Electrochemical surface modification of Single walled carbon nanotubes and graphene-based electrodes for (bio)sensing applications

Sensors are devices that have shown widespread use, from the detection of gas molecules to the tracking of chemical signals in biological cells. Single walled carbon nanotube (SWCNT) and graphene based electrodes have demonstrated to be an excellent material for the development of electrochemical biosensors as they display remarkable electronic properties and the ability to act as individual nanoelectrodes, display an excellent low-dimensional charge carrier transport, and promote surface electrocatalysis. The present work aims at the preparation and investigation of electrochemically modified SWCNT and graphene-based electrodes for applications in the field of biosensors. We initially studied SWCNT films and focused on their topography and surface composition, electrical and optical properties. Parallel to SWCNTs, graphene films were investigated. Higher resistance values were obtained in comparison with nanotubes films. The electrochemical surface modification of both electrodes was investigated following two routes (i) the electrografting of aryl diazonium salts, and (ii) the electrophylic addition of 1, 3-benzodithiolylium tetrafluoroborate (BDYT). Both the qualitative and quantitative characteristics of the modified electrode surfaces were studied such as the degree of functionalization and their surface composition. The combination of Raman, X-ray photoelectron spectroscopy, atomic force microscopy, electrochemistry and other techniques, has demonstrated that selected precursors could be covalently anchored to the nanotubes and graphene-based electrode surfaces through novel carbon-carbon formation.

Elastic Propagation in random media: applications to the imaging of volcano structures

High-frequency seismograms contain features that reflect the random inhomogeneities of the earth. In this work I use an imaging method to locate the high contrast small- scale heterogeneity respect to the background earth medium. This method was first introduced by Nishigami (1991) and than applied to different volcanic and tectonically active areas (Nishigami, 1997, Nishigami, 2000, Nishigami, 2006). The scattering imaging method is applied to two volcanic areas: Campi Flegrei and Mt. Vesuvius. Volcanic and seismological active areas are often characterized by complex velocity structures, due to the presence of rocks with different elastic properties. I introduce some modifications to the original method in order to make it suitable for small and highly complex media. In particular, for very complex media the single scattering approximation assumed by Nishigami (1991) is not applicable as the mean free path becomes short. The multiple scattering or diffusive approximation become closer to the reality. In this thesis, differently from the ordinary Nishigami’s method (Nishigami, 1991), I use the mean of the recorded coda envelope as reference curve and calculate the variations from this average envelope. In this way I implicitly do not assume any particular scattering regime for the "average" scattered radiation, whereas I consider the variations as due to waves that are singularly scattered from the strongest heterogeneities. The imaging method is applied to a relatively small area (20 x 20 km), this choice being justified by the small length of the analyzed codas of the low magnitude earthquakes. I apply the unmodified Nishigami’s method to the volcanic area of Campi Flegrei and compare the results with the other tomographies done in the same area. The scattering images, obtained with frequency waves around 18 Hz, show the presence of high scatterers in correspondence with the submerged caldera rim in the southern part of the Pozzuoli bay. Strong scattering is also found below the Solfatara crater, characterized by the presence of densely fractured, fluid-filled rocks and by a strong thermal anomaly. The modified Nishigami’s technique is applied to the Mt. Vesuvius area. Results show a low scattering area just below the central cone and a high scattering area around it. The high scattering zone seems to be due to the contrast between the high rigidity body located beneath the crater and the low rigidity materials located around it. The central low scattering area overlaps the hydrothermal reservoirs located below the central cone. An interpretation of the results in terms of geological properties of the medium is also supplied, aiming to find a correspondence of the scattering properties and the geological nature of the material. A complementary result reported in this thesis is that the strong heterogeneity of the volcanic medium create a phenomenon called "coda localization". It has been verified that the shape of the seismograms recorded from the stations located at the top of the volcanic edifice of Mt. Vesuvius is different from the shape of the seismograms recorded at the bottom. This behavior is justified by the consideration that the coda energy is not uniformly distributed within a region surrounding the source for great lapse time.

