Simulation of Smart Materials

The aim of this thesis is the elucidation of structure-properties relationship of molecular semiconductors for electronic devices. This involves the use of a comprehensive set of simulation techniques, ranging from quantum-mechanical to numerical stochastic methods, and also the development of ad-hoc computational tools. In more detail, the research activity regarded two main topics: the study of electronic properties and structural behaviour of liquid crystalline (LC) materials based on functionalised oligo(p-phenyleneethynylene) (OPE), and the investigation on the electric field effect associated to OFET operation on pentacene thin film stability. In this dissertation, a novel family of substituted OPE liquid crystals with applications in stimuli-responsive materials is presented. In more detail, simulations can not only provide evidence for the characterization of the liquid crystalline phases of different OPEs, but elucidate the role of charge transfer states in donor-acceptor LCs containing an endohedral metallofullerene moiety. Such systems can be regarded as promising candidates for organic photovoltaics. Furthermore, exciton dynamics simulations are performed as a way to obtain additional information about the degree of order in OPE columnar phases. Finally, ab initio and molecular mechanics simulations are used to investigate the influence of an applied electric field on pentacene reactivity and stability. The reaction path of pentacene thermal dimerization in the presence of an external electric field is investigated; the results can be related to the fatigue effect observed in OFETs, that show significant performance degradation even in the absence of external agents. In addition to this, the effect of the gate voltage on a pentacene monolayer are simulated, and the results are then compared to X-ray diffraction measurements performed for the first time on operating OFETs.

Distributed Smart City Services for Urban Ecosystems

A Smart City is a high-performance urban context, where citizens live independently and are more aware of the surrounding opportunities, thanks to forward-looking development of economy politics, governance, mobility and environment. ICT infrastructures play a key-role in this new research field being also a mean for society to allow new ideas to prosper and new, more efficient approaches to be developed. The aim of this work is to research and develop novel solutions, here called smart services, in order to solve several upcoming problems and known issues in urban areas and more in general in the modern society context. A specific focus is posed on smart governance and on privacy issues which have been arisen in the cellular age.

Ultra-Low Power and Non-intrusive Wireless Monitoring for Smart Buildings

Wireless Sensor Networks (WSNs) offer a new solution for distributed monitoring, processing and communication. First of all, the stringent energy constraints to which sensing nodes are typically subjected. WSNs are often battery powered and placed where it is not possible to recharge or replace batteries. Energy can be harvested from the external environment but it is a limited resource that must be used efficiently. Energy efficiency is a key requirement for a credible WSNs design. From the power source's perspective, aggressive energy management techniques remain the most effective way to prolong the lifetime of a WSN. A new adaptive algorithm will be presented, which minimizes the consumption of wireless sensor nodes in sleep mode, when the power source has to be regulated using DC-DC converters. Another important aspect addressed is the time synchronisation in WSNs. WSNs are used for real-world applications where physical time plays an important role. An innovative low-overhead synchronisation approach will be presented, based on a Temperature Compensation Algorithm (TCA). The last aspect addressed is related to self-powered WSNs with Energy Harvesting (EH) solutions. Wireless sensor nodes with EH require some form of energy storage, which enables systems to continue operating during periods of insufficient environmental energy. However, the size of the energy storage strongly restricts the use of WSNs with EH in real-world applications. A new approach will be presented, which enables computation to be sustained during intermittent power supply. The discussed approaches will be used for real-world WSN applications. The first presented scenario is related to the experience gathered during an European Project (3ENCULT Project), regarding the design and implementation of an innovative network for monitoring heritage buildings. The second scenario is related to the experience with Telecom Italia, regarding the design of smart energy meters for monitoring the usage of household's appliances.

