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The increasing energy demand and the ever more pressing need for clean technologies of energy conversion pose one of the most urgent and complicated issues of our age. Thermoelectricity, namely the direct conversion of waste heat into electricity, is a promising technique based on a long-standing physical phenomenon, which still has not fully developed its potential, mainly due to the low efficiency of the process. In order to improve the thermoelectric performance, a huge effort is being made by physicists, materials scientists and engineers, with the primary aims of better understanding the fundamental issues ruling the improvement of the thermoelectric figure of merit, and finally building the most efficient thermoelectric devices. In this Roadmap an overview is given about the most recent experimental and computational results obtained within the Italian research community on the optimization of composition and morphology of some thermoelectric materials, as well as on the design of thermoelectric and hybrid thermoelectric/photovoltaic devices.

An innovative consolidation strategy for degraded paper is presented based on the reversible application of cellulose nanocrystals as sustainable fillers to reinforce mechanical properties and resistance to further degradation. The compatibility and efficacy of the proposed consolidation treatment are assessed first on pure cellulose paper, used as a model, by reliable techniques such as field emission scanning electron microscopy, atomic force microscopy, tensile tests, X-ray powder diffraction, and Fourier transform infrared spectroscopy, evidencing the influence of the surface functionalization of nanocellulose on the consolidation and protection effects. Then, the consolidation technique is applied to real aged paper samples from Breviarium romanum ad usum Fratrum Minorum S.P. (1738), demonstrating the promising potential of the suggested approach. Amperometric measurements, carried out with a smart electrochemical tool developed in our laboratory, demonstrate the reversibility of the proposed treatment by removal of the nanocrystalline cellulose from the paper surface with a suitable cleaning hydrogel. This completely new feature of the consolidation treatment proposed here satisfies a pivotal requisite in cultural heritage conservation because the methodological requirement for the ″reversibility″ of any conservation measure is a fundamental goal for restorers. A paper artifact, in fact, is subject to a number of natural and man-made hazards, inducing continuous degradation. With time, monitoring and consolidation actions need to be often performed to ensure conservation, and this tends to modify the status quo and compromise the artifact integrity. Removable treatments can potentially avoid erosion of the artifact integrity.

Treatment of vascular disease, from peripheral ischemia to coronary heart disease (CHD), is poised for transformation with the introduction of transient implants designed to "scaffold" regeneration of blood vessels and ultimately leave nothing behind. Improved materials could expand the use of these devices. Here, we examine one of the leading polymers for bioresorbable scaffolds (BRS), polylactide (PLA), as the matrix of nanocomposites with tungsten disulfide (WS2) nanotubes (WSNT), which may provide mechanical reinforcement and enhance radio-opacity. We evaluate in vitro cytotoxicity using vascular cells, flow-induced crystallization and radio-opacity of PLA-WSNT nanocomposites at low WSNT concentration. A small amount of WSNT (0.1 wt%) can effectively promote oriented crystallization of PLA without compromising molecular weight. And radio-opacity improves significantly: as little as 0.5 to 1 wt% WSNT doubles the radio-opacity of PLA-WSNT relative to PLA at 17 keV. The results suggest that a single component, WSNT, has the potential to increase the strength of BRS to enable thinner devices and increase radio-opacity to improve intraoperative visualization. The in vitro toxicity results indicate that PLA-WSNT nanocomposites are worthy of investigation in vivo. Although substantial further preclinical studies are needed, PLA-WSNT nanocomposites may provide a complement of material properties that may improve BRS and expand the range of lesions that can be treated using transient implants. STATEMENT OF SIGNIFICANCE: Bioresorbable Scaffolds (BRSs) support regeneration of arteries without permanent mechanical constraint. Poly-L-lactide (PLLA) is the structural material of the first approved BRS for coronary heart disease (ABSORB BVS), withdrawn due to adverse events in years 1-3. Here, we examine tungsten disulfide (WS2) nanotubes (WSNT) in PLA to address two contributors to early complications: (1) reinforce PLLA (enable thinner BRS), and (2) increase radiopacity (provide intraoperative visibility). For BRS, it is significant that WSNT disperse, remain dispersed, reduce friction and improve mechanical properties without additional chemicals or surface modifications. Like WS2 nanospheres, bare WSNT and PLA-WSNT nanocomposites show low cytotoxicity in vitro. PLA-WSNT show enhanced flow-induced crystallization relative to PLA, motivating future study of the processing behavior and strength of these materials.

