Objective: To identify whether perceived stress is a risk-factor for higher cortisol levels and greater insulin resistance in Type 2 diabetic patients, using data from participants with and without diabetes in the National Survey of Midlife Development in the United States (MIDUS), specifically MIDUS II, Project 4. The following hypotheses were tested: (H1a) greater perceived stress would be associated with higher cortisol for Type 2 diabetic participants, (H1b) the perceived stress/cortisol relationship would be stronger for people with Type 2 diabetes than for those without it, (H2) greater perceived stress would be associated with higher Homeostatic Model Assessment-Insulin Resistance (HOMA-IR, insulin-resistance) for Type 2 diabetic participants, (H3a) subjective well-being would moderate the perceived stress/insulin resistance relationship for Type 2 diabetic participants, and (H3b) depression would moderate the perceived stress/insulin resistance relationship for Type 2 diabetic participants. Method: MIDUS, a longitudinal study of over 7,000 American adults, explores biopsychosocial factors that could contribute to variance in mental/physical health. Only complete data were utilized. Type 2 participants (n=115) consisted of 54 males and 62 females ranging in age from 36 to 81 years. Non-diabetic participants (n=1097) consisted of 470 males and 627 females ranging in age from 34 to 84 years. Results: None of the predicted relationships were statistically significant. Waist to hip ratio was significantly related to insulin resistance (r = .31, p = .001). Conclusions: Future studies should collect information about the type and duration of stressors in addition to perceptions about stress for those with Type 2 diabetes.

La théorie de l'information développée par Claude Shannon (1916 - 2001) met en évidence le fait que pour accroître la capacité d'un canal de transmission, il est préférable d'élargir la bande de fréquences sur laquelle les informations sont émises plutôt que les puissances d'émissions. Cette constatation est le point de départ de nombreux travaux de recherche sur les communications Ultra-Large Bande (ULB) qui ont abouti en 2002 à la création aux Etats-Unis d'une bande fréquence dîtes ULB où aucun mode de communication n'est privilégié. C'est ainsi que 2 années plus tard ont débuté à l'IM2NP des travaux portant sur les communications ULB impulsionnelles, et notamment la conception d'amplificateur faible bruit, de détecteur d'énergie, mais également de générateurs d'impulsions qui est l'élément clé des émetteurs impulsionnels. Ces derniers constituent la base des travaux présentés dans le manuscrit qui se sont déroulés de 2008 à 2011. La nature discontinue des communications impulsionnelles a tout d'abord impliquée l'introduction de nouvelles figures de mérite permettant de mesurer les performances des générateurs d'impulsions. Ensuite, il est question de méthodes de conception permettant de dimensionner des structures fonctionnant aux fréquences en jeu mais également d'en réduire les consommations statiques principalement de fuite, et ce en vue de répondre aux contraintes de consommation des systèmes embarqués. Enfin sont développées 3 architectures de générateurs d'impulsions, chacune permettant de répondre à des contraintes différentes en termes de bande de fréquences, de consommation et de portée. / The information theory developed by Claude Shannon (1916 - 2001) highlights the fact that in order to increase the capacity of a transmission channel, it is preferable to extend the bandwidth used rather than the transmission power. This finding is the starting point of many papers on Ultra-Wideband (UWB) which led to the creation in the United States of UWB band since 2002 where no modulation is privileged. Two years later, many works on Impulsionnal Radio UWB (IR-UWB) communications began at IM2NP including the design of low noise amplifier, power detector, but also pulse generators which is the key element of IR-UWB emitters. These form basis of works presented in the manuscript that took place from 2008 to 2011. The discontinuous nature of communications impulse was first implied the introduction of new figures of merit for measuring performances of pulse generators. Then it deals with design techniques for sizing structures operating at frequencies involved, but also to reduce consumption and especially static leakage to reduce enough power consumption for embedded systems. Finally three architectures of pulse generators are developed, each one responding to different constraints in terms of frequency, consumption and range.

