Studies of pure rotational spectra of isolated molecules and molecular adducts using pulsed jet Fourier transform microwave (PJ-FTM) spectroscopy

This thesis focuses on studying molecular structure and internal dynamics by using pulsed jet Fourier transform microwave (PJ-FTMW) spectroscopy combined with theoretical calculations. Several kinds of interesting chemical problems are investigated by analyzing the MW spectra of the corresponding molecular systems. First, the general aspects of rotational spectroscopy are summarized, and then the basic theory on molecular rotation and experimental method are described briefly. ab initio and density function theory (DFT) calculations that used in this thesis to assist the assignment of rotational spectrum are also included. From chapter 3 to chapter 8, several molecular systems concerning different kind of general chemical problems are presented. In chapter 3, the conformation and internal motions of dimethyl sulfate are reported. The internal rotations of the two methyl groups split each rotational transition into several components line, allowing for the determination of accurate values of the V3 barrier height to internal rotation and of the orientation of the methyl groups with respect to the principal axis system. In chapter 4 and 5, the results concerning two kinds of carboxylic acid bi-molecules, formed via two strong hydrogen bonds, are presented. This kind of adduct is interesting also because a double proton transfer can easily take place, connecting either two equivalent or two non-equivalent molecular conformations. Chapter 6 concerns a medium strong hydrogen bonded molecular complex of alcohol with ether. The dimer of ethanol-dimethylether was chosen as the model system for this purpose. Chapter 7 focuses on weak halogen…H hydrogen bond interaction. The nature of O-H…F and C-H…Cl interaction has been discussed through analyzing the rotational spectra of CH3CHClF/H2O. In chapter 8, two molecular complexes concerning the halogen bond interaction are presented.

Design and Fabrication of Bond Wire Micro-Magnetics

This thesis presents a new approach for the design and fabrication of bond wire magnetics for power converter applications by using standard IC gold bonding wires and micro-machined magnetic cores. It shows a systematic design and characterization study for bond wire transformers with toroidal and race-track cores for both PCB and silicon substrates. Measurement results show that the use of ferrite cores increases the secondary self-inductance up to 315 µH with a Q-factor up to 24.5 at 100 kHz. Measurement results on LTCC core report an enhancement of the secondary self-inductance up to 23 µH with a Q-factor up to 10.5 at 1.4 MHz. A resonant DC-DC converter is designed in 0.32 µm BCD6s technology at STMicroelectronics with a depletion nmosfet and a bond wire micro-transformer for EH applications. Measures report that the circuit begins to oscillate from a TEG voltage of 280 mV while starts to convert from an input down to 330 mV to a rectified output of 0.8 V at an input of 400 mV. Bond wire magnetics is a cost-effective approach that enables a flexible design of inductors and transformers with high inductance and high turns ratio. Additionally, it supports the development of magnetics on top of the IC active circuitry for package and wafer level integrations, thus enabling the design of high density power components. This makes possible the evolution of PwrSiP and PwrSoC with reliable highly efficient magnetics.

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.

Effect of pulsed electromagnetic fields (pemfs) on muscle activity, tissue oxygenation and vo2 during exercise.

PEMF are a medical and non-invasive therapy successfully used for clinical treatments of bone disease, due to the piezoelectric effect that improve bone mass and density, by the stimulation of osteoblastogenesis, with modulation of calcium storages and mineral metabolism. PEMF enhance tissue oxygenation, microcirculation and angiogenesis, in rats and cells erythrocytes, in cells-free assay. Such responses could be caused by a modulation of nitric oxide signal and interaction between PEMF and Ca2+/NO/cGMP/PKG signal. PEMF improve blood flow velocity of smallest vein without changing their diameter. PEMF therapy helpful in patients with diabetes, due to increased microcirculation trough enhance capillary blood velocity and diameter. We investigated the influence of stimulation on muscular activity, tissue oxygenation and pulmonary VO2, during exercise, on different intensity, as heavy or moderate, different subjects, as a athlete or sedentary, and different sport activity, as a cycling or weightlifting. In athletes, we observed a tendency for a greater change and a faster kinetic of HHb concentration. PEMF increased the velocity and the quantity of muscle O2 available, leading to accelerate the HHb kinetics. Stimulation induced a bulk muscle O2 availability and a greater muscle O2 extraction, leading to a reduced time delay of the HHb slow component. Stimulation increased the amplitude of muscle activity under different conditions, likely caused by the effect of PEMF on contraction mechanism of muscular fibers, by the change of membrane permeability and Ca2+ channel conduction. In athletes, we observed an increase of overall activity during warm-up. In sedentary people, stimulation increased the magnitude of muscle activity during moderate constant-load exercise and warm-up. In athletes and weightlifters, stimulation caused an increase of blood lactate concentration during exercise, confirming a possible influence of stimulation on muscle activity and on glycolytic metabolism of type-II muscular fibers.