Cellulose nanopaper (CNP) features appealing properties, including transparency, flatness, a low thermal expansion coefficient and thermal stability, often outperforming conventional paper. However, free-standing crystalline cellulose films usually swell in water or upon moisture sorption, compromising part of their outstanding properties. This remains a major problem whenever working in a water environment is required. Freestanding cellulose nanopaper is prepared by solution casting water suspensions of cellulose nanocrystals with an average width of 10 nm and an average aspect ratio of 28, isolated from Avicel by acid hydrolysis and extensively characterized by AFM and FE-SEM measurements and GPC detection of their degree of polymerization. We demonstrate by elemental analyses, FT-IR, Raman spectroscopy, XRD measurements and water contact angle detection that wet treatment with lauroyl chloride results in surface hydrophobization of nanopaper. The hydrophobized nanopaper, C12-CNP, shows a more compact surface morphology than the starting CNP, due to the effect of chemical functionalization, and presents enhanced resistance to water, as assessed by electrochemical permeation experiments. The new hydrophobized nanopaper is a promising substrate for thin film devices designed to work in a humid environment.

The project stems from an agreement between the regional transport company COTRAL spa and the Department of Architecture of the University of Roma Tre. The need for a new bus exchange node arises following the earthquake of August 24th 2016 that destroyed the city of Amatrice and damaged the neighboring areas. The project is designed for areas subjected to earthquakes, it is therefore an opportunity to tackle the difficulties at national level starting from the solution of the local problem. It is a wooden building, environmentally aware, combining active and passive strategies together with the technological innovation of the modular systems of which it is composed, with the objective of reducing costs and consumption. The drafting of the project documents, the choice of technology to be used in the nodes and the prefabrication system was all realized in the BIM environment. The aim of the University convention with COTRAL spa is not to deliver only the graphic works, but a complete package that simultaneously considers the project in three dimensions, the detailed nodes, the quantification of the materials used, and the solar contribution given by the its geo-location. The opportunity arising from the agreement, therefore, lends itself to become a case study, a virtuous example of research on how architecture can intervene quickly and concretely on the territory. An intervention with an open look at the future of design and representation.

Pd+ ions (90 keV) were implanted at normal incidence and at room temperature in different highly insulating (>200 GΩ) thermoplastic polymers (poly(methyl methacrylate), polypropylene, polyethylene terephthalate glycol-modified, and polycarbonate). At high fluence and optimized process parameters, the ion implantation gives rise to the formation of a nanocomposite thin surface layer constituted by Pd nanoclusters and carbonaceous material (nanographite/amorphous carbon). The morphological, microstructural, and microanalytical properties of the nanocomposite layers were investigated by He-ion microscopy, glancing incidence X-ray diffraction, and Raman scattering, respectively. The electrical properties were characterized by resistance, van der Pauw, and Hall measurements. We performed accurate simultaneous deformation/bending experiments and electrical resistance measurements. We show that the electrical resistance varies linearly with the mechanical deformation (beam deflection) applied. The experimental results are interpreted by “hopping conductivity” model considering the nanostructure configuration of the nanocomposite layers. A gauge factor in the range between 4 and 8, depending on the ion-implanted polymer, was obtained for prototype strain gauge devices.

Poly(L-lactide) (PLLA) is a semicrystalline, biocompatible and biodegradable polymer widely employed in many applications (food packaging, biomedical devices, drug delivery systems). This work deals with nanocomposites of PLLA and tungsten disulfide (WS2) nanotubes (NTs) as a novel material to obtain thinner and stronger bioresorbable vascular scaffolds. We studied the influence of WS2 NTs on the mechanical properties of PLLA-WS2 films. Polarized optical microscopy reveals a high degree of orientation of the polymer molecules in stretched films that further increases with a post-stretching annealing treatment. At the same time, X-ray diffraction (XRD) and Raman spectroscopy confirm enhancement of the crystallinity induced by the WS2 NTs. © 2018 Author(s).