Synthesis, multiscale-multiphase characterization and applications of thiophene-based biohybrids

Biohybrid derivatives of π-conjugated materials are emerging as powerful tools to study biological events through the (opto)electronic variations of the π-conjugated moieties, as well as to direct and govern the self-assembly properties of the organic materials through the organization principles of the bio component. So far, very few examples of thiophene-based biohybrids have been reported. The aim of this Ph. D thesis has been the development of oligothiophene-oligonucleotide hybrid derivatives as tools, on one side, to detect DNA hybridisation events and, on the other, as model compounds to investigate thiophene-nucleobase interactions in the solid state. To obtain oligothiophene bioconjugates with the required high level of purity, we first developed new synthetic ecofriendly protocols for the synthesis of thiophene oligomers. Our innovative heterogeneous Suzuki coupling methodology, carried out in EtOH/water or isopropanol under microwave irradiation, allowed us to obtain alkyl substituted oligothiophenes and thiophene based co-oligomers in high yields and very short reaction times, free from residual metals and with improved film forming properties. These methodologies were subsequently applied in the synthesis of oligothiophene-oligonucleotide conjugates. Oligothiophene-5-labeled deoxyuridines were synthesized and incorporated into 19-meric oligonucletide sequences. We showed that the oligothiophene-labeled oligonucletide sequences obtained can be used as probes to detect a single nucleotide polymorphism (SNP) in complementary DNA target sequences. In fact, all the probes showed marked variations in emission intensity upon hybridization with a complementary target sequence. The observed variations in emitted light were comparable or even superior to those reported in similar studies, showing that the biohybrids can potentially be useful to develop biosensors for the detection of DNA mismatches. Finally, water-soluble, photoluminescent and electroactive dinucleotide-hybrid derivatives of quaterthiophene and quinquethiophene were synthesized. By means of a combination of spectroscopy and microscopy techniques, electrical characterizations, microfluidic measurements and theoretical calculations, we were able to demonstrate that the self-assembly modalities of the biohybrids in thin films are driven by the interplay of intra and intermolecular interactions in which the π-stacking between the oligothiophene and nucleotide bases plays a major role.

Two fluid numerical model for coastal applications

Wave breaking is an important coastal process, influencing hydro-morphodynamic processes such as turbulence generation and wave energy dissipation, run-up on the beach and overtopping of coastal defence structures. During breaking, waves are complex mixtures of air and water (“white water”) whose properties affect velocity and pressure fields in the vicinity of the free surface and, depending on the breaker characteristics, different mechanisms for air entrainment are usually observed. Several laboratory experiments have been performed to investigate the role of air bubbles in the wave breaking process (Chanson & Cummings, 1994, among others) and in wave loading on vertical wall (Oumeraci et al., 2001; Peregrine et al., 2006, among others), showing that the air phase is not negligible since the turbulent energy dissipation involves air-water mixture. The recent advancement of numerical models has given valuable insights in the knowledge of wave transformation and interaction with coastal structures. Among these models, some solve the RANS equations coupled with a free-surface tracking algorithm and describe velocity, pressure, turbulence and vorticity fields (Lara et al. 2006 a-b, Clementi et al., 2007). The single-phase numerical model, in which the constitutive equations are solved only for the liquid phase, neglects effects induced by air movement and trapped air bubbles in water. Numerical approximations at the free surface may induce errors in predicting breaking point and wave height and moreover, entrapped air bubbles and water splash in air are not properly represented. The aim of the present thesis is to develop a new two-phase model called COBRAS2 (stands for Cornell Breaking waves And Structures 2 phases), that is the enhancement of the single-phase code COBRAS0, originally developed at Cornell University (Lin & Liu, 1998). In the first part of the work, both fluids are considered as incompressible, while the second part will treat air compressibility modelling. The mathematical formulation and the numerical resolution of the governing equations of COBRAS2 are derived and some model-experiment comparisons are shown. In particular, validation tests are performed in order to prove model stability and accuracy. The simulation of the rising of a large air bubble in an otherwise quiescent water pool reveals the model capability to reproduce the process physics in a realistic way. Analytical solutions for stationary and internal waves are compared with corresponding numerical results, in order to test processes involving wide range of density difference. Waves induced by dam-break in different scenarios (on dry and wet beds, as well as on a ramp) are studied, focusing on the role of air as the medium in which the water wave propagates and on the numerical representation of bubble dynamics. Simulations of solitary and regular waves, characterized by both spilling and plunging breakers, are analyzed with comparisons with experimental data and other numerical model in order to investigate air influence on wave breaking mechanisms and underline model capability and accuracy. Finally, modelling of air compressibility is included in the new developed model and is validated, revealing an accurate reproduction of processes. Some preliminary tests on wave impact on vertical walls are performed: since air flow modelling allows to have a more realistic reproduction of breaking wave propagation, the dependence of wave breaker shapes and aeration characteristics on impact pressure values is studied and, on the basis of a qualitative comparison with experimental observations, the numerical simulations achieve good results.

