Understanding and controlling the efficiency of Au24M(SR)18 nanoclusters as singlet-oxygen photosensitizers

Atomically precise Au24M(SR)18 clusters were used as singlet-oxygen photosensitizers. Comprehensive kinetic analysis provided insights into the mechanism and driving-force dependence of the quenching of 1O2 by gold nanoclusters

Hybrid Copper-Nanowire–Reduced-Graphene-Oxide Coatings: A “Green Solution” Toward Highly Transparent, Highly Conductive, and Flexible Electrodes for (Opto)Electronics

This study reports a novel green chemistry approach to assemble copper-nanowires/reduced-graphene-oxide hybrid coatings onto inorganic and organic supports. Such films are robust and combine sheet resistances ( 70%) that are rivalling those of indium–tin oxide. These electrodes are suitable for flexible electronic applications as they show a sheet resistance change of <4% after 10 000 bending cycles at a bending radius of 1.0 cm, when supported on polyethylene terephthalate foils. Significantly, the wet-chemistry method involves the preparation of dispersions in environmentally friendly solvents and avoids the use of harmful reagents. Such inks are processed at room temperature on a wide variety of surfaces by spray coating. As a proof-of-concept, this study demonstrates the successful use of such coatings as electrodes in high-performance electrochromic devices. The robustness of the electrodes is demonstrated by performing several tens of thousands of cycles of device operation. These unique conducting coatings hold potential for being exploited as transparent electrodes in numerous optoelectronic applications such as solar cells, light-emitting diodes, and displays

Tuning the energetics and tailoring the optical properties of silver clusters confined in zeolites

The integration of metal atoms and clusters in well-defined dielectric cavities is a powerful strategy to impart new properties to them that depend on the size and geometry of the confined space as well as on metal-host electrostatic interactions. Here, we unravel the dependence of the electronic properties of metal clusters on space confinement by studying the ionization potential of silver clusters embedded in four different zeolite environments over a range of silver concentrations. Extensive characterization reveals a strong influence of silver loading and host environment on the cluster ionization potential, which is also correlated to the cluster's optical and structural properties. Through fine-tuning of the zeolite host environment, we demonstrate photoluminescence quantum yields approaching unity. This work extends our understanding of structure property relationships of small metal clusters and applies this understanding to develop highly photoluminescent materials with potential applications in optoelectronics and bioimaging

Design and Characterization of New Luminescent Sensors and Labels

The aim of this Ph.D. project has been the design and characterization of new and more efficient luminescent tools, in particular sensors and labels, for analytical chemistry, medical diagnostics and imaging. Actually both the increasing temporal and spatial resolutions that are demanded by those branches, coupled to a sensitivity that is required to reach the single molecule resolution, can be provided by the wide range of techniques based on luminescence spectroscopy. As far as the development of new chemical sensors is concerned, as chemists we were interested in the preparation of new, efficient, sensing materials. In this context, we kept developing new molecular chemosensors, by exploiting the supramolecular approach, for different classes of analytes. In particular we studied a family of luminescent tetrapodal-hosts based on aminopyridinium units with pyrenyl groups for the detection of anions. These systems exhibited noticeable changes in the photophysical properties, depending on the nature of the anion; in particular, addition of chloride resulted in a conformational change, giving an initial increase in excimeric emission. A good selectivity for dicarboxylic acid was also found. In the search for higher sensitivities, we moved our attention also to systems able to perform amplification effects. In this context we described the metal ion binding properties of three photoactive poly-(arylene ethynylene) co-polymers with different complexing units and we highlighted, for one of them, a ten-fold amplification of the response in case of addition of Zn2+, Cu2+ and Hg2+ ions. In addition, we were able to demonstrate the formation of complexes with Yb3+ an Er3+ and an efficient sensitization of their typical metal centered NIR emission upon excitation of the polymer structure, this feature being of particular interest for their possible applications in optical imaging and in optical amplification for telecommunication purposes. An amplification effect was also observed during this research in silica nanoparticles derivatized with a suitable zinc probe. In this case we were able to prove, for the first time, that nanoparticles can work as “off-on” chemosensors with signal amplification. Fluorescent silica nanoparticles can be thus seen as innovative multicomponent systems in which the organization of photophysically active units gives rise to fruitful collective effects. These precious effects can be exploited for biological imaging, medical diagnostic and therapeutics, as evidenced also by some results reported in this thesis. In particular, the observed amplification effect has been obtained thanks to a suitable organization of molecular probe units onto the surface of the nanoparticles. In the effort of reaching a deeper inside in the mechanisms which lead to the final amplification effects, we also attempted to find a correlation between the synthetic route and the final organization of the active molecules in the silica network, and thus with those mutual interactions between one another which result in the emerging, collective behavior, responsible for the desired signal amplification. In this context, we firstly investigated the process of formation of silica nanoparticles doped with pyrene derivative and we showed that the dyes are not uniformly dispersed inside the silica matrix; thus, core-shell structures can be formed spontaneously in a one step synthesis. Moreover, as far as the design of new labels is concerned, we reported a new synthetic approach to obtain a class of robust, biocompatible silica core-shell nanoparticles able to show a long-term stability. Taking advantage of this new approach we also showed the synthesis and photophysical properties of core-shell NIR absorbing and emitting materials that proved to be very valuable for in-vivo imaging. In general, the dye doped silica nanoparticles prepared in the framework of this project can conjugate unique properties, such as a very high brightness, due to the possibility to include many fluorophores per nanoparticle, high stability, because of the shielding effect of the silica matrix, and, to date, no toxicity, with a simple and low-cost preparation. All these features make these nanostructures suitable to reach the low detection limits that are nowadays required for effective clinical and environmental applications, fulfilling in this way the initial expectations of this research project