In this work, we report on the synthesis of CdTe nanocrystals (NCs) by using of two different saturated long-chain capping ligands, oleic (OA) and myristic acids (MA), and investigate their influence on the nanocrystals optical properties. The main goal of our study is to identify the ligand that allows slowing down the growth rate of the NCs after nucleation, in order to obtain small enough nanocrystals emitting in the blue-green part of the optical spectrum. Our results show clearly that oleic acid allows a good control on the CdTe NCs growth, finally leading to a fine-tuning of the NCs size-dependent emission from the green to the yellow part of the spectrum. Instead, a faster reaction kinetics, which arises in a lower possibility to produce small NCs emitting in the green part of the spectrum, was noticed using myristic acid. (© 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

A new procedure for the alignment of carbon nanotubes in a thermosetting matrix is proposed in this study. The two-step approach is based on (i) the alignment of carbon nanotubes (CNTs) in thermoplastic fibres by electrospinning and (ii) the transfer of these nanocompositefibres into a reactive thermosetting resin, in which they are easily soluble. After fibre dissolution, the CNTs remain aligned in the cured thermosetting matrix.The proof of concept is demonstrated by producing electrospunpolymethyl methacrylate (PMMA) fibres filled with single wall carbon nanotubes (SWCNTs) in the form of unidirectional tape, which are then solubilised into a vinylester (VE) matrix. The PMMA is easily dissolved by the styrene present in the VE resin, leaving SWCNTs aligned in the cured VE network, as confirmed by Raman spectroscopy studies. A 50% increase in elastic modulus (SWCNT 1.3. wt.%) has been obtained by dynamic mechanical analysis carried out in tensile mode at 1. Hz. Thanks to its ability to orient carbon nanotubes in a thermosetting matrix, the proposed method can be exploited also to transfer oriented nanofillers into continuous fibre composites, thus obtaining multiscale or hierarchical composites. © 2014 Elsevier Ltd.

We report on the synthesis and characterization of a hyperbranched polymer englobing single-wall carbon nanotubes (SWCNTs). This new material was obtained by using SWCNTs functionalized with carboxylic groups as starting reagent. The acid groups were firstly converted in acyl chloride moieties and afterwards were bound to hexamethylenediamine (HMDA) via formation of amide functionality. The acquired spectra of attenuated total reflectance and the analysis performed through x-ray photoelectron spectroscopy confirmed the amide bond formation. The hyperbranched polymer characterization was completed by using scanning and transmission electron microscopy, thermo-gravimetric analysis and Raman spectroscopy. The electron microscopy analyses showed the formation of an amorphous polymeric material englobing a dense network of SWCNTs without phase segregation, demonstrating that the reaction with HMDA allows a reorganization of SWCNTs in a complex three-dimensional network.

A straightforward, electron-beam induced synthesis and patterning approach to the in situ generation of CdS nanocrystals in nanocomposite films and light-emitting electrospun nanofibers is used. Smartly combining room-temperature nanoimprinting, electrospinning, and electron-beam decomposition of nanocrystal precursors and subsequent nucleation of nanoparticles in a polymer matrix allows exploitation of the most favorable flow conditions of organics to produce various nanocomposite nanostructures.

A study was conducted to demonstrate lasing action by composite electrospun polymer nanofibers emitting in the visible and near-infrared (NIR) spectral region. It also demonstrated the significant potential of electrospun and flexible gain nanofibers as active waveguides and lasers. Single-mode optically pumped lasing sources on individual electrospun nanofibers emitting at 585 nm with linewidth 0.3 nm and excitation threshold fluence of 60 μJ cm -2 were demonstrated as a prototype system. The single fiber surface was found to exhibit a root-mean-square roughness of about 6 nm using atomic force microscopy (AFM). The fibers were tested for laser emission and it was revealed that each fiber constituted a Fabry-Pérot cavity for spectral selection and light amplification, due to the high confinement of the emitted light.

The realization of isolated light-emitting dots, with lateral dimension down to a few tens of nanometers, by direct particle replication in nonwetting templates (PRINT) on dissolved conjugated polymers, and on their optical characterization.

A straight synthetic route to fabricate hybrid nanocomposite films of well-dispersed CdS nanocrystals (NCs) in poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV) is reported. A soluble cadmium complex [Cd(SBz)2]2·MI, obtained by incorporating a Lewis base (1-methylimidazole, MI) on the cadmium bis(benzyl)thiol, is used as starting reagent in an in situ thermolytic process. CdS NCs with spherical shape nucleate and grow well below 200°C in a relatively short time (30 min). Photoluminescence spectroscopy measurements performed on CdS/MEH-PPV nanocomposites show that CdS photoluminescence peaks are totally quenched inside MEH-PPV, if compared to CdS/PMMA nanocomposites, as expected due to overlapping of the polymer absorption and CdS emission spectra. The CdS NCs are well-dispersed in size and homogeneously distributed within MEH-PPV matrix as proved by transmission electron microscopy. Nanocomposites with different precursor/polymer weight ratios were prepared in the range from 1:4 to 4:1. Highly dense materials, without NCs clustering, were obtained for a weight/weight ratio of 2:3 between precursor and polymer, making these nanocomposites particularly suitable for optoelectronic and solar energy conversion applications.