Scene Reconstruction And Understanding By RGB-D Sensors

This thesis investigates interactive scene reconstruction and understanding using RGB-D data only. Indeed, we believe that depth cameras will still be in the near future a cheap and low-power 3D sensing alternative suitable for mobile devices too. Therefore, our contributions build on top of state-of-the-art approaches to achieve advances in three main challenging scenarios, namely mobile mapping, large scale surface reconstruction and semantic modeling. First, we will describe an effective approach dealing with Simultaneous Localization And Mapping (SLAM) on platforms with limited resources, such as a tablet device. Unlike previous methods, dense reconstruction is achieved by reprojection of RGB-D frames, while local consistency is maintained by deploying relative bundle adjustment principles. We will show quantitative results comparing our technique to the state-of-the-art as well as detailed reconstruction of various environments ranging from rooms to small apartments. Then, we will address large scale surface modeling from depth maps exploiting parallel GPU computing. We will develop a real-time camera tracking method based on the popular KinectFusion system and an online surface alignment technique capable of counteracting drift errors and closing small loops. We will show very high quality meshes outperforming existing methods on publicly available datasets as well as on data recorded with our RGB-D camera even in complete darkness. Finally, we will move to our Semantic Bundle Adjustment framework to effectively combine object detection and SLAM in a unified system. Though the mathematical framework we will describe does not restrict to a particular sensing technology, in the experimental section we will refer, again, only to RGB-D sensing. We will discuss successful implementations of our algorithm showing the benefit of a joint object detection, camera tracking and environment mapping.

Modelling and analysis of networked control strategies in smart power distribution grids: development of co-simulation tools

This thesis is focused on Smart Grid applications in medium voltage distribution networks. For the development of new applications it appears useful the availability of simulation tools able to model dynamic behavior of both the power system and the communication network. Such a co-simulation environment would allow the assessment of the feasibility of using a given network technology to support communication-based Smart Grid control schemes on an existing segment of the electrical grid and to determine the range of control schemes that different communications technologies can support. For this reason, is presented a co-simulation platform that has been built by linking the Electromagnetic Transients Program Simulator (EMTP v3.0) with a Telecommunication Network Simulator (OPNET-Riverbed v18.0). The simulator is used to design and analyze a coordinate use of Distributed Energy Resources (DERs) for the voltage/var control (VVC) in distribution network. This thesis is focused control structure based on the use of phase measurement units (PMUs). In order to limit the required reinforcements of the communication infrastructures currently adopted by Distribution Network Operators (DNOs), the study is focused on leader-less MAS schemes that do not assign special coordinating rules to specific agents. Leader-less MAS are expected to produce more uniform communication traffic than centralized approaches that include a moderator agent. Moreover, leader-less MAS are expected to be less affected by limitations and constraint of some communication links. The developed co-simulator has allowed the definition of specific countermeasures against the limitations of the communication network, with particular reference to the latency and loss and information, for both the case of wired and wireless communication networks. Moreover, the co-simulation platform has bee also coupled with a mobility simulator in order to study specific countermeasures against the negative effects on the medium voltage/current distribution network caused by the concurrent connection of electric vehicles.

Sviluppo di una infrastruttura location-based per l'auto-organizzazione di smart-devices.

La tesi consiste nel realizzare una infrastruttura che mantenga il modello tipico dello Spatial Computing e coniughi al meglio le tecnologie location-based come GPS, NFC e BLE, per permettere ai moderni smart-devices Android di cooperare e auto-organizzarsi al fine di compiere un certo task definito a livello applicativo.

Assessment of gait spatio-temporal parameters in neurological disorders using wearable inertial sensors

Movement analysis carried out in laboratory settings is a powerful, but costly solution since it requires dedicated instrumentation, space and personnel. Recently, new technologies such as the magnetic and inertial measurement units (MIMU) are becoming widely accepted as tools for the assessment of human motion in clinical and research settings. They are relatively easy-to-use and potentially suitable for estimating gait kinematic features, including spatio-temporal parameters. The objective of this thesis regards the development and testing in clinical contexts of robust MIMUs based methods for assessing gait spatio-temporal parameters applicable across a number of different pathological gait patterns. First, considering the need of a solution the least obtrusive as possible, the validity of the single unit based approach was explored. A comparative evaluation of the performance of various methods reported in the literature for estimating gait temporal parameters using a single unit attached to the trunk first in normal gait and then in different pathological gait conditions was performed. Then, the second part of the research headed towards the development of new methods for estimating gait spatio-temporal parameters using shank worn MIMUs on different pathological subjects groups. In addition to the conventional gait parameters, new methods for estimating the changes of the direction of progression were explored. Finally, a new hardware solution and relevant methodology for estimating inter-feet distance during walking was proposed. Results of the technical validation of the proposed methods at different walking speeds and along different paths against a gold standard were reported and showed that the use of two MIMUs attached to the lower limbs associated with a robust method guarantee a much higher accuracy in determining gait spatio-temporal parameters. In conclusion, the proposed methods could be reliably applied to various abnormal gaits obtaining in some cases a comparable level of accuracy with respect to normal gait.