Design of optical networks for advanced applications

Nowadays, computing is migrating from traditional high performance and distributed computing to pervasive and utility computing based on heterogeneous networks and clients. The current trend suggests that future IT services will rely on distributed resources and on fast communication of heterogeneous contents. The success of this new range of services is directly linked to the effectiveness of the infrastructure in delivering them. The communication infrastructure will be the aggregation of different technologies even though the current trend suggests the emergence of single IP based transport service. Optical networking is a key technology to answer the increasing requests for dynamic bandwidth allocation and configure multiple topologies over the same physical layer infrastructure, optical networks today are still “far” from accessible from directly configure and offer network services and need to be enriched with more “user oriented” functionalities. However, current Control Plane architectures only facilitate efficient end-to-end connectivity provisioning and certainly cannot meet future network service requirements, e.g. the coordinated control of resources. The overall objective of this work is to provide the network with the improved usability and accessibility of the services provided by the Optical Network. More precisely, the definition of a service-oriented architecture is the enable technology to allow user applications to gain benefit of advanced services over an underlying dynamic optical layer. The definition of a service oriented networking architecture based on advanced optical network technologies facilitates users and applications access to abstracted levels of information regarding offered advanced network services. This thesis faces the problem to define a Service Oriented Architecture and its relevant building blocks, protocols and languages. In particular, this work has been focused on the use of the SIP protocol as a inter-layers signalling protocol which defines the Session Plane in conjunction with the Network Resource Description language. On the other hand, an advantage optical network must accommodate high data bandwidth with different granularities. Currently, two main technologies are emerging promoting the development of the future optical transport network, Optical Burst and Packet Switching. Both technologies respectively promise to provide all optical burst or packet switching instead of the current circuit switching. However, the electronic domain is still present in the scheduler forwarding and routing decision. Because of the high optics transmission frequency the burst or packet scheduler faces a difficult challenge, consequentially, high performance and time focused design of both memory and forwarding logic is need. This open issue has been faced in this thesis proposing an high efficiently implementation of burst and packet scheduler. The main novelty of the proposed implementation is that the scheduling problem has turned into simple calculation of a min/max function and the function complexity is almost independent of on the traffic conditions.

NMR, Metabonomics and Molecular Profiles: Applications to the Quality Assessment of Foodstuffs

Nuclear Magnetic Resonance (NMR) is a branch of spectroscopy that is based on the fact that many atomic nuclei may be oriented by a strong magnetic field and will absorb radiofrequency radiation at characteristic frequencies. The parameters that can be measured on the resulting spectral lines (line positions, intensities, line widths, multiplicities and transients in time-dependent experi-ments) can be interpreted in terms of molecular structure, conformation, molecular motion and other rate processes. In this way, high resolution (HR) NMR allows performing qualitative and quantitative analysis of samples in solution, in order to determine the structure of molecules in solution and not only. In the past, high-field NMR spectroscopy has mainly concerned with the elucidation of chemical structure in solution, but today is emerging as a powerful exploratory tool for probing biochemical and physical processes. It represents a versatile tool for the analysis of foods. In literature many NMR studies have been reported on different type of food such as wine, olive oil, coffee, fruit juices, milk, meat, egg, starch granules, flour, etc using different NMR techniques. Traditionally, univariate analytical methods have been used to ex-plore spectroscopic data. This method is useful to measure or to se-lect a single descriptive variable from the whole spectrum and , at the end, only this variable is analyzed. This univariate methods ap-proach, applied to HR-NMR data, lead to different problems due especially to the complexity of an NMR spectrum. In fact, the lat-ter is composed of different signals belonging to different mole-cules, but it is also true that the same molecules can be represented by different signals, generally strongly correlated. The univariate methods, in this case, takes in account only one or a few variables, causing a loss of information. Thus, when dealing with complex samples like foodstuff, univariate analysis of spectra data results not enough powerful. Spectra need to be considered in their wholeness and, for analysing them, it must be taken in consideration the whole data matrix: chemometric methods are designed to treat such multivariate data. Multivariate data analysis is used for a number of distinct, differ-ent purposes and the aims can be divided into three main groups: • data description (explorative data structure modelling of any ge-neric n-dimensional data matrix, PCA for example); • regression and prediction (PLS); • classification and prediction of class belongings for new samples (LDA and PLS-DA and ECVA). The aim of this PhD thesis was to verify the possibility of identify-ing and classifying plants or foodstuffs, in different classes, based on the concerted variation in metabolite levels, detected by NMR spectra and using the multivariate data analysis as a tool to inter-pret NMR information. It is important to underline that the results obtained are useful to point out the metabolic consequences of a specific modification on foodstuffs, avoiding the use of a targeted analysis for the different metabolites. The data analysis is performed by applying chemomet-ric multivariate techniques to the NMR dataset of spectra acquired. The research work presented in this thesis is the result of a three years PhD study. This thesis reports the main results obtained from these two main activities: A1) Evaluation of a data pre-processing system in order to mini-mize unwanted sources of variations, due to different instrumental set up, manual spectra processing and to sample preparations arte-facts; A2) Application of multivariate chemiometric models in data analy-sis.