Water is “the matrix of life” for its fascinating properties. The well-known simple water molecule consists of one oxygen atom and two hydrogen atoms, covering most of planet earth’ssurface. It is the most studied element in science; however, its properties are still not fully understood. Another essential building block of life is proteins, which manifest naturally in aqueous environments. The protein activity is controlled by the protein folding process that is dependent on the surrounding environment. It is hypothesized that the hydrogen bond network of water plays an important role in the folding process. Here, we investigate the protein lysozyme in liquid water as well as in the crystalline state ice Ih, exploring various temperatures, using FT-IR and XRD. Our main finding is that a transition occurs at approximately T=210 K, indicative of the hypothesised protein dynamic “glass” transitionobserved by previous studies in supercooled water at similar temperatures.

For a PV plant it is of fundamental importance that the operation of the PV modules is free from faults or at least that the faults can be detected early, to ensure efficient electricity production. Some defects such as cracks can be seen in visible light while microcracks and damage to the silicon material can only be seen through special lighting. This study focuses on the most common defects in photovoltaic (PV) systems. Compare the infrared (IR) technology with the new ultraviolet (UV) fluorescence image technique for PV characterization, based on their accuracy and uncertainty factors under an experimental field investigation. In this study, first a literature study was conducted to the most common defects in PV system and their impact on electricity generation. Then a simulation model of a PV system was created in PVsyst and exported to Microsoft Excel which was used to evaluate how different defects at different stages of the PV cell's life cycle impact electricity generation, performance parameters and economic exchange. Furthermore, experiments with UV and IR was implemented at a PV system located in Dalarna and some PV modules at MDH. It was conducted that occurrence of snail tracks, delamination and hot spots in combination with bypass failures and non-functioning cell will affect the economic profitability in the long run and the payback time will increase since their impacts on electricity generation and performance parameters are huge. The worst case is when PV modules are affected by the fault in bypass diode and non-functioning cell which result to a payback time longer than the module's lifetime and huge amount electricity losses in different bypass diodes configurations. Since UV and IR are two different methods that are performed in two different ways, different errors occurred during the measurements. The biggest external factor was the weather that determined if the experiment could be implemented. The IR method gave decent results and was quicker to use, but the UV method highlighted some defect which could not be seen with the IR technology.

Le présent travail de thèse se propose de développer des techniques innovantes pour l'automatisation de tri de déchets de bois. L'idée est de combiner les techniques de spectrométrie proche-infra-rouge à des méthodes robustes de traitement de données pour la classification. Après avoir exposé le contexte du travail dans le premier chapitre, un état de l'art sur la classification de données spectrales est présenté dans le chapitre 2. Le troisième chapitre traite du problème de sélection de variables par des approches parcimonieuses. En particulier nous proposons d'étendre quelques méthodes gloutonnes pour l'approximation parcimonieuse simultanée. Les simulations réalisées pour l'approximation d'une matrice d'observations montrent l'intérêt des approches proposées. Dans le quatrième chapitre, nous développons des méthodes de sélection de variables basées sur la représentation parcimonieuse simultanée et régularisée, afin d'augmenter les performances du classifieur SVM pour la classification des spectres IR ainsi que des images hyperspectrales de déchets de bois. Enfin, nous présentons dans le dernier chapitre les améliorations apportées aux systèmes de tri de bois existants. Les résultats des tests réalisés avec logiciel de traitement mis en place, montrent qu'un gain considérable peut être atteint en termes de quantités de bois recyclées / In this thesis, innovative techniques for sorting wood wastes are developed. The idea is to combine infrared spectrometry techniques with robust data processing methods for classification task. After exposing the context of the work in the first chapter, a state of the art on the spectral data classification is presented in the chapter 2. The third chapter deals with variable selection problem using sparse approaches. In particular we propose to extend some greedy methods for the simultaneous sparse approximation. The simulations performed for the approximation of an observation matrix validate the advantages of the proposed approaches. In the fourth chapter, we develop variable selection methods based on simultaneous sparse and regularized representation, to increase the performances of SVM classifier for the classification of NIR spectra and hyperspectral images of wood wastes. In the final chapter, we present the improvements made to the existing sorting systems. The results of the conducted tests using the processing software confirm that significant benefits can be achieved in terms of recycled wood quantities

