Application of Pulsed Electric Fields for the Modulation of Chemico-Physical Properties of Different Foods

Pulsed electric field technology is one of the most attractive new non-thermal technology thanks to its lower energy consumption and short treatment times. It consists of an electric treatment of short duration (from several ns to several ms) with electric field strengths from 0.1 to 80 kV/cm that lead to an increase in the permeability of the cell membrane. In this PhD thesis, PEF technology was investigated with the aim of improving mass transfer in plant and animal foods by using it alone or in combination with conventional food processes. Different methods of evaluating electroporation for optimizing PEF processing parameters were investigated. In this respect, the degree of membrane permeabilization in plant and animal food matrices was investigated using electrical impedance spectroscopy, current-voltage measurements and magnetic resonance imaging. The research findings provided useful insights and calls for critical choice of electroporation assessment methods for the selection of adequate PEF treatment conditions. It was outlined that the effect of electroporation is highly dependent on the properties of the food matrix and secondary phenomena occurring in the cell structure undergoing PEF treatment, such as the water re-distribution in the tissue due to the exchange of fluids between intra- and extra-cellular environments. This study also confirmed the great potential of combining PEF technology with conventional food processes, with the main purpose of improving the quality of the food material and accelerating the kinetics of mass transfers, in both plant and animal tissues. Consistent reduction of acrylamide formation in potato crisps was achieved by monitoring key PEF process parameters and subsequent manufacturing steps. Kiwifruit snacks showed a significant reduction in drying kinetics when pre-treated with PEF, while their quality was well maintained. Finally, the research results showed that PEF pre-treatments can shorten the brine process as well as the rehydration kinetics of fish muscles.

On the degradation mechanisms under the influence of pedological factors through the study of archeological bronze patina

This experimental thesis concerns the study of the long-term behaviour of ancient bronzes recently excavated from burial conditions. The scientific interest is to clarify the effect of soil parameters on the degradation mechanisms of ancient bronze alloy. The work took into consideration bronzes recovered from the archaeological sites in the region of Dobrudja, Romania. The first part of research work was dedicated to the characterization of bronze artefacts using non destructive (micro-FTIR, reflectance mode) and micro-destructive (based on sampling and analysis of a stratigraphical section by OM and SEM-EDX) methods. Burial soils were geologically classified and analyzed by chemical methods (pH, conductivity, anions content). Most of objects analyzed showed a coarse and inhomogeneous corroded structure, often made up of several corrosion layers. This has been explained by the silt nature of soils, which contain low amount of clay and are, therefore, quite accessible to water and air. The main cause of a high dissolution rate of bronze alloys is the alternate water saturation and instauration of the soil, for example on a seasonal scale. Moreover, due to the vicinity of the Black Sea, the detrimental effect of chlorine has been evidenced for few objects, which were affected by the bronze disease. A general classification of corrosion layers was achieved by comparing values of the ratio Cu/Sn in the alloy and in the patina. Decuprification is a general trend, and enrichment of copper within the corrosion layers, due to the formation of thick layers of cuprite (Cu2O), is pointed out as well. Uncommon corrosion products and degradation patterns were presented as well, and they are probably due to peculiar local conditions taking place during the burial time, such as anaerobic conditions or fluctuating environmental conditions. In order to acquire a better insight into the corrosion mechanisms, the second part of the thesis has regarded simulation experiments, which were conducted on commercial Cu-Sn alloys, whose composition resembles those of ancient artefacts one. Electrochemical measurements were conducted in natural electrolytes, such as solutions extracted from natural soil (sampled at the archaeological sites) and seawater. Cyclic potentiodynamic experiments allowed appreciating the mechanism of corrosion in both cases. Soil extract’s electrolyte has been evaluated being a non aggressive medium, while artificial solution prepared by increasing the concentration of anions caused the pitting corrosion of the alloy, which is demonstrated by optical observations. In particular, electrochemical impedance spectroscopy allows assessing qualitatively the nature of corroded structures formed in soil and seawater. A double-structured layer is proposed, which differ, in the two cases, for the nature of the internal passive layer, which result defectiveness and porous in case of seawater.