Development and characterization of non-oxide ceramic composites for mechanical and tribological applications

The main reasons for the attention focused on ceramics as possible structural materials are their wear resistance and the ability to operate with limited oxidation and ablation at temperatures above 2000°C. Hence, this work is devoted to the study of two classes of materials which can satisfy these requirements: silicon carbide -based ceramics (SiC) for wear applications and borides and carbides of transition metals for ultra-high temperatures applications (UHTCs). SiC-based materials: Silicon carbide is a hard ceramic, which finds applications in many industrial sectors, from heat production, to automotive engineering and metals processing. In view of new fields of uses, SiC-based ceramics were produced with addition of 10-30 vol% of MoSi2, in order to obtain electro conductive ceramics. MoSi2, indeed, is an intermetallic compound which possesses high temperature oxidation resistance, high electrical conductivity (21·10-6 Ω·cm), relatively low density (6.31 g/cm3), high melting point (2030°C) and high stiffness (440 GPa). The SiC-based ceramics were hot pressed at 1900°C with addition of Al2O3-Y2O3 or Y2O3-AlN as sintering additives. The microstructure of the composites and of the reference materials, SiC and MoSi2, were studied by means of conventional analytical techniques, such as X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (SEM-EDS). The composites showed a homogeneous microstructure, with good dispersion of the secondary phases and low residual porosity. The following thermo-mechanical properties of the SiC-based materials were measured: Vickers hardness (HV), Young’s modulus (E), fracture toughness (KIc) and room to high temperature flexural strength (σ). The mechanical properties of the composites were compared to those of two monolithic SiC and MoSi2 materials and resulted in a higher stiffness, fracture toughness and slightly higher flexural resistance. Tribological tests were also performed in two configurations disco-on-pin and slideron cylinder, aiming at studying the wear behaviour of SiC-MoSi2 composites with Al2O3 as counterfacing materials. The tests pointed out that the addition of MoSi2 was detrimental owing to a lower hardness in comparison with the pure SiC matrix. On the contrary, electrical measurements revealed that the addition of 30 vol% of MoSi2, rendered the composite electroconductive, lowering the electrical resistance of three orders of magnitude. Ultra High Temperature Ceramics: Carbides, borides and nitrides of transition metals (Ti, Zr, Hf, Ta, Nb, Mo) possess very high melting points and interesting engineering properties, such as high hardness (20-25 GPa), high stiffness (400-500 GPa), flexural strengths which remain unaltered from room temperature to 1500°C and excellent corrosion resistance in aggressive environment. All these properties place the UHTCs as potential candidates for the development of manoeuvrable hypersonic flight vehicles with sharp leading edges. To this scope Zr- and Hf- carbide and boride materials were produced with addition of 5-20 vol% of MoSi2. This secondary phase enabled the achievement of full dense composites at temperature lower than 2000°C and without the application of pressure. Besides the conventional microstructure analyses XRD and SEM-EDS, transmission electron microscopy (TEM) was employed to explore the microstructure on a small length scale to disclose the effective densification mechanisms. A thorough literature analysis revealed that neither detailed TEM work nor reports on densification mechanisms are available for this class of materials, which however are essential to optimize the sintering aids utilized and the processing parameters applied. Microstructural analyses, along with thermodynamics and crystallographic considerations, led to disclose of the effective role of MoSi2 during sintering of Zrand Hf- carbides and borides. Among the investigated mechanical properties (HV, E, KIc, σ from room temperature to 1500°C), the high temperature flexural strength was improved due to the protective and sealing effect of a silica-based glassy phase, especially for the borides. Nanoindentation tests were also performed on HfC-MoSi2 composites in order to extract hardness and elastic modulus of the single phases. Finally, arc jet tests on HfC- and HfB2-based composites confirmed the excellent oxidation behaviour of these materials under temperature exceeding 2000°C; no cracking or spallation occurred and the modified layer was only 80-90 μm thick.