Ce travail de doctorat consiste à valoriser les coproduits issus des industries d’agrumes par des technologies innovantes. Le pressage des agrumes produit des millions de tonnes de déchets par an dans le monde. Ces déchets (peaux, pulpes et pépins) sont généralement dédiés à l’alimentation animale ou bien éliminés par compostage ou incinération. Cependant leur contenu en molécules bioactives conduit à plusieurs voies de valorisation. Vu que les peaux constituent à peu près la moitié de la masse des déchets d’agrumes, les études ont été faites sur la valorisation des peaux de différents types d’agrumes. Les méthodes conventionnelles généralement utilisées pour l’extraction des molécules d’intérêt (extraction solide-liquide, hydrodistillation) présentent plusieurs désavantages tels que l’utilisation des solvants coûteux et toxiques, les longues durées d’extraction et la consommation élevée en énergie. Pour cette raison plusieurs technologies innovantes non thermiques telles que les Champs Electriques Pulsés (CEP), les Décharges Électriques de Haute Tension (DEHT) et les ultrasons (US) et thermiques comme les microondes (MO) et les infrarouges (IR) ont été testées dans ce travail de thèse, pour la valorisation des coproduits d’agrumes. Les agrumes entiers (oranges, pomelos, citrons) sont traités par les CEP à une intensité de 3 kV/cm et l’extraction du jus d’agrumes et des polyphénols a été réalisée par pressage. L’étude de la perméabilisation cellulaire induite par les CEP a été réalisée par plusieurs méthodes et a montré que les degrés d’endommagement diffèrent selon le type d’agrumes traités. L’électroporation des cellules, induite par les CEP a permis d’augmenter les rendements en jus après pressage et d’améliorer le passage des polyphénols des peaux d’agrumes dans le jus. Ce qui explique la possibilité d’obtention d’un jus riche en polyphénols en traitant les agrumes par les CEP avant leur pressage. Parmi les solvants testés pour l’extraction des polyphénols à partir des peaux d’agrumes, l’eau est le moins efficace. L’ajout de 20% de glycérol dans l’eau a modifié la polarité du milieu et a amélioré l’extraction des polyphénols. L’utilisation d’un mélange enzymatique a favorisé la libération des polyphénols piégés dans les polysaccharides. Les solvants eutectiques profonds préparés, ont été aussi efficaces que les mélanges hydro éthanoliques. Pour améliorer d’avantages l’extraction dans les différents solvants verts ou dans le mélange enzymatique, les peaux d’agrumes ont été prétraitées par les DEHT dans l’eau. L’effet mécanique des DEHT, capable de fragmenter les peaux a permis d’améliorer l’extraction des polyphénols 6 dans les différents solvants. L’intensification de l’extraction des polyphénols a été aussi réalisée par les IR et les US. L’extraction des polyphénols par les IR a été optimisée en ayant recours à la méthodologie de surface de réponse. Le chauffage par les IR n’a pas altéré les polyphénols extraits qui ont gardé des activités antifongiques et anti-mycotoxinogènes importantes. Le prétraitement des peaux d’agrumes par les IR sans solvant a fragilisé les structures cellulaires, ce qui a permis d’augmenter la diffusion des polyphénols durant le traitement avec les US. / This work consists of the valorization of citrus by-products with innovative technologies. Citrus pressing produces millions of tons of waste per year worldwide. This waste (peels, pulps and seeds) is generally dedicated to animal feed or eliminated by composting or incineration. However its content in bioactive molecules leads to several ways of valorization. Since peels present about half of the citrus waste mass, studies have been focused on the valorization of citrus peels by the extraction of bioactive compounds. Conventional methods generally used for the extraction of bioactive compounds (solid-liquid extraction, hydrodistillation) have several disadvantages such as the use of expensive and toxic solvents, long extraction times and high energy consumption. For this reason, several innovative non-thermal technologies such as Pulsed Electric Fields (PEF), High Voltage Electrical Discharges (HVED) and Ultrasounds (US) and thermal treatments such as microwaves (MO) and infrared (IR) have been tested for the valorization of citrus by-products. Whole citrus fruits (oranges, pomelos, lemons) were PEF treated at an intensity of 3 kV/cm, then citrus juice and polyphenols were extracted by pressing. The study of the PEF-induced cell permeabilization was conducted by several methods and showed that the degree of damage varied according to the type of the treated fruit. The electroporation of the cells induced by the PEF, allowed an increase the juice yields after pressing and improved the liberation of the polyphenols from the citrus peels into the juice. This explains the possibility of obtaining a juice rich in polyphenols by treating the whole fruits with PEF before pressing. Among the solvents tested for the extraction of polyphenols from citrus peels, water is the least effective. The addition of 20% glycerol to water changed the polarity of the medium and improved the extraction of the polyphenols. The use of an enzyme mixture enhanced the release of the polyphenols related to the polysaccharides. Deep eutectic solvents have been as effective as hydroethanolic mixtures. To improve the yields and the kinetics of extractions in the different green solvents and in the enzyme mixture, citrus peels were pretreated with HVED in water. The mechanical effect of HVED, based on the fragmentation of the peels has improved the extraction of polyphenols in the various solvents. The intensification of polyphenols extraction was also conducted by IR and US. The extraction of polyphenols by IR was optimized using the surface response methodology. IR heating did not alter the extracted polyphenols which have significant antifungal and anti-mycotoxinogenic activities. The pretreatment of citrus peels with IR weakened the cell structures, increasing thus the diffusion of polyphenols during US treatment.

