Characterization of optical transduction-based molecular systems and nanoparticles for the development of chemical sensors

With the increasing importance that nanotechnologies have in everyday life, it is not difficult to realize that also a single molecule, if properly designed, can be a device able to perform useful functions: such a chemical species is called chemosensor, that is a molecule of abiotic origin that signals the presence of matter or energy. Signal transduction is the mechanism by which an interaction of a sensor with an analyte yields a measurable form of energy. When dealing with the design of a chemosensor, we need to take into account a “communication requirement” between its three component: the receptor unit, responsible for the selective analyte binding, the spacer, which controls the geometry of the system and modulates the electronic interaction between the receptor and the signalling unit, whose physico-chemical properties change upon complexation. A luminescent chemosensor communicates a variation of the physico-chemical properties of the receptor unit with a luminescence output signal. This thesis work consists in the characterization of new molecular and nanoparticle-based system which can be used as sensitive materials for the construction of new optical transduction devices able to provide information about the concentration of analytes in solution. In particular two direction were taken. The first is to continue in the development of new chemosensors, that is the first step for the construction of reliable and efficient devices, and in particular the work will be focused on chemosensors for metal ions for biomedical and environmental applications. The second is to study more efficient and complex organized systems, such as derivatized silica nanoparticles. These system can potentially have higher sensitivity than molecular systems, and present many advantages, like the possibility to be ratiometric, higher Stokes shifts and lower signal-to-noise ratio.

Middleware per la gestione di interfacce di comunicazione e di sorgenti di contesto in ambienti wireless eterogenei

The full exploitation of multi-hop multi-path connectivity opportunities offered by heterogeneous wireless interfaces could enable innovative Always Best Served (ABS) deployment scenarios where mobile clients dynamically self-organize to offer/exploit Internet connectivity at best. Only novel middleware solutions based on heterogeneous context information can seamlessly enable this scenario: middleware solutions should i) provide a translucent access to low-level components, to achieve both fully aware and simplified pre-configured interactions, ii) permit to fully exploit communication interface capabilities, i.e., not only getting but also providing connectivity in a peer-to-peer fashion, thus relieving final users and application developers from the burden of directly managing wireless interface heterogeneity, and iii) consider user mobility as crucial context information evaluating at provision time the suitability of available Internet points of access differently when the mobile client is still or in motion. The novelty of this research work resides in three primary points. First of all, it proposes a novel model and taxonomy providing a common vocabulary to easily describe and position solutions in the area of context-aware autonomic management of preferred network opportunities. Secondly, it presents PoSIM, a context-aware middleware for the synergic exploitation and control of heterogeneous positioning systems that facilitates the development and portability of location-based services. PoSIM is translucent, i.e., it can provide application developers with differentiated visibility of data characteristics and control possibilities of available positioning solutions, thus dynamically adapting to application-specific deployment requirements and enabling cross-layer management decisions. Finally, it provides the MMHC solution for the self-organization of multi-hop multi-path heterogeneous connectivity. MMHC considers a limited set of practical indicators on node mobility and wireless network characteristics for a coarsegrained estimation of expected reliability/quality of multi-hop paths available at runtime. In particular, MMHC manages the durability/throughput-aware formation and selection of different multi-hop paths simultaneously. Furthermore, MMHC provides a novel solution based on adaptive buffers, proactively managed based on handover prediction, to support continuous services, especially by pre-fetching multimedia contents to avoid streaming interruptions.