Parallel modeling of the electric field distribution in the brain

The term "Brain Imaging" identi�es a set of techniques to analyze the structure and/or functional behavior of the brain in normal and/or pathological situations. These techniques are largely used in the study of brain activity. In addition to clinical usage, analysis of brain activity is gaining popularity in others recent �fields, i.e. Brain Computer Interfaces (BCI) and the study of cognitive processes. In this context, usage of classical solutions (e.g. f MRI, PET-CT) could be unfeasible, due to their low temporal resolution, high cost and limited portability. For these reasons alternative low cost techniques are object of research, typically based on simple recording hardware and on intensive data elaboration process. Typical examples are ElectroEncephaloGraphy (EEG) and Electrical Impedance Tomography (EIT), where electric potential at the patient's scalp is recorded by high impedance electrodes. In EEG potentials are directly generated from neuronal activity, while in EIT by the injection of small currents at the scalp. To retrieve meaningful insights on brain activity from measurements, EIT and EEG relies on detailed knowledge of the underlying electrical properties of the body. This is obtained from numerical models of the electric �field distribution therein. The inhomogeneous and anisotropic electric properties of human tissues make accurate modeling and simulation very challenging, leading to a tradeo�ff between physical accuracy and technical feasibility, which currently severely limits the capabilities of these techniques. Moreover elaboration of data recorded requires usage of regularization techniques computationally intensive, which influences the application with heavy temporal constraints (such as BCI). This work focuses on the parallel implementation of a work-flow for EEG and EIT data processing. The resulting software is accelerated using multi-core GPUs, in order to provide solution in reasonable times and address requirements of real-time BCI systems, without over-simplifying the complexity and accuracy of the head models.

Heterogeneous multicore systems for signal processing

This thesis explores the capabilities of heterogeneous multi-core systems, based on multiple Graphics Processing Units (GPUs) in a standard desktop framework. Multi-GPU accelerated desk side computers are an appealing alternative to other high performance computing (HPC) systems: being composed of commodity hardware components fabricated in large quantities, their price-performance ratio is unparalleled in the world of high performance computing. Essentially bringing “supercomputing to the masses”, this opens up new possibilities for application fields where investing in HPC resources had been considered unfeasible before. One of these is the field of bioelectrical imaging, a class of medical imaging technologies that occupy a low-cost niche next to million-dollar systems like functional Magnetic Resonance Imaging (fMRI). In the scope of this work, several computational challenges encountered in bioelectrical imaging are tackled with this new kind of computing resource, striving to help these methods approach their true potential. Specifically, the following main contributions were made: Firstly, a novel dual-GPU implementation of parallel triangular matrix inversion (TMI) is presented, addressing an crucial kernel in computation of multi-mesh head models of encephalographic (EEG) source localization. This includes not only a highly efficient implementation of the routine itself achieving excellent speedups versus an optimized CPU implementation, but also a novel GPU-friendly compressed storage scheme for triangular matrices. Secondly, a scalable multi-GPU solver for non-hermitian linear systems was implemented. It is integrated into a simulation environment for electrical impedance tomography (EIT) that requires frequent solution of complex systems with millions of unknowns, a task that this solution can perform within seconds. In terms of computational throughput, it outperforms not only an highly optimized multi-CPU reference, but related GPU-based work as well. Finally, a GPU-accelerated graphical EEG real-time source localization software was implemented. Thanks to acceleration, it can meet real-time requirements in unpreceeded anatomical detail running more complex localization algorithms. Additionally, a novel implementation to extract anatomical priors from static Magnetic Resonance (MR) scansions has been included.

Analog Signal Acquisition and Conditioning for Near-Field Capacitive Communication and Active Combined EEG-EIT Monitoring

The work of the present thesis is focused on the implementation of microelectronic voltage sensing devices, with the purpose of transmitting and extracting analog information between devices of different nature at short distances or upon contact. Initally, chip-to-chip communication has been studied, and circuitry for 3D capacitive coupling has been implemented. Such circuits allow the communication between dies fabricated in different technologies. Due to their novelty, they are not standardized and currently not supported by standard CAD tools. In order to overcome such burden, a novel approach for the characterization of such communicating links has been proposed. This results in shorter design times and increased accuracy. Communication between an integrated circuit (IC) and a probe card has been extensively studied as well. Today wafer probing is a costly test procedure with many drawbacks, which could be overcome by a different communication approach such as capacitive coupling. For this reason wireless wafer probing has been investigated as an alternative approach to standard on-contact wafer probing. Interfaces between integrated circuits and biological systems have also been investigated. Active electrodes for simultaneous electroencephalography (EEG) and electrical impedance tomography (EIT) have been implemented for the first time in a 0.35 um process. Number of wires has been minimized by sharing the analog outputs and supply on a single wire, thus implementing electrodes that require only 4 wires for their operation. Minimization of wires reduces the cable weight and thus limits the patient's discomfort. The physical channel for communication between an IC and a biological medium is represented by the electrode itself. As this is a very crucial point for biopotential acquisitions, large efforts have been carried in order to investigate the different electrode technologies and geometries and an electromagnetic model is presented in order to characterize the properties of the electrode to skin interface.