Diversified applications of supplemental LED light for greenhouse tomato production in the Mediterranean context

Among the various aspects to be investigated for a technological and productive upgrade of tomato greenhouse production in the Mediterranean area, the application of supplementary LED interlighting still shows limited interest. However, high-density tomato cultivation with intensive high-wire systems could lead to mutual shading and consequent reduction in photosynthesis and yield, even in case of appreciable amounts of external solar radiation, as in Southern Europe. Applications of interest could also involve off-season production or Building-Integrated Agriculture (BIA) such as rooftop greenhouses, where municipal regulations for structure and fire safety could limit the incoming radiation in the growing area. The aim of this research was to investigate diversified applications of supplemental LED interlighting for greenhouse tomato production (Solanum lycopersicum) in the Mediterranean countries. The diversified applications included: effects on post-harvest quality, shading reduction in BIA, tailored seedlings production, and off-season cultivation. The results showed that the application of supplemental LED light on greenhouse-grown tomato in Mediterranean countries (Italy and Spain) has potential to foster diverse applications. In particular, it can increase production in case of the limited solar radiation in rooftop greenhouses, maintain quality and reduce losses during post-harvest, help producing high quality and tailored seedlings, and increase yield during wintertime. Despite the positive results obtained, some aspects of the application of additional LED light in Southern Europe countries still need to be deepened and improved. In particular, given the current increase of electricity cost, future research should focus on more economically valuable methods of managing supplemental lighting, such as the application of shorter photoperiods or lower intensities, or techniques that can provide energy savings such as the pulsed light.

Analysis and improvements of four-wire power converters for electric vehicle chargers

A robust and well-distributed backbone charging network is the priority to ensure widespread electrification of road transport, providing a driving experience similar to that of internal combustion engine vehicles. International standards set multiple technical targets for on-board and off-board electric vehicle chargers; output voltage levels, harmonic emissions, and isolation requirements strongly influence the design of power converters. Additionally, smart-grid services such as vehicle-to-grid and vehicle-to-vehicle require the implementation of bi-directional stages that inevitably increase system complexity and component count. To face these design challenges, the present thesis provides a rigorous analysis of four-leg and split-capacitor three-phase four-wire active front-end topologies focusing on the harmonic description under different modulation techniques and conditions. The resulting analytical formulation paves the way for converter performance improvements while maintaining regulatory constraints and technical requirements under control. Specifically, split-capacitor inverter current ripple was characterized as providing closed-form formulations valid for every sub-case ranging from synchronous to interleaved PWM. Outcomes are the base for a novel variable switching PWM technique capable of mediating harmonic content limitation and switching loss reduction. A similar analysis is proposed for four-leg inverters with a broad range of continuous and discontinuous PWM modulations. The general superiority of discontinuous PWM modulation in reducing switching losses and limiting harmonic emission was demonstrated. Developments are realized through a parametric description of the neutral wire inductor. Finally, a novel class of integrated isolated converter topologies is proposed aiming at the neutral wire delivery without employing extra switching components rather than the one already available in typical three-phase inverter and dual-active-bridge back-to-back configurations. The fourth leg was integrated inside the dual-active-bridge input bridge providing relevant component count savings. A novel modified single-phase-shift modulation technique was developed to ensure a seamless transition between working conditions like voltage level and power factor. Several simulations and experiments validate the outcomes.