Atomically Precise Metal Nanoclusters: Novel Building Blocks for Hierarchical Structures

Atomically precise ligand-protected nanoclusters (NCs) constitute an important class of compounds that exhibit well-defined structures and, when sufficiently small, evident molecular properties. NCs provide versatile building blocks to fabricate hierarchical superstructures. The assembly of NCs indeed offers opportunities to devise new materials with given structures and able to carry out specific functions. In this Concept article, we highlight the possibilities offered by NCs in which the physicochemical properties are controlled by the introduction of foreign metal atoms and/or modification of the composition of the capping monolayer with functional ligands. Different approaches to assemble NCs into dimers and higher hierarchy structures and the corresponding changes in physicochemical properties are also described

Self-organizing core-shell nanostructures: Spontaneous accumulation of dye in the core of doped silica nanoparticles

The process of formation of silica nanoparticles doped with a newly synthesized pyrene derivative has been investigated by means of fluorescence steady-state and time-resolved spectroscopy. The changes in the photophysical properties of the fluorophore were correlated to the increase of the nanoparticles hydrodynamic volume measured via dynamic light scattering (DLS) allowing us to determine the radial profile of the concentration of the dye. Experiments performed at a '' low '' degree of doping show that the fluorophore is almost completely included considerably before the end of the nanoparticles growth, allowing us to identify a self-organizing core-shell substructure. A strong enhancement of the fluorescence of the dye and a corresponding increase of its excited-state lifetime was observed upon its inclusion as a result of the shielding effect from molecular oxygen due to the silica matrix, a situation confirmed by the absence of the oxygen singlet emission in the near-infrared luminescence spectra. In the case of '' high '' loading, on the other hand, a heavily doped core showing an excimeric-like emission is first formed. Further growth leads to the formation of layers where the concentration of dye gradually decreases and the monomeric emission becomes relevant. The effect of the degree of doping on the kinetics of growth is also reported. At both concentration regimes, ultrafiltration experiments revealed the complete inclusion of the dye molecules. The average number of dye molecule per nanoparticles was also determined

Energy transfer processes in dye-doped nanostructures yield cooperative and versatile fluorescent probes

Fast and efficient energy transfer among dyes confined in nanocontainers provides the basis of outstanding functionalities in new-generation luminescent probes. This feature article provides an overview of recent research achievements on luminescent Pluronic-Silica NanoParticles (PluS NPs), a class of extremely monodisperse core-shell nanoparticles whose design can be easily tuned to match specific needs for diverse applications based on luminescence, and that have already been successfully tested in in vivo imaging. An outline of their outstanding properties, such as tuneability, bright and photoswitchable fluorescence and electrochemiluminescence, will be supported by a critical discussion of our recent works in this field. Furthermore, novel data and simulations will be presented to (i) thoroughly examine common issues arising from the inclusion of multiple dyes in a small silica core, and (ii) show the emergence of a cooperative behaviour among embedded dyes. Such cooperative behaviour provides a handle for fine control of brightness, emission colour and self-quenching phenomena in PluS NPs, leading to significantly enhanced signal to noise ratios

Should I Stay or Should I Go? Seasonal Fluctuations of Wood Mouse Populations in Fields Surrounded by Woodlands

The wood mouse Apodemus sylvaticus is common in woodlands and open areas of the Western Palearctic. Despite extensive research, little is known about its population ecology in fields in the Mediterranean area, where the climate involves great seasonal changes in environmental features. Here, we investigated wood mice seasonal fluctuations in the number of captures and population structure by sampling long-fallow fields and woodlands, i.e., oak forest and conifer plantation, in a heterogeneous landscape of central Italy. Mice were live-trapped every two months for three years (23.814 trap-days). The number of captures, mice body weight, and proportion of adult, residents and breeding individuals were analyzed. Mice dynamics changed across seasons and habitats. In fields, we recorded more captures, more reproductive individuals, and fewer non-adults and resident individuals in the warmer months compared to the colder months; mice were heavier in warmer months. During the cold season, the captures and adult proportion in fields were lower than in resource-rich woodlands. Breeding and non-resident mice were more abundant in fields than in woodlands in warmer months. Overall, the seasonal demographic variations we recorded provide evidence that fields can represent a suboptimal habitat in Mediterranean heterogeneous landscapes, acting nonetheless as a source of food resources, cover, and mates for mice in spring–summer