Adubação de capim-elefante com composto orgânico produzido com resíduos animais.

Resumo: A utilização do composto orgânico proveniente de resíduos da criação e abate de pequenos ruminantes pode elevar a produção de matéria seca do capim-elefante, tendo em vista o teor de nutrientes contidos nesse fertilizante orgânico, diminuindo os impactos da produção animal sobre o ambiente e reduzindo os custos de produção na área de capineira de capim-elefante. Dada à escassez de informações na literatura e a importância do manejo adequado da adubação orgânica na agropecuária, objetivou-se avaliar os atributos químicos e físicos do solo, o estado nutricional e a produção do capim-elefante submetido à aplicação de doses do composto orgânico proveniente de resíduos da produção e abate de pequenos ruminantes. O delineamento experimental adotado foi em parcelas subdivididas, com medidas repetidas no tempo, sendo as parcelas as doses (0; 13,3; 26,6; 39,9; 52,3; 79,8 t ha-1 ) de composto orgânico e um tratamento adicional com adubos minerais e as subparcelas os ciclos (1, 2, 3 e 4) com 4 blocos, totalizando 28 parcelas. As variáveis mensuradas foram atributos físicos e químicos do solo, a diagnose foliar e a produtividade de capim-elefante. Para o fator ciclo, a adubação orgânica incrementou a umidade gravimétrica e umidade volumétrica e ainda houve diminuição da densidade de partículas em função dos ciclos. Com as doses do fertilizante orgânico houve aumento nas concentrações da matéria orgânica, amônio, nitrato, amônio + nitrato, fósforo e saturação por base; houve redução do valor da acidez potencial, além da elevação dos teores de nitrogênio e fósforo nas plantas. As doses de composto orgânico aumentaram a biomassa de forragem total de capim elefante. A adubação mineral proporcionou maior incremento da produção do capim em relação à adubação orgânica no decorrer dos ciclos. Abstract: The use of organic compost from residues of production and slaughter of small ruminants can increase dry matter production of elephant grass, in due function of quantity nutrients in this compost, thus reducing the animal production impacts in the environment and production costs in elephant grass fields. Due to the Lack of information in literature and the importance regarding organic fertilization in agriculture, the aim of this work was evaluate chemical and physical soil attributes, nutritional status in plants and production of elephant grass in function of doses of organic compound of residues of production and slaughter of small ruminants. The experimental design was in split-plot, with the main treatment the doses (0; 13,3; 26,6; 39,9; 52,3; 79,8 t ha-1 ) of organic compost and one additional treatment with mineral fertilization and secondary treatments was the cycles (1, 2, 3 and 4) with 4 blocks, and 28 plots. The measured variables were physical and chemical attributes in the soil, nutritional diagnosis in plants and production of elephant grass. For cycle factor the organic fertilization increased gravimetric and volumetric humidity, yet, occurred decrease of density in function of cycles. With the doses of organic compost increased organic matter, ammonium, nitrate, ammonium + nitrate, phosphor and base saturation; and decreased the value of potential acidity; and increased content of N and P in plants. The doses of organic compost increased the elephant grass production. The mineral fertilization increased the elephant grass production in relation of organic fertilization over the cycles.

Complexes cationiques POCOP de nickel : synthèse, caractérisation, réactivité et étude catalytique

Ce mémoire traite de la chimie des complexes pinceurs de nickel (II) cationiques ayant un ligand de type POCOP. Elle se divise en deux parties. La première traite de la synthèse, de la caractérisation et de la réactivité des complexes cationiques pinceurs de Ni(II) de type POCOP (POCOP = 1,3-bis(phosphinitobenzene), où C fait partie d’un cycle benzénique et est lié au métal, et P est un ligand phosphoré aussi lié au métal). Ces complexes ont un ligand acétonitrile coordonné au centre métallique et sont du type [(R-POCOPR’)Ni(NCMe)][OSO2CF3], où R est un substituant du cycle benzénique et R’ est un substituant sur le ligand phosphoré (R’ = iPr: R = H (1), p-Me(2), p-OMe(3), p-CO2Me(4), p-Br(5), m,m-tBu2(6), m-OMe(7), m-CO2Me(8); R’ = t-Bu : R = H (9), p-CO2Me(10)). Les complexes cationiques sont préparés en faisant réagir le dérivé Ni(II) neutre correspondant R-(POCOPR’)Ni-Br avec Ag(OSO2CF3¬) dans l’acétonitrile à température ambiante. L’impact des groupements R et R’ du ligand POCOP sur la structure et sur les propriétées électroniques du complexe a été étudié par spectroscopies RMN, UV-VIS et IR, analyse électrochimique, et diffraction des rayons X. Les valeurs de fréquence du lien C≡N (ν(C≡N)) augmentent avec le caractère électroattracteur du complexe, dans l’ordre 7 < 3 ~ 2 ~ 6 < 1 < 5 ~ 8 < 4 et 9 < 10. Ces résultats sont en accord avec le fait qu’une augmentation du caractère électrophile du centre métallique devrait résulter en une augmentation de la donation σ MeCN→Ni. De plus, les complexes cationiques montrent tous un potentiel d’oxydation Ni(II)/Ni(III) plus élevé que leurs analogues neutres Ni-Br. Ensuite, une étude d’équilibre entre un complexe neutre (R-POCOPR’)NiBr et un complexe cationique [(R-POCOPR’)Ni(NCMe)][OSO2CF3] démontre l’échange facile des ligands MeCN et Br. La deuxième partie de ce mémoire consiste en deux chapitres. Le premier (Chapitre 3) est une étude structurelle permettant une meilleure compréhension du mécanisme d’hydroamination des oléfines activées promue par les complexes présentés au chapitre 1, suivi de tentatives de synthèse de nouveaux composés POCOP cationiques comportant un ligand amine et nitrile, et de déplacement du groupement amine par un groupement nitrile. Le deuxième chapitre (4) décrit la réactivité et la cinétique de la réaction d’hydroamination et d’hydroalkoxylation d’oléfines activées, qui permet ainsi de mieux comprendre l’impact des différentes variables du système (groupements R et R’, température, substrats, solvent, etc.) sur la réactivité catalytique.