Rod-shaped plasmonic sensors

Plasmonic nanoparticles exhibit strong light scattering efficiency due to the oscillations of their conductive electrons (plasmon), which are excited by light. For rod-shaped nanoparticles, the resonance position is highly tunable by the aspect ratio (length/width) and the sensitivity to changes in the refractive index in the local environment depends on their diameter, hence, their volume. Therefore, rod-shaped nanoparticles are highly suitable as plasmonic sensors.rnWithin this thesis, I study the formation of gold nanorods and nanorods from a gold-copper alloy using a combination of small-angle X-ray scattering and optical extinction spectroscopy. The latter represents one of the first metal alloy nanoparticle synthesis protocols for producing rod-shaped single crystalline gold-copper (AuxCu(1-x)) alloyed nanoparticles. I find that both length and width independently follow an exponential growth behavior with different time-constants, which intrinsically leads to a switch between positive and negative aspect ratio growth during the course of the synthesis. In a parameter study, I find linear relations for the rate constants as a function of [HAuCl4]/[CTAB] ratio and [HAuCl4]/[seed] ratio. Furthermore, I find a correlation of final aspect ratio and ratio of rate constants for length and width growth rate for different [AgNO3]/[HAuCl4] ratios. I identify ascorbic acid as the yield limiting species in the reaction by the use of spectroscopic monitoring and TEM. Finally, I present the use of plasmonic nanorods that absorb light at 1064nm as contrast agents for photoacoustic imaging (BMBF project Polysound). rnIn the physics part, I present my automated dark-field microscope that is capable of collecting spectra in the range of 450nm to 1750 nm. I show the characteristics of that setup for the spectra acquisition in the UV-VIS range and how I use this information to simulate measurements. I show the major noise sources of the measurements and ways to reduce the noise and how the combination of setup charactersitics and simulations of sensitivity and sensing volume can be used to select appropriate gold rods for single unlabeled protein detection. Using my setup, I show how to estimate the size of gold nano-rods directly from the plasmon linewidth measured from optical single particle spectra. Then, I use this information to reduce the distribution (between particles) of the measured plasmonic sensitivity S by 30% by correcting for the systematic error introduced from the variation in particle size. I investigate the single particle scattering of bowtie structures — structures consisting of two (mostly) equilateral triangles pointing one tip at each other. I simulate the spectra of the structures considering the oblique illumination angle in my setup, which leads to additional plasmon modes in the spectra. The simulations agree well with the measurements form a qualitative point of view.rn

Simulation of visible light communications in vehicular networks

The rapid development in the field of lighting and illumination allows low energy consumption and a rapid growth in the use, and development of solid-state sources. As the efficiency of these devices increases and their cost decreases there are predictions that they will become the dominant source for general illumination in the short term. The objective of this thesis is to study, through extensive simulations in realistic scenarios, the feasibility and exploitation of visible light communication (VLC) for vehicular ad hoc networks (VANETs) applications. A brief introduction will introduce the new scenario of smart cities in which visible light communication will become a fundamental enabling technology for the future communication systems. Specifically, this thesis focus on the acquisition of several, frequent, and small data packets from vehicles, exploited as sensors of the environment. The use of vehicles as sensors is a new paradigm to enable an efficient environment monitoring and an improved traffic management. In most cases, the sensed information must be collected at a remote control centre and one of the most challenging aspects is the uplink acquisition of data from vehicles. My thesis discusses the opportunity to take advantage of short range vehicle-to-vehicle (V2V) and vehicle-to-roadside (V2R) communications to offload the cellular networks. More specifically, it discusses the system design and assesses the obtainable cellular resource saving, by considering the impact of the percentage of vehicles equipped with short range communication devices, of the number of deployed road side units, and of the adopted routing protocol. When short range communications are concerned, WAVE/IEEE 802.11p is considered as standard for VANETs. Its use together with VLC will be considered in urban vehicular scenarios to let vehicles communicate without involving the cellular network. The study is conducted by simulation, considering both a simulation platform (SHINE, simulation platform for heterogeneous interworking networks) developed within the Wireless communication Laboratory (Wilab) of the University of Bologna and CNR, and network simulator (NS3). trying to realistically represent all the wireless network communication aspects. Specifically, simulation of vehicular system was performed and introduced in ns-3, creating a new module for the simulator. This module will help to study VLC applications in VANETs. Final observations would enhance and encourage potential research in the area and optimize performance of VLC systems applications in the future.