A hybrid technology for parallel recording of single ion channels

Hybrid technologies, thanks to the convergence of integrated microelectronic devices and new class of microfluidic structures could open new perspectives to the way how nanoscale events are discovered, monitored and controlled. The key point of this thesis is to evaluate the impact of such an approach into applications of ion-channel High Throughput Screening (HTS)platforms. This approach offers promising opportunities for the development of new classes of sensitive, reliable and cheap sensors. There are numerous advantages of embedding microelectronic readout structures strictly coupled to sensing elements. On the one hand the signal-to-noise-ratio is increased as a result of scaling. On the other, the readout miniaturization allows organization of sensors into arrays, increasing the capability of the platform in terms of number of acquired data, as required in the HTS approach, to improve sensing accuracy and reliabiity. However, accurate interface design is required to establish efficient communication between ionic-based and electronic-based signals. The work made in this thesis will show a first example of a complete parallel readout system with single ion channel resolution, using a compact and scalable hybrid architecture suitable to be interfaced to large array of sensors, ensuring simultaneous signal recording and smart control of the signal-to-noise ratio and bandwidth trade off. More specifically, an array of microfluidic polymer structures, hosting artificial lipid bilayers blocks where single ion channel pores are embededed, is coupled with an array of ultra-low noise current amplifiers for signal amplification and data processing. As demonstrating working example, the platform was used to acquire ultra small currents derived by single non-covalent molecular binding between alpha-hemolysin pores and beta-cyclodextrin molecules in artificial lipid membranes.

Novel tools for conservation genetics in marine fish: population structure and evolution of the European hake (Merluccius merluccius) inferred by SNP variation and applications to traceability

The research presented in my PhD thesis is part of a wider European project, FishPopTrace, focused on traceability of fish populations and products. My work was aimed at developing and analyzing novel genetic tools for a widely distributed marine fish species, the European hake (Merluccius merluccius), in order to investigate population genetic structure and explore potential applications to traceability scenarios. A total of 395 SNPs (Single Nucleotide Polymorphisms) were discovered from a massive collection of Expressed Sequence Tags, obtained by high-throughput sequencing, and validated on 19 geographic samples from Atlantic and Mediterranean. Genome-scan approaches were applied to identify polymorphisms on genes potentially under divergent selection (outlier SNPs), showing higher genetic differentiation among populations respect to the average observed across loci. Comparative analysis on population structure were carried out on putative neutral and outlier loci at wide (Atlantic and Mediterranean samples) and regional (samples within each basin) spatial scales, to disentangle the effects of demographic and adaptive evolutionary forces on European hake populations genetic structure. Results demonstrated the potential of outlier loci to unveil fine scale genetic structure, possibly identifying locally adapted populations, despite the weak signal showed from putative neutral SNPs. The application of outlier SNPs within the framework of fishery resources management was also explored. A minimum panel of SNP markers showing maximum discriminatory power was selected and applied to a traceability scenario aiming at identifying the basin (and hence the stock) of origin, Atlantic or Mediterranean, of individual fish. This case study illustrates how molecular analytical technologies have operational potential in real-world contexts, and more specifically, potential to support fisheries control and enforcement and fish and fish product traceability.