Applications of advanced and dual energy computed tomography in proton therapy

This thesis focuses on advanced reconstruction methods and Dual Energy (DE) Computed Tomography (CT) applications for proton therapy, aiming at improving patient positioning and investigating approaches to deal with metal artifacts. To tackle the first goal, an algorithm for post-processing input DE images has been developed. The outputs are tumor- and bone-canceled images, which help in recognising structures in patient body. We proved that positioning error is substantially reduced using contrast enhanced images, thus suggesting the potential of such application. If positioning plays a key role in the delivery, even more important is the quality of planning CT. For that, modern CT scanners offer possibility to tackle challenging cases, like treatment of tumors close to metal implants. Possible approaches for dealing with artifacts introduced by such rods have been investigated experimentally at Paul Scherrer Institut (Switzerland), simulating several treatment plans on an anthropomorphic phantom. In particular, we examined the cases in which none, manual or Iterative Metal Artifact Reduction (iMAR) algorithm were used to correct the artifacts, using both Filtered Back Projection and Sinogram Affirmed Iterative Reconstruction as image reconstruction techniques. Moreover, direct stopping power calculation from DE images with iMAR has also been considered as alternative approach. Delivered dose measured with Gafchromic EBT3 films was compared with the one calculated in Treatment Planning System. Residual positioning errors, daily machine dependent uncertainties and film quenching have been taken into account in the analyses. Although plans with multiple fields seemed more robust than single field, results showed in general better agreement between prescribed and delivered dose when using iMAR, especially if combined with DE approach. Thus, we proved the potential of these advanced algorithms in improving dosimetry for plans in presence of metal implants.

Complexes cationiques POCOP de nickel : synthèse, caractérisation, réactivité et étude catalytique

Ce mémoire traite de la chimie des complexes pinceurs de nickel (II) cationiques ayant un ligand de type POCOP. Elle se divise en deux parties. La première traite de la synthèse, de la caractérisation et de la réactivité des complexes cationiques pinceurs de Ni(II) de type POCOP (POCOP = 1,3-bis(phosphinitobenzene), où C fait partie d’un cycle benzénique et est lié au métal, et P est un ligand phosphoré aussi lié au métal). Ces complexes ont un ligand acétonitrile coordonné au centre métallique et sont du type [(R-POCOPR’)Ni(NCMe)][OSO2CF3], où R est un substituant du cycle benzénique et R’ est un substituant sur le ligand phosphoré (R’ = iPr: R = H (1), p-Me(2), p-OMe(3), p-CO2Me(4), p-Br(5), m,m-tBu2(6), m-OMe(7), m-CO2Me(8); R’ = t-Bu : R = H (9), p-CO2Me(10)). Les complexes cationiques sont préparés en faisant réagir le dérivé Ni(II) neutre correspondant R-(POCOPR’)Ni-Br avec Ag(OSO2CF3¬) dans l’acétonitrile à température ambiante. L’impact des groupements R et R’ du ligand POCOP sur la structure et sur les propriétées électroniques du complexe a été étudié par spectroscopies RMN, UV-VIS et IR, analyse électrochimique, et diffraction des rayons X. Les valeurs de fréquence du lien C≡N (ν(C≡N)) augmentent avec le caractère électroattracteur du complexe, dans l’ordre 7 < 3 ~ 2 ~ 6 < 1 < 5 ~ 8 < 4 et 9 < 10. Ces résultats sont en accord avec le fait qu’une augmentation du caractère électrophile du centre métallique devrait résulter en une augmentation de la donation σ MeCN→Ni. De plus, les complexes cationiques montrent tous un potentiel d’oxydation Ni(II)/Ni(III) plus élevé que leurs analogues neutres Ni-Br. Ensuite, une étude d’équilibre entre un complexe neutre (R-POCOPR’)NiBr et un complexe cationique [(R-POCOPR’)Ni(NCMe)][OSO2CF3] démontre l’échange facile des ligands MeCN et Br. La deuxième partie de ce mémoire consiste en deux chapitres. Le premier (Chapitre 3) est une étude structurelle permettant une meilleure compréhension du mécanisme d’hydroamination des oléfines activées promue par les complexes présentés au chapitre 1, suivi de tentatives de synthèse de nouveaux composés POCOP cationiques comportant un ligand amine et nitrile, et de déplacement du groupement amine par un groupement nitrile. Le deuxième chapitre (4) décrit la réactivité et la cinétique de la réaction d’hydroamination et d’hydroalkoxylation d’oléfines activées, qui permet ainsi de mieux comprendre l’impact des différentes variables du système (groupements R et R’, température, substrats, solvent, etc.) sur la réactivité catalytique.