We demonstrate the multilevel patterning of organic light-emitting polymers by room-temperature nanoimprint lithography (RT-NIL), which is impossible to obtain by conventional hot embossing. In particular, we realize one- and two-dimensional photonic crystals with 500 nm periodic features and investigate the changes in the optical properties (luminescence and quantum yield) of the organic active layer. An increase of the quantum yield by 2.4% for the patterned film with respect to the untextured one and the enhancement of the output light emitted at a particular angle (Theta = 69 degrees) are observed for gratings whose Bragg periodicity matched the emission wavelength of the polymer. The employment of RT-NIL to pattern polymer semiconductors without degradation of their optical properties represents a strategic route for the realization of novel nanopatterned optoelectronic devices.

Elastomeric polymeric microspheres are employed as a direct-writing tool for the continuous delivery of molecular materials. The mechanical properties enabling patterning are investigated and modelled. The proposed approach provides a low cost and versatile lithographic method for transferring features with real-time dynamic control. This journal is © 2013 The Royal Society of Chemistry.

We report on the simple, in situ generation of CdS nanocrystals inside electrospun polymer fibres by thermal decomposition of a cadmium thiolate precursor, leading to nanocomposite light-emitting fibres. The modifications induced in the precursor by the thermal decomposition are investigated by a morphological, structural and spectroscopic analysis of the resulting nanocomposite fibres. This approach allows us to overcome nanofabrication difficulties related to disfavoured micro- or nanofluidic molecular flow as given by the direct incorporation of particles in the electrospinning solution. This method therefore enables the synthesis of luminescent, CdS-based composite fibres with emission peaked in the visible range, suitable as building blocks for nanophotonic devices based on light-emitting nanomaterials.

The authors demonstrate full color tunability in the visible range, including white emission, by polymer nanofibers based on binary blends of conjugated materials. The nanofibers are realized by electrospinning and their emission is based on the dipole-dipole energy transfer from a blue-emitting donor and a red-emitting acceptor conjugated polymer. The fibers are characterized by scanning electron microscopy and time-resolved and cw photoluminescence. Light emission is tuned from blue to red, including bright white with color coordinates (0.38, 0.34) according to the standard of the Commission Internationale de l’Eclairage. Polymer nanofibers based on blends of conjugated compounds turn out to be a promising class of organic semiconductor building blocks for nanophotonics.

Organic materials have revolutionized optoelectronics by their processability, flexibility and low cost, with application to light-emitting devices for full-colour screens, solar cells and lasers. Some low-dimensional organic semiconductor structures exhibit properties resembling those of inorganics, such as polarized emission and enhanced electroluminescence. One-dimensional metallic, III-V and II-VI nanostructures have also been the subject of intense investigation as building blocks for nanoelectronics and photonics. Given that one-dimensional polymer nanostructures, such as polymer nanofibres, are compatible with sub-micrometre patterning capability and electromagnetic confinement within subwavelength volumes, they can offer the benefits of organic light sources to nanoscale optics. Here we report on the optical properties of fully conjugated, electrospun polymer nanofibres. We assess their waveguiding performance and emission tuneability in the whole visible range. We demonstrate the enhancement of the fibre forward emission through imprinting periodic nanostructures using room-temperature nanoimprint lithography, and investigate the angular dispersion of differently polarized emitted light.

We report on the use of nanoimprint lithography at room temperature (RT-NIL) for the direct structuring of polyfluorene and poly(phenylenevinylene) derivatives and of their blends without the degradation of the emissive characteristics of the active molecules. We apply RT-NIL for the fabrication of periodic one- and two-dimensional gratings with feature width that varies from 100 to 500 nm. Moreover, we analysed the effects that a superimposed periodic corrugation induces on the emitted light in terms of spectral properties and luminescence efficiency, thus ruling out any degradation of the emission. In particular, the combination of nanopatterning and active blends opens new perspectives for the control of the emitted colour from conjugated polymer films.

This work describes the successful micropatterning of hybrid systems consisting of hydrogel-dispersed optically active and controllable proteins on solid surfaces without degradation of the photophysical properties of the light-emitting biomolecules. It demonstrates the preservation of the luminescence properties of proteins entrapped into isolated microstructures of poly(acrylamide) gel. This way we can exploit both the structural and function-preserving properties of the hydrogels and the functionality of light-emitting proteins. We believe that this approach can open the way to the realization of nanopatterned optical memories based on photochromic biomolecules.