Business Clusters in Eastern Europe: Policy Analysis and Cluster Performance

Clusters have increasingly become an essential part of policy discourses at all levels, EU, national, regional, dealing with regional development, competitiveness, innovation, entrepreneurship, SMEs. These impressive efforts in promoting the concept of clusters on the policy-making arena have been accompanied by much less academic and scientific research work investigating the actual economic performance of firms in clusters, the design and execution of cluster policies and going beyond singular case studies to a more methodologically integrated and comparative approach to the study of clusters and their real-world impact. The theoretical background is far from being consolidated and there is a variety of methodologies and approaches for studying and interpreting this phenomenon while at the same time little comparability among studies on actual cluster performances. The conceptual framework of clustering suggests that they affect performance but theory makes little prediction as to the ultimate distribution of the value being created by clusters. This thesis takes the case of Eastern European countries for two reasons. One is that clusters, as coopetitive environments, are a new phenomenon as the previous centrally-based system did not allow for such types of firm organizations. The other is that, as new EU member states, they have been subject to the increased popularization of the cluster policy approach by the European Commission, especially in the framework of the National Reform Programmes related to the Lisbon objectives. The originality of the work lays in the fact that starting from an overview of theoretical contributions on clustering, it offers a comparative empirical study of clusters in transition countries. There have been very few examples in the literature that attempt to examine cluster performance in a comparative cross-country perspective. It adds to this an analysis of cluster policies and their implementation or lack of such as a way to analyse the way the cluster concept has been introduced to transition economies. Our findings show that the implementation of cluster policies does vary across countries with some countries which have embraced it more than others. The specific modes of implementation, however, are very similar, based mostly on soft measures such as funding for cluster initiatives, usually directed towards the creation of cluster management structures or cluster facilitators. They are essentially founded on a common assumption that the added values of clusters is in the creation of linkages among firms, human capital, skills and knowledge at the local level, most often perceived as the regional level. Often times geographical proximity is not a necessary element in the application process and cluster application are very similar to network membership. Cluster mapping is rarely a factor in the selection of cluster initiatives for funding and the relative question about critical mass and expected outcomes is not considered. In fact, monitoring and evaluation are not elements of the cluster policy cycle which have received a lot of attention. Bulgaria and the Czech Republic are the countries which have implemented cluster policies most decisively, Hungary and Poland have made significant efforts, while Slovakia and Romania have only sporadically and not systematically used cluster initiatives. When examining whether, in fact, firms located within regional clusters perform better and are more efficient than similar firms outside clusters, we do find positive results across countries and across sectors. The only country with negative impact from being located in a cluster is the Czech Republic.

Dye doped, core / shell silica nanoparticles: synthesis, characterization, & biotechnological applications

The aim of this thesis was to design, synthesize and develop a nanoparticle based system to be used as a chemosensor or as a label in bioanalytical applications. A versatile fluorescent functionalizable nanoarchitecture has been effectively produced based on the hydrolysis and condensation of TEOS in direct micelles of Pluronic® F 127, obtaining highly monodisperse silica - core / PEG - shell nanoparticles with a diameter of about 20 nm. Surface functionalized nanoparticles have been obtained in a one-pot procedure by chemical modification of the hydroxyl terminal groups of the surfactant. To make them fluorescent, a whole library of triethoxysilane fluorophores (mainly BODIPY based), encompassing the whole visible spectrum has been synthesized: this derivatization allows a high degree of doping, but the close proximity of the molecules inside the silica matrix leads to the development of self - quenching processes at high doping levels, with the concomitant fall of the fluorescence signal intensity. In order to bypass this parasite phenomenon, multichromophoric systems have been prepared, where highly efficient FRET processes occur, showing that this energy pathway is faster than self - quenching, recovering the fluorescence signal. The FRET efficiency remains very high even four dye nanoparticles, increasing the pseudo Stokes shift of the system, attractive feature for multiplexing analysis. These optimized nanoparticles have been successfully exploited in molecular imaging applications such as in vitro, in vivo and ex vivo imaging, proving themselves superior to conventional molecular fluorophores as signaling units.

Life Cycle Assessment of Peach Nectar: a comparative analysis between conventional and bioenergy-from-waste integrated food chains

Modern food systems are characterized by a high energy intensity as well as by the production of large amounts of waste, residuals and food losses. This inefficiency presents major consequences, in terms of GHG emissions, waste disposal, and natural resource depletion. The research hypothesis is that residual biomass material could contribute to the energetic needs of food systems, if recovered as an integrated renewable energy source (RES), leading to a sensitive reduction of the impacts of food systems, primarily in terms of fossil fuel consumption and GHG emissions. In order to assess these effects, a comparative life cycle assessment (LCA) has been conducted to compare two different food systems: a fossil fuel-based system and an integrated system with the use of residual as RES for self-consumption. The food product under analysis has been the peach nectar, from cultivation to end-of-life. The aim of this LCA is twofold. On one hand, it allows an evaluation of the energy inefficiencies related to agro-food waste. On the other hand, it illustrates how the integration of bioenergy into food systems could effectively contribute to reduce this inefficiency. Data about inputs and waste generated has been collected mainly through literature review and databases. Energy balance, GHG emissions (Global Warming Potential) and waste generation have been analyzed in order to identify the relative requirements and contribution of the different segments. An evaluation of the energy “loss” through the different categories of waste allowed to provide details about the consequences associated with its management and/or disposal. Results should provide an insight of the impacts associated with inefficiencies within food systems. The comparison provides a measure of the potential reuse of wasted biomass and the amount of energy recoverable, that could represent a first step for the formulation of specific policies on the integration of bioenergies for self-consumption.