The electric Joule heating of solid materials through direct current excitation can be used to generate a temperature profile throughout a powdermetallic (P/M) compact. When recording the surface temperature distribution with an infrared (IR) camera important information regarding the integrity of the sample can be gained. This research will concentrate on the formulation of a mathematical model capable of predicting the temperature distribution and heat flow behavior in P/M parts and its relations to the supplied current, injection method, geometric shape as well as the thermo-physical properties. This theoretical model will subsequently be employed as a tool to aid in the actual measurements of infrared signatures over the sample surface and their correlation with the detection of surface and subsurface flaws. In this work we will develop the theoretical background of IR testing of green-state and sintered P/M compacts in terms of stating the governing equations and boundary conditions, followed by devising analytical and numerical solutions. Our main emphasis is placed on modeling various flaw sizes and orientations in an effort to determine flaw resolution limits as a function of minimally detectable temperature distributions. Preliminary measurements with controlled and industrial samples have shown that this IR testing methodology can successfully be employed to test both green-state and sintered P/M compacts.

"Thermal infrared (IR) imaging systems are widely used in medical, industrial, and defense applications. IR imaging systems utilize a lens to focus IR radiation onto a focal plane array (FPA) of IR detectors, which transduce the IR radiation from the scene into signals that can be further processed. In conventional IR imaging systems, electronic readout integrated circuitry (ROIC) is used to read out the information from the FPA, and computer signal processing allows for an IR image to be displayed on an electronic screen. However, the ROIC decreases the thermal isolation and sensitivity of the IR detectors in the FPA, and the computer processing and electronic display increase the cost, weight, and complexity of the IR imaging system. This thesis focuses on the development of an IR direct viewing system that does not require any ROIC, computer signal processing, or electronic display. This is accomplished through the use of microelectromechanical systems (MEMS) uncooled IR imaging detectors, which consist of arrays of bimaterial thermomechanical cantilever structures that tilt as a function of IR radiation from a scene. Other members of the WPI-ME/CHSLT group have previously shown that an interferometric optical readout mechanism based on digital holography and computer processing can eliminate the need for ROIC and be used to measure the nanometer scale tilt of the structures in a MEMS-based IR imaging system that was found to have a responsivity of 1.5 nm/K. However, these previously demonstrated results required significant computer processing and an electronic display. The hypothesis of the current work is that an optomechanical readout mechanism can be used to realize an IR direct viewer without the use of ROIC, computer signal processing, or an electronic display. Three optical readout mechanisms were identified for transducing the nanometer scale deformations of the MEMS structures in the FPA into a directly observable visible light image. Two of these, one using live holography and the other using Nomarski differential interference contrast (DIC), were based on interferometry, while the third, using reflectometry, was based on geometrical optics. The identified optical readout mechanisms were analytically evaluated based on the performance and perception of the human vision system (HVS), and preliminary experimental results were obtained using optical setups constructed for all three readout mechanisms. Based on the analytical and experimental investigations, reflectometry was selected as the most suitable readout mechanism for a direct viewer. A visible light camera was used with custom software to determine a temperature sensitivity of 137 mK for the reflectometry readout, and thermal images of scenes at human body temperature were demonstrated using limited computer processing. A false color, direct view, live IR imaging system was then demonstrated based on a two color reflectometry readout and the output was characterized with respect to the color differentiation sensitivity of the HVS. The system temperature sensitivity, based on the theoretical color differentiation sensitivity of a human observer, was found to be on the order of 10 K across a measuring range of roughly 400 °C, and objects with a temperature as low as approximately 150 °C were distinguishable. The advantages and limitations of the developed IR imaging system are identified and recommendations for further developments and future work are provided."