In order to observe in real-time and to accurately measure the filling speed during the capillary process in planar microfluidic devices, we integrated a ruler in the silicon master structures, side by side with the channels, and replicated it into the elastomeric elements. The time dependence of the covered length (z, t) and of the filling rate (v, t) under different temperature and surface functionalization conditions was then exactly determined by optical microscopy. This allowed us to quantitatively assess the strong dependence of v on the process environmental conditions, and to discard in real-time the presence of impurities on employed substrates, thus allowing one to strongly improve the throughput of the microfluidic-based soft lithography for nanotechnology applications.

The fabrication of polymeric fibers by soft lithography is demonstrated. Polyurethane, patterned by capillarity-induced molding with high-resolution elastomeric templates, forms mm-long fibers with a diameter below 0.3 mu m. The Young's modulus of the fabricated structures, evaluated by force-distance scanning probe spectroscopy, has a value of 0.8 MPa. This is an excellent example of nanostructures feasible by the combination of soft nanopatterning and high-resolution fabrication approaches for master templates, and particularly electron-beam lithography.

We demonstrate that a combination of ion sputtering and soft lithography is an alternative and effective way of nanostructuring soft matter. We create self-organized nanoscale structures on a glass template by irradiating the surface with a defocused, low energy Ar ion beam. Capillary force lithography is then used to transfer the pattern, exploiting the glass transition of polymeric layers. In particular, we demonstrate the pattern transfer of a periodic 150 nm ripple structure onto an organic compound. This new, unconventional combination is then a low-cost strategy that opens the way to a variety of applications in the field of organic-based devices.

The growing demand for new solutions to pursue the trend of micro- and nanoelectronics predicted by Moore's law is stimulating the development of new high-resolution, low-cost lithographies. Here we demonstrate that several bottom-up approaches can be used to increase the throughput of soft lithography by exploiting the enhanced hydrophilicity, the low viscosity, and the fragility of the employed materials. In particular, the customized functionalization of the involved surfaces to improve the wettability to polymer fluids and the dramatic decrease of the viscosity of polymer compounds as the temperature is increased, together with the good thermal stability of the functionalized surfaces, allow a faster filling of elastomeric channels, up to almost an order of magnitude with respect to conventional microfluidics.

Physiological patterns of the extracellular matrix protein, laminin-1, were obtained on glass substrates by physisorption-assisted microcontact printing. Besides the well-retained antigenicity confirmed by indirect immunofluorescence assays, we investigated the supramolecular organization of the proteins by atomic force microscopy. We found the characteristic protein self-assembling in polygonal networks with well-defined sub-100 nm quaternary structures of laminin. The formation of these physiological mesh-like protein matrices was obtained by means of one-step soft lithography without any preliminary functionalization of glass, which can be exploited for many possible applications for cell cultures and biomolecular devices.

We demonstrate a multiple molding procedure based on the combination of replica molding, in situ patterning of an ultraviolet curable epoxy resist, micromachining by elastomeric elements, and nanoimprinting lithography. The pattern, with features down to the 100 nm scale, is sequentially transferred to several different polymers, allowing one to realize high-resolution organic molds for imprinting compounds of lower glass-transition temperature. The intimate integration of soft and nanoimprinting lithographies enables a combined, multistep mechanical patterning, which can be very useful for a great range of applications for molecular lithography and devices. (c) 2006 American Vacuum Society.

This study explores a novel conversion of CO2into the chemicals hydroxyectoine and ectoine, which are compounds with high retail values in the pharmaceutical industry. Firstly, 11 species of microbes able to use CO2and H2and that have the genes for ectoines synthesis (ectABCD) were identified through literature search and genomic mining. Laboratory tests were then conducted to ascertain the capacity of these microbes to produce ectoines from CO2. Results showed that the most promising bacteria for CO2to ectoines bioconversion areHydrogenovibrio marinus, Rhodococcus opacus,andHydrogenibacillus schlegelii.Upon salinity and H2/CO2/O2ratio optimization,H. marinusaccumulated 85mg of ectoine g biomass−1. Interestingly,R.opacusandH. schlegeliimainly produced hydroxyectoine (53 and 62mgg biomass−1), which has a higher commercial value. Overall, these results constitute the first proof of a novel valorization platform of CO2and lay the foundation for a new economic niche aimed at CO2recircularization into pharmaceuticals.