained were employed as an input for the simulation of building integrated multifunctional windows. This multidisciplinary activity aims at achieving relevant feedbacks from the simulation of real large area devices in order to adjust and even direct further experimental efforts, before reaching the production phase. Devices having different electrochromic capacitances were used and the optical measurements became useful inputs for the simulation task. Simulation's results turned into feedbacks concerning the modulation of the transmittance spectra, the colour of bleached devices, the scale-up of PVCCs. Devices used in the current work showed a power peak of 4.22 mW/cm(2) at the maximum power point and a smart modulation of optical transmittance of 50.16% (at 700 nm). Simulations of natural light penetration in office buildings showed that the integration of PVCCs in traditional windows could dramatically increase indoor visual comfort. An increase of the average UDI for a typical room up to 71.8% and a decrease of intolerable glare levels (DGP higher than 0.45) down to 12% were the major benefits of the substitution of traditional clear glasses with integrated PVCCs. (C) 2013 Elsevier B.V. All rights reserved.

The development of alternative deposition techniques of conjugated polymeric compounds is an important step towards the fabrication of low cost multi-layered organic light emitting diodes suitable for display or lighting applications. In this work we show a white light -emitting polymeric hetero-structured diode consisting of three-stacked blue, red and green light emitting polymers. In order to circumvent the issue of selecting orthogonal solvents in solution -deposition approaches, we combine spin-coating with the Matrix Assisted Pulsed Laser Evaporation technique, resulting in the realization of a polymeric multilayered stack. By controlling the carriers and the energy transfer across the three light emitting layers interfaces, as well as the interplay between the deposition parameters, a pure white colour emission with Commission Internationale de l'Éclairage coordinates (X=0.327, Y=0.374) and a Color Rendering Index of 70 have been achieved. Our study represents the first proof of a light emitting diode made by multilayer polymeric thin films emitting white light.

This manuscript reports on the synthesis, the photophysical study and the electroluminescent properties of a series of heteroleptic cyclometalated iridium(III) complexes based on 2,5-diaryl-pyridines as C^N cyclometalating ligands and acetylacetonate as ancillary ligand. The complexes were characterised by elemental analysis, ESI-MS, multinuclear NMR, TGA and electrochemistry. Their optical properties were investigated by UV-Vis and photoluminescence. DFT and TD-DFT calculations provided further insights into the effects of the 5-aryl substitution on the electronic and photophysical properties of the new complexes. The presence of suitable π-extended ligands exerts a beneficial effect on the performances of the corresponding solution-processed light-emitting diodes, leading to a maximum brightness of 10 620 cd m−2 at a current efficiency of 10.0 cd A−1.

New random poly(arylene-vinylene)s obtained by combining different amounts of benzo[2,1,3]thiadiazole units with 9,9-dialkylfluorene and/or 1,4-dialkoxybenzene building blocks were synthesized by the Suzuki-Heck polymerization and characterized for use in bulk hetero-junction solar cells. Their optical, electrochemical, morphological and photovoltaic features were investigated. Notwithstanding the relatively low weight-average molecular weights of the obtained polymers (7000–13000 Da), they formed good quality films by spin-coating. UV–Vis measurements permitted the evaluation of their band gap (1.77–2.12 eV), enabling them to harvest a broad portion of the solar spectrum from 350 nm to 650–700 nm. An electrochemical study revealed that the copolymers are endowed with HOMO/LUMO energy levels suitable for both an efficient electron transfer and a high open circuit voltage (Voc) for devices embodying the polymer/PCBM blends. This investigation pinpoints the important role of the copolymer composition (in terms of molar ratio of the monomeric units) on the performance of the donors in BHJs. In fact, in disagreement with the presumed Voc and current densities, the terpolymer poly[1,4-bis(2-ethylhexyloxy)-2,5-phenylene-vinylene-co-9,9-bis(2-ethylhexyl)-2,7-fluorenylene-vinylene-co-4,7-benzo[2,1,3]thiadiazolylene-vinylene] showed the best performance of the copolymer series, with a PCE of 0.4% and a Voc of 0.76 V, probably due to the favorable phase separation in the blend and consequently a better exciton dissociation.

The article reports on the properties of a new class of arylene–ethynylene semiconductors incorporating anthracene and the bridged bithiophene dithienopyrrole. Two monodispersed structures were synthesised: the first with a dithienopyrrole core bound to two anthracenyl–ethynyl side groups namely the 2,6-bis(anthracen-9-ylethynyl)-4-(2-ethylhexyl)-4H-dithieno[3,2-b:2′,3′-d]pyrrole (ADA); in the second structure the anthracene core was functionalised with two dithienopyrrolylethynyl groups, obtaining 9,10-bis((4-(2-ethylhexyl)-4H-dithieno[3,2-b:2′,3′-d]pyrrol-2-yl)ethynyl)anthracene (DAD). The properties of these materials were compared with those of the corresponding polymer: poly[4-(2-ethylhexyl)-4H-dithieno[3,2-b:2′,3′-d]pyrrole-2,6-diylethynylene-anthracen-9,10-diylethynylene] (polyAD). Devices employing PC61BM as an electron acceptor revealed that the monodispersed materials (ADA and DAD) were better performing than polyAD, seemingly due to the better homogeneity of the donor–acceptor blend, as revealed by AFM. The PCE value (1.3%) obtained with DAD ranks among the highest reported for non-polymeric small molecule-based BHJ solar cells constructed without the use of additives or annealing processes, thus demonstrating that ethynylene-containing electron-rich systems are promising donors for organic solar cell applications.

Novel co-sensitizers have been structurally tailored and implemented in multi-sensitized devices demonstrating synergic efficiency enhancement attributable to improved light-harvesting as well as prevention of charge recombination.

The present invention provides methods for inhibiting or preventing cancer cell growth using silver nanoparticles

An organic light emitting diode (OLED) emitting light downward through a transparent substrate (240) is described. The OLED embeds a microcavity (220) formed between a cathode (210) and an anode (230) and includes a plurality of organic layers comprising a light emitting layer (225). It is characterized in that the plurality of organic layers includes at least a first layer (229) made of an organic doped material aimed at enhancing the transport of holes; the plurality of organic layers also includes at least a second layer (221) made of an organic doped material aimed at enhancing the transport of electrons. The OLED is further characterized in that the anode i (230) is obtained by deposition of a semi transparent layer of silver (Ag) over the transparent substrate to be directly in contact with the first doped organic layer (229). Then, thicknesses of the first and second doped organic layers can be freely adapted to best adjust the optical characteristics of the microcavity for the wavelength of monochromatic light to be produced by the OLED.

L’invenzione fa riferimento ad un nuovo concetto di finestra intelligente in cui le funzionalità di oscuramento, produzione di energia ed illuminazione artificiale sono integrate su un unico subtrato (vetro o plastica). Grazie all’impiego di materiali multifunzionali e un design innovativo dell’architettura, la seguente tecnologia è pertanto in grado di produrre energia per conversione fotovoltaica, modulare in modo dinamico le proprietà termiche ed il cambiamento di colore e trasparenza della vetrata per effetto elettrocromico, ed infine produrre luce artificiale mediante la tecnologia OLED. L’originalità e la peculiarità di questa invenzione risiede inoltre nella possibilità di fabbricare la tecnologia su un unico substrato mediante processi a basso impatto ambientale e di essere installata su qualsiasi tipo di finestra senza essere sostituita.