Implementation of a VLSI amplifier interfaced with biomedical sensors for ultra wide band data transmission

This thesis presents a CMOS Amplifier with High Common Mode rejection designed in UMC 130nm technology. The goal is to achieve a high amplification factor for a wide range of biological signals (with frequencies in the range of 10Hz-1KHz) and to reject the common-mode noise signal. It is here presented a Data Acquisition System, composed of a Delta-Sigma-like Modulator and an antenna, that is the core of a portable low-complexity radio system; the amplifier is designed in order to interface the data acquisition system with a sensor that acquires the electrical signal. The Modulator asynchronously acquires and samples human muscle activity, by sending a Quasi-Digital pattern that encodes the acquired signal. There is only a minor loss of information translating the muscle activity using this pattern, compared to an encoding technique which uses astandard digital signal via Impulse-Radio Ultra-Wide Band (IR-UWB). The biological signals, needed for Electromyographic analysis, have an amplitude of 10-100μV and need to be highly amplified and separated from the overwhelming 50mV common mode noise signal. Various tests of the firmness of the concept are presented, as well the proof that the design works even with different sensors, such as Radiation measurement for Dosimetry studies.

Smart magnetic dispersions - from switchable release to well-defined hybrid nanofibers

The synthesis, characterization and application of aqueous dispersions of superparamagnetic/polymer hybrid nanoparticles and capsules is described. Implementation of the superparamagnetic moiety into the polymer matrix enables a response of the nanomaterials towards an external magnetic field. Application of the external field is used for two main purposes: i) As heat generator, when an alternating magnetic field is applied. ii) As structuring agent to self-assemble superparamagnetic nanoparticles in the external field.rnIn the first part, superparamagnetic nanoparticles were used as heat generators in order to achieve a magnetic field induced release of an active compound from nanocontainers. To achieve such a release in remote-controlled fashion, the encapsulation of superparamagnetic nanoparticles into polymer nanocapsules was combined with the integration of a thermolabile compound into the shell of the nanocontainers. The magnetic nanoparticles acted as generators for heat, which decomposed the thermolabile compound. Pores were created in the degrading shell and an active substance was released.rn Additionally, the self-assembly of polymer nanoparticles, which were labeled with a superparamagnetic moiety as structuring agent, could be demonstrated. A combination of a magnetic field induced self-assembly and a sintering of neighboring particles upon an increase in temperature above the glass transition temperature of the polymer was used to form stable architectures. Various structures with tunable periodicity could be obtained ranging from smooth linear nanofibers to zigzag fibers. Besides solely creating linear architectures, the frugal process additionally allowed the creation of arrangements in analogy to more complex polymer architectures: By the introduction of defined junction points, the generation of branched structures and networks was demonstrated. Additionally, by tailoring the interaction of differently sized particles, the preparation of nanoparticle arrangements in statistical or block copolymer fashion was shown. Moreover, a reversible linear assembly and linkage of the nanoparticles was demonstrated following a lock/unlock mechanism. Therefore, the particles were locked in their linear assembly by a stable iron(III) hydroxamato-complex and unlocked by addition of a reducing agent and formation of a less stable iron(II)-complex.Further, in various projects with collaboration partners, nanoparticles and nanocapsules were labeled with a superparamagnetic moiety for their use as contrast agents in magnetic resonance imaging or as magnetically separable dispersions.

Discovery di dispositivi embedded e raccolta di dati con bluetooth e bluetooth smart

L'obbiettivo di questa tesi è la produzione del prototipo di un sistema che sia in grado di ottenere dati da un insieme di sensori per poterli poi trasmettere all’utente, in modo che esso sia maggiormente cosciente del mondo che lo circonda. Affronteremo la sfida in uno scenario medico / di soccorso, dove un operatore si avvicinerà ad un gruppo di pazienti con l’intenzione di ottenere i parametri vitali di uno di essi. All'interno del documento saranno descritte le tecnologie sfruttate per la realizzazione del prototipo: Bluetooth e Bluetooth Smart, il sistema operativo Linux in esecuzione su un Raspberry Pi dotato di sensori, il sistema operativo Android in esecuzione su smartphone o tablet e iBeacon. Verranno poi analizzati i requisiti del sistema da realizzare. Infine verrà descritta l'implementazione utilizzata nel prototipo e analizzato il suo comportamento.