Advanced CMOS Interfaces for Bio-Nanosensors

The improvement of devices provided by Nanotechnology has put forward new classes of sensors, called bio-nanosensors, which are very promising for the detection of biochemical molecules in a large variety of applications. Their use in lab-on-a-chip could gives rise to new opportunities in many fields, from health-care and bio-warfare to environmental and high-throughput screening for pharmaceutical industry. Bio-nanosensors have great advantages in terms of cost, performance, and parallelization. Indeed, they require very low quantities of reagents and improve the overall signal-to-noise-ratio due to increase of binding signal variations vs. area and reduction of stray capacitances. Additionally, they give rise to new challenges, such as the need to design high-performance low-noise integrated electronic interfaces. This thesis is related to the design of high-performance advanced CMOS interfaces for electrochemical bio-nanosensors. The main focus of the thesis is: 1) critical analysis of noise in sensing interfaces, 2) devising new techniques for noise reduction in discrete-time approaches, 3) developing new architectures for low-noise, low-power sensing interfaces. The manuscript reports a multi-project activity focusing on low-noise design and presents two developed integrated circuits (ICs) as examples of advanced CMOS interfaces for bio-nanosensors. The first project concerns low-noise current-sensing interface for DC and transient measurements of electrophysiological signals. The focus of this research activity is on the noise optimization of the electronic interface. A new noise reduction technique has been developed so as to realize an integrated CMOS interfaces with performance comparable with state-of-the-art instrumentations. The second project intends to realize a stand-alone, high-accuracy electrochemical impedance spectroscopy interface. The system is tailored for conductivity-temperature-depth sensors in environmental applications, as well as for bio-nanosensors. It is based on a band-pass delta-sigma technique and combines low-noise performance with low-power requirements.

Hybrid portable systems for bio-nanosensors

The promising development in the routine nanofabrication and the increasing knowledge of the working principles of new classes of highly sensitive, label-free and possibly cost-effective bio-nanosensors for the detection of molecules in liquid environment, has rapidly increased the possibility to develop portable sensor devices that could have a great impact on many application fields, such as health-care, environment and food production, thanks to the intrinsic ability of these biosensors to detect, monitor and study events at the nanoscale. Moreover, there is a growing demand for low-cost, compact readout structures able to perform accurate preliminary tests on biosensors and/or to perform routine tests with respect to experimental conditions avoiding skilled personnel and bulky laboratory instruments. This thesis focuses on analysing, designing and testing novel implementation of bio-nanosensors in layered hybrid systems where microfluidic devices and microelectronic systems are fused in compact printed circuit board (PCB) technology. In particular the manuscript presents hybrid systems in two validating cases using nanopore and nanowire technology, demonstrating new features not covered by state of the art technologies and based on the use of two custom integrated circuits (ICs). As far as the nanopores interface system is concerned, an automatic setup has been developed for the concurrent formation of bilayer lipid membranes combined with a custom parallel readout electronic system creating a complete portable platform for nanopores or ion channels studies. On the other hand, referring to the nanowire readout hybrid interface, two systems enabling to perform parallel, real-time, complex impedance measurements based on lock-in technique, as well as impedance spectroscopy measurements have been developed. This feature enable to experimentally investigate the possibility to enrich informations on the bio-nanosensors concurrently acquiring impedance magnitude and phase thus investigating capacitive contributions of bioanalytical interactions on biosensor surface.

Polyaniline-based materials and nanocomposites: from energy storage to sensing applications

The research work described in this thesis concerns materials for both energy storage and sensoristics applications. Firstly, the synthesis and characterization of magnetite (Fe3O4) functionalyzed with [3-(2-propynylcarbamate)propyl]triethoxysilane (PPTEOS) capable to reduce the gold precursor chloroauric acid (HAuCl4) without the need of additional reducing or stabilising agents is described. These nanoparticles were tested to improve performances of symmetric capacitors based on polyaniline and graphite foil. Energy storage applications were investigated also during six months stay at EPFL University of Lausanne where an investigation about different tailored catalysts for Oxygen Evolution Reaction in a particular Redox Flow Battery was carried out. For what concerns sensing applications, new materials based on cellulose modified with polyaniline and poly(2-acrylamido-2-methyl-1-propanesulfonic acid) (PAAMPSA) were synthesized, characterized and applied to monitor pressure, humidity, heart rate and lastly, bread fermentation in collaboration with the University of Fribourg and Zurich. The characterizations of all the materials investigated compriseed numerous techniques such as infrared attenuated total reflectance spectroscopy (IR-ATR), thermogravimetric analysis (TGA), scanning and transmission electron microscopy (SEM and TEM), alongside linear and cyclic voltammetry (LSV and CV), electrochemical impedance spectroscopy (EIS) and chronoamperometric analyses.