Continuos Flow Single Cell Separation into Open Microwell Arrays

A novel design based on electric field-free open microwell arrays for the automated continuous-flow sorting of single or small clusters of cells is presented. The main feature of the proposed device is the parallel analysis of cell-cell and cell-particle interactions in each microwell of the array. High throughput sample recovery with a fast and separate transfer from the microsites to standard microtiter plates is also possible thanks to the flexible printed circuit board technology which permits to produce cost effective large area arrays featuring geometries compatible with laboratory equipment. The particle isolation is performed via negative dielectrophoretic forces which convey the particles’ into the microwells. Particles such as cells and beads flow in electrically active microchannels on whose substrate the electrodes are patterned. The introduction of particles within the microwells is automatically performed by generating the required feedback signal by a microscope-based optical counting and detection routine. In order to isolate a controlled number of particles we created two particular configurations of the electric field within the structure. The first one permits their isolation whereas the second one creates a net force which repels the particles from the microwell entrance. To increase the parallelism at which the cell-isolation function is implemented, a new technique based on coplanar electrodes to detect particle presence was implemented. A lock-in amplifying scheme was used to monitor the impedance of the channel perturbed by flowing particles in high-conductivity suspension mediums. The impedance measurement module was also combined with the dielectrophoretic focusing stage situated upstream of the measurement stage, to limit the measured signal amplitude dispersion due to the particles position variation within the microchannel. In conclusion, the designed system complies with the initial specifications making it suitable for cellomics and biotechnology applications.

Development of methodologies for fish freshness assessment using metabonomics applications.

This study focuses on the use of metabonomics applications in measuring fish freshness in various biological species and in evaluating how they are stored. This metabonomic approach is innovative and is based upon molecular profiling through nuclear magnetic resonance (NMR). On one hand, the aim is to ascertain if a type of fish has maintained, within certain limits, its sensory and nutritional characteristics after being caught; and on the second, the research observes the alterations in the product’s composition. The spectroscopic data obtained through experimental nuclear magnetic resonance, 1H-NMR, of the molecular profiles of the fish extracts are compared with those obtained on the same samples through analytical and conventional methods now in practice. These second methods are used to obtain chemical indices of freshness through biochemical and microbial degradation of the proteic nitrogen compounds and not (trimethylamine, N-(CH3)3, nucleotides, amino acids, etc.). At a later time, a principal components analysis (PCA) and a linear discriminant analysis (PLS-DA) are performed through a metabonomic approach to condense the temporal evolution of freshness into a single parameter. In particular, the first principal component (PC1) under both storage conditions (4 °C and 0 °C) represents the component together with the molecular composition of the samples (through 1H-NMR spectrum) evolving during storage with a very high variance. The results of this study give scientific evidence supporting the objective elements evaluating the freshness of fish products showing those which can be labeled “fresh fish.”

Spectrum Sensing Algorithms for Cognitive Radio Applications

Future wireless communications systems are expected to be extremely dynamic, smart and capable to interact with the surrounding radio environment. To implement such advanced devices, cognitive radio (CR) is a promising paradigm, focusing on strategies for acquiring information and learning. The first task of a cognitive systems is spectrum sensing, that has been mainly studied in the context of opportunistic spectrum access, in which cognitive nodes must implement signal detection techniques to identify unused bands for transmission. In the present work, we study different spectrum sensing algorithms, focusing on their statistical description and evaluation of the detection performance. Moving from traditional sensing approaches we consider the presence of practical impairments, and analyze algorithm design. Far from the ambition of cover the broad spectrum of spectrum sensing, we aim at providing contributions to the main classes of sensing techniques. In particular, in the context of energy detection we studied the practical design of the test, considering the case in which the noise power is estimated at the receiver. This analysis allows to deepen the phenomenon of the SNR wall, providing the conditions for its existence and showing that presence of the SNR wall is determined by the accuracy of the noise power estimation process. In the context of the eigenvalue based detectors, that can be adopted by multiple sensors systems, we studied the practical situation in presence of unbalances in the noise power at the receivers. Then, we shift the focus from single band detectors to wideband sensing, proposing a new approach based on information theoretic criteria. This technique is blind and, requiring no threshold setting, can be adopted even if the statistical distribution of the observed data in not known exactly. In the last part of the thesis we analyze some simple cooperative localization techniques based on weighted centroid strategies.