Sistema Multi Smart-Camera per la localizzazione e la guida di un drone

Con un sistema di multivisione correttamente installato e calibrato, si è tracciato il moto di un drone a seguito di operazioni di triangolazione e ne si è controllata automaticamente la traiettoria.

Novel metallo-porphyrin based colourimetric amine sensors and their processing via plasma enhanced chemical vapour deposition at atmospheric pressure : synthesis, characterisation and mechanistic studies

Volatile amines are prominent indicators of food freshness, as they are produced during many microbiological food degradation processes. Monitoring and indicating the volatile amine concentration within the food package by intelligent packaging solutions might therefore be a simple yet powerful way to control food safety throughout the distribution chain.rnrnIn this context, this work aims to the formation of colourimetric amine sensing surfaces on different substrates, especially transparent PET packaging foil. The colour change of the deposited layers should ideally be discernible by the human eye to facilitate the determination by the end-user. rnrnDifferent tailored zinc(II) and chromium(III) metalloporphyrins have been used as chromophores for the colourimetric detection of volatile amines. A new concept to increase the porphyrins absorbance change upon exposure to amines is introduced. Moreover, the novel porphyrins’ processability during the deposition process is increased by their enhanced solubility in non-polar solvents.rnrnThe porphyrin chromophores have successfully been incorporated into polysiloxane matrices on different substrates via a dielectric barrier discharge enhanced chemical vapour deposition. This process allows the use of nitrogen as a cheap and abundant plasma gas, produces minor amounts of waste and by-products and can be easily introduced into (existing) roll-to-roll production lines. The formed hybrid sensing layers tightly incorporate the porphyrins and moreover form a porous structure to facilitate the amines diffusion to and interaction with the chromophores.rnrnThe work is completed with the thorough analysis of the porphyrins’ amine sensing performance in solution as well as in the hybrid coatings . To reveal the underlying interaction mechanisms, the experimental results are supported by DFT calculations. The deposited layers could be used for the detection of NEt3 concentrations below 10 ppm in the gas phase. Moreover, the coated foils have been tested in preliminary food storage experiments. rnrnThe mechanistic investigations on the interaction of amines with chromium(III) porphyrins revealed a novel pathway to the formation of chromium(IV) oxido porphyrins. This has been used for electrochemical epoxidation reactions with dioxygen as the formal terminal oxidant.rn

Plasmonic nanoparticles as sensors : a novel approach to quantify adsorption and diffusion kinetics

Biosensors find wide application in clinical diagnostics, bioprocess control and environmental monitoring. They should not only show high specificity and reproducibility but also a high sensitivity and stability of the signal. Therefore, I introduce a novel sensor technology based on plasmonic nanoparticles which overcomes both of these limitations. Plasmonic nanoparticles exhibit strong absorption and scattering in the visible and near-infrared spectral range. The plasmon resonance, the collective coherent oscillation mode of the conduction band electrons against the positively charged ionic lattice, is sensitive to the local environment of the particle. I monitor these changes in the resonance wavelength by a new dark-field spectroscopy technique. Due to a strong light source and a highly sensitive detector a temporal resolution in the microsecond regime is possible in combination with a high spectral stability. This opens a window to investigate dynamics on the molecular level and to gain knowledge about fundamental biological processes.rnFirst, I investigate adsorption at the non-equilibrium as well as at the equilibrium state. I show the temporal evolution of single adsorption events of fibrinogen on the surface of the sensor on a millisecond timescale. Fibrinogen is a blood plasma protein with a unique shape that plays a central role in blood coagulation and is always involved in cell-biomaterial interactions. Further, I monitor equilibrium coverage fluctuations of sodium dodecyl sulfate and demonstrate a new approach to quantify the characteristic rate constants which is independent of mass transfer interference and long term drifts of the measured signal. This method has been investigated theoretically by Monte-Carlo simulations but so far there has been no sensor technology with a sufficient signal-to-noise ratio.rnSecond, I apply plasmonic nanoparticles as sensors for the determination of diffusion coefficients. Thereby, the sensing volume of a single, immobilized nanorod is used as detection volume. When a diffusing particle enters the detection volume a shift in the resonance wavelength is introduced. As no labeling of the analyte is necessary the hydrodynamic radius and thus the diffusion properties are not altered and can be studied in their natural form. In comparison to the conventional Fluorescence Correlation Spectroscopy technique a volume reduction by a factor of 5000-10000 is reached.