Study of materials and interphases for electrochemical energy storage from renewable sources

Batteries should be refined depending on their application for a future in which the sustainable energy demand increases. On the one hand, it is fundamental to improve their safety, prevent failures, increase energy density, and reduce production costs. On the other hand, new battery materials and architecture are required to satisfy the growing demand. This thesis explores different electrochemical energy storage systems and new methodologies to investigate complex and dynamic processes. Lithium-ion batteries are described in all their cell components. In these systems, this thesis investigates negative electrodes. Both the development of new sustainable materials and new in situ electrode characterization methods were explored. One strategy to achieve high-energy systems is employing lithium metal anodes. In this framework, ammonium hexafluorophosphate is demonstrated to be a suitable additive for stabilizing the interphase and preventing uncontrolled dendritic deposition. Deposition/stripping cycles, electrochemical impedance spectroscopy, in situ optical microscopy, and operando confocal Raman spectroscopy have been used to study lithium metal-electrolyte interphase in the presence of the additive. Redox Flow Batteries (RFBs) are proposed as a sustainable alternative for stationary applications. An all-copper aqueous RFB (CuRFB) has been studied in all its aspects. For the electrolyte optimization, spectro-electrochemical tests in diluted solution have been used to get information on the electrolyte’s electrochemical behaviour with different copper complexes distributions. In concentrated solutions, the effects of copper-to-ligand ratios, the concentration, and the counter-ion of the complexing agent were evaluated. Electrode thermal treatment was optimized, finding a compromise between the electrochemical performance and the carbon footprint. On the membrane side, a new method for permeability studies was designed using scanning electrochemical microscopy (SECM). The Cu(II) permeability of several membranes was tested, obtaining direct visualization of Cu(II) concentration in space. Also, two spectrophotometric approaches were designed for SoC monitoring systems for negative and positive half-cells.

Data driven regularization models of non-linear ill-posed inverse problems in imaging

Imaging technologies are widely used in application fields such as natural sciences, engineering, medicine, and life sciences. A broad class of imaging problems reduces to solve ill-posed inverse problems (IPs). Traditional strategies to solve these ill-posed IPs rely on variational regularization methods, which are based on minimization of suitable energies, and make use of knowledge about the image formation model (forward operator) and prior knowledge on the solution, but lack in incorporating knowledge directly from data. On the other hand, the more recent learned approaches can easily learn the intricate statistics of images depending on a large set of data, but do not have a systematic method for incorporating prior knowledge about the image formation model. The main purpose of this thesis is to discuss data-driven image reconstruction methods which combine the benefits of these two different reconstruction strategies for the solution of highly nonlinear ill-posed inverse problems. Mathematical formulation and numerical approaches for image IPs, including linear as well as strongly nonlinear problems are described. More specifically we address the Electrical impedance Tomography (EIT) reconstruction problem by unrolling the regularized Gauss-Newton method and integrating the regularization learned by a data-adaptive neural network. Furthermore we investigate the solution of non-linear ill-posed IPs introducing a deep-PnP framework that integrates the graph convolutional denoiser into the proximal Gauss-Newton method with a practical application to the EIT, a recently introduced promising imaging technique. Efficient algorithms are then applied to the solution of the limited electrods problem in EIT, combining compressive sensing techniques and deep learning strategies. Finally, a transformer-based neural network architecture is adapted to restore the noisy solution of the Computed Tomography problem recovered using the filtered back-projection method.

Fabrication, Electrical Characterization and Simulation of Thin Film Solar Cells: CdTe and CIGS Materials

CdTe and Cu(In,Ga)Se2 (CIGS) thin film solar cells are fabricated, electrically characterized and modelled in this thesis. We start from the fabrication of CdTe thin film devices where the R.F. magnetron sputtering system is used to deposit the CdS/CdTe based solar cells. The chlorine post-growth treatment is modified in order to uniformly cover the cell surface and reduce the probability of pinholes and shunting pathways creation which, in turn, reduces the series resistance. The deionized water etching is proposed, for the first time, as the simplest solution to optimize the effect of shunt resistance, stability and metal-semiconductor inter-diffusion at the back contact. In continue, oxygen incorporation is proposed while CdTe layer deposition. This technique has been rarely examined through R.F sputtering deposition of such devices. The above experiments are characterized electrically and optically by current-voltage characterization, scanning electron microscopy, x-ray diffraction and optical spectroscopy. Furthermore, for the first time, the degradation rate of CdTe devices over time is numerically simulated through AMPS and SCAPS simulators. It is proposed that the instability of electrical parameters is coupled with the material properties and external stresses (bias, temperature and illumination). Then, CIGS materials are simulated and characterized by several techniques such as surface photovoltage spectroscopy is used (as a novel idea) to extract the band gap of graded band gap CIGS layers, surface or bulk defect states. The surface roughness is scanned by atomic force microscopy on nanometre scale to obtain the surface topography of the film. The modified equivalent circuits are proposed and the band gap graded profiles are simulated by AMPS simulator and several graded profiles are examined in order to optimize their thickness, grading strength and electrical parameters. Furthermore, the transport mechanisms and Auger generation phenomenon are modelled in CIGS devices.