Transport Properties and Novel Sensing Applications of Organic Semiconducting Crystals

The present thesis is focused on the study of Organic Semiconducting Single Crystals (OSSCs) and crystalline thin films. In particular solution-grown OSSC, e.g. 4-hdroxycyanobenzene (4HCB) have been characterized in view of their applications as novel sensors of X-rays, gamma-rays, alpha particles radiations and chemical sensors. In the field of ionizing radiation detection, organic semiconductors have been proposed so far mainly as indirect detectors, i.e. as scintillators or as photodiodes. I first study the performance of 4HCB single crystals as direct X-ray detector i.e. the direct photon conversion into an electrical signal, assessing that they can operate at room temperature and in atmosphere, showing a stable and linear response with increasing dose rate. A dedicated study of the collecting electrodes geometry, crystal thickness and interaction volume allowed us to maximize the charge collection efficiency and sensitivity, thus assessing how OSSCs perform at low operating voltages and offer a great potential in the development of novel ionizing radiation sensors. To better understand the processes generating the observed X-ray signal, a comparative study is presented on OSSCs based on several small-molecules: 1,5-dinitronaphthalene (DNN), 1,8-naphthaleneimide (NTI), Rubrene and TIPS-pentacene. In addition, the proof of principle of gamma-rays and alpha particles has been assessed for 4HCB single crystals. I have also carried out an investigation of the electrical response of OSSCs exposed to vapour of volatile molecules, polar and non-polar. The last chapter deals with rubrene, the highest performing molecular crystals for electronic applications. We present an investigation on high quality, millimeter-sized, crystalline thin films (10 – 100 nm thick) realized by exploiting organic molecular beam epitaxy on water-soluble substrates. Space-Charge-Limited Current (SCLC) and photocurrent spectroscopy measurements have been carried out. A thin film transistor was fabricated onto a Cytop® dielectric layer. The FET mobility exceeding 2 cm2/Vs, definitely assess the quality of RUB films.

Power Converters and Electric Drives for Smart Grid Applications

The present dissertation aims to explore, theoretically and experimentally, the problems and the potential advantages of different types of power converters for “Smart Grid” applications, with particular emphasis on multi-level architectures, which are attracting a rising interest even for industrial requests. The models of the main multilevel architectures (Diode-Clamped and Cascaded) are shown. The best suited modulation strategies to function as a network interface are identified. In particular, the close correlation between PWM (Pulse Width Modulation) approach and SVM (Space Vector Modulation) approach is highlighted. An innovative multilevel topology called MMC (Modular Multilevel Converter) is investigated, and the single-phase, three-phase and "back to back" configurations are analyzed. Specific control techniques that can manage, in an appropriate way, the charge level of the numerous capacitors and handle the power flow in a flexible way are defined and experimentally validated. Another converter that is attracting interest in “Power Conditioning Systems” field is the “Matrix Converter”. Even in this architecture, the output voltage is multilevel. It offers an high quality input current, a bidirectional power flow and has the possibility to control the input power factor (i.e. possibility to participate to active and reactive power regulations). The implemented control system, that allows fast data acquisition for diagnostic purposes, is described and experimentally verified.

Photoactive nanodevices for potential biological applications

Biological systems are complex and highly organized architectures governed by noncovalent interactions, which are responsible for molecular recognition, self-assembly, self-organization, adaptation and evolution processes. These systems provided the inspiration for the development of supramolecular chemistry, that aimed at the design of artificial multicomponent molecular assemblies, namely supramolecular systems, properly designed to perform different operations: each constituting unit performs a single act, whereas the entire supramolecular system is able to execute a more complex function, resulting from the cooperation of the constituting components. Supramolecular chemistry deals with the development of molecular systems able to mimic naturally occurring events, for example complexation and self-assembly through the establishment of noncovalent interactions. Moreover, the application of external stimuli, such as light, allows to perform these operations in a time- and space-controlled manner. These systems can interact with biological systems and, thus, can be applied for bioimaging, therapeutic and drug delivery purposes. In this work the study of biocompatible supramolecular species able to interact with light is presented. The first part deals with the photophysical, photochemical and electrochemical characterization of water-soluble blue emitting triazoloquinolinium and triazolopyridinium salts. Moreover, their interaction with DNA has been explored, in the perspective of developing water-soluble systems for bioimaging applications. In the second part, the effect exerted by the presence of azobenzene-bearing supramolecular species in liposomes, inserted both in the phospholipid bilayer and in the in the aqueous core of vesicles has been studied, in order to develop systems able to deliver small molecules and ions in a photocontrolled manner. Moreover, the versatility of azobenzene and its broad range of applications have been highlighted, since conjugated oligoazobenzene derivatives proved not to be adequate to be inserted in the phospholipid bilayer of liposomes, but their electrochemical properties made them interesting candidates as electron acceptor materials for photovoltaic applications.