Made available in DSpace on 2017-07-24T19:38:04Z (GMT). No. of bitstreams: 1 Mariana Negrelli.pdf: 2632259 bytes, checksum: 8ffb18e87e90aff84b82a1268dc4596f (MD5) Previous issue date: 2011-02-25 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / This work describes the conformational analysis of cis/trans ethyl-2 hydroxycyclohexanecarboxylate. For this, were analyzed data obtained by ab initio theoretical calculations, the nuclear magnetic resonance spectroscopy (coupling constants 3JHH) and infrared (carbonyl stretch). Were performed calculations for the isolated molecule and calculations with solvation routines to assess the conformational preference in different ways. With the aid of maps of electrostatic potential, was possible to observe the main negative centers where are located the reactive sites involved in organic synthesis. According to the calculations of NBO was analyzed how interactions affect the stability of each conformation. The compounds cis/trans ethyl-2-hydroxycyclohexanecarboxylate presented each, two preferred conformers, which were observed by both theoretical calculations and IR. The NMR spectroscopy was very useful because with the use of the same was possible to characterize the majority conformer of each equilibrium. / Neste trabalho é apresentado o estudo conformacional do cis/trans-2-hidroxicicloexanocarboxilato de etila. Para tanto, foram realizadas análises a partir de dados obtidos pelos cálculos teóricos ab initio e pelas espectroscopias de ressonância magnética nuclear (constantes de acoplamento 3JHH) e na região do infravermelho (estiramento da carbonila). Foram realizados cálculos para a molécula isolada bem como cálculos com rotinas de solvatação, para avaliar a preferência conformacional em diferentes meios. Com o auxílio de mapas de potencial eletrostático, foi possível observar os principais centros negativos onde estão localizados os sítios reativos envolvidos em sínteses orgânicas. Pelos cálculos de NBO, foi analisado como as interações afetam a estabilidade de cada conformação. Os compostos cis/trans-2-hidroxicicloexanocarboxilato de etila apresentaram cada um, dois confôrmeros preferenciais, os quais foram observados tanto pelos cálculos teóricos como por IV. A espectroscopia de RMN foi muito útil, pois com o emprego da mesma foi possível caracterizar o confôrmero majoritário de cada equilíbrio.

In this thesis complexes of acylchalcogoureas with cadmium (II), lead (II) and nickel (II) have been synthesised and investigated as single source precursors for the formation of metal chalcogenide thin films viaaerosol assisted chemical vapour deposition (AACVD). Routes to binary thin films have been explored using homoleptic complexes of the general structure bis(N,N-diethyl-N'-naphthoylchalcogoureato)metal(II). Analysis of the thin films produced showed the successful deposition of the binary materials from the synthesised complexes when characterised by powder XRD, ICP-OES, SEM and EDX. Routes to ternary thin films with the general structure MExE'1-x, where M represents a metal (Cd, Ni and Pb); and E chalcogen (S or Se) have been investigated using heteroleptic metal complexes of cadmium, nickel or lead including different chalcogen containing N,N-diethyl-N'-naphthoylchalcogoureato ligands and diethyldithiocarbamate. The precursors were fully characterised and novel compounds had their crystal structures determined. The heteroleptic complexes were thermolysed by AACVD forming the MExE'1-x thin films. In the cases of lead, nickel and cadmium the thin films produced showed that the composition of the film tended heavily towards the metal selenide. Ternary films of type MS1-xSex was prepared by mixing their binary precursors of type bis(N,N-diethyl-N'-naphthoylselenoureato)metal(II) and bis(N,N-diethyl-N'-naphthoylthioureato)metal(II) [metal = Cd, Ni and Pb]. In the case of lead and cadmium chalcogenide films variation of the ratio of sulphur and selenium containing precursors allowed for the full transition in composition between metal sulphide and metal selenide. In the case of CdS1-xSexthe band gap of the films was determined from UV-visible spectroscopy to vary from 2.4 eV (CdS) to 1.7 eV(CdSe). In the case of NiS1-xSex the movement from sulphide to selenide was less simple with multiple phases of nickel chalcogenides produced.