Adubação de capim-elefante com composto orgânico produzido com resíduos animais.

A utilização do composto orgânico proveniente de resíduos da criação e abate de pequenos ruminantes pode elevar a produção de matéria seca do capim-elefante, tendo em vista o teor de nutrientes contidos nesse fertilizante orgânico, diminuindo os impactos da produção animal sobre o ambiente e reduzindo os custos de produção na área de capineira de capim-elefante. Dada à escassez de informações na literatura e a importância do manejo adequado da adubação orgânica na agropecuária, objetivou-se avaliar os atributos químicos e físicos do solo, o estado nutricional e a produção do capim-elefante submetido à aplicação de doses do composto orgânico proveniente de resíduos da produção e abate de pequenos ruminantes. O delineamento experimental adotado foi em parcelas subdivididas, com medidas repetidas no tempo, sendo as parcelas as doses (0; 13,3; 26,6; 39,9; 52,3; 79,8 t ha-1) de composto orgânico e um tratamento adicional com adubos minerais e as subparcelas os ciclos (1, 2, 3 e 4) com 4 blocos, totalizando 28 parcelas. As variáveis mensuradas foram atributos físicos e químicos do solo, a diagnose foliar e a produtividade de capim-elefante. Para o fator ciclo, a adubação orgânica incrementou a umidade gravimétrica e umidade volumétrica e ainda houve diminuição da densidade de partículas em função dos ciclos. Com as doses do fertilizante orgânico houve aumento nas concentrações da matéria orgânica, amônio, nitrato, amônio + nitrato, fósforo e saturação por base; houve redução do valor da acidez potencial, além da elevação dos teores de nitrogênio e fósforo nas plantas. As doses de composto orgânico aumentaram a biomassa de forragem total de capimelefante. A adubação mineral proporcionou maior incremento da produção do capim em relação à adubação orgânica no decorrer dos ciclos. Abstract: The use of organic compost from residues of production and slaughter of small ruminants can increase dry matter production of elephant grass, in due function of quantity nutrients in this compost, thus reducing the animal production impacts in the environment and production costs in elephant grass fields. Due to the Lack of information in literature and the importance regarding organic fertilization in agriculture, the aim of this work was evaluate chemical and physical soil attributes, nutritional status in plants and production of elephant grass in function of doses of organic compound of residues of production and slaughter of small ruminants. The experimental design was in split-plot, with the main treatment the doses (0; 13,3; 26,6; 39,9; 52,3; 79,8 t ha-1 ) of organic compost and one additional treatment with mineral fertilization and secondary treatments was the cycles (1, 2, 3 and 4) with 4 blocks, and 28 plots. The measured variables were physical and chemical attributes in the soil, nutritional diagnosis in plants and production of elephant grass. For cycle factor the organic fertilization increased gravimetric and volumetric humidity, yet, occurred decrease of density in function of cycles. With the doses of organic compost increased organic matter, ammonium, nitrate, ammonium + nitrate, phosphor and base saturation; and decreased the value of potential acidity; and increased content of N and P in plants. The doses of organic compost increased the elephant grass production. The mineral fertilization increased the elephant grass production in relation of organic fertilization over the cycles.

Hybrid lead-halide perovskites as novel materials for thin film direct and flexible ionizing radiation detectors

Ionizing radiations are important tools employed every day in the modern society. For example, in medicine they are routinely used for diagnostic and therapy. The large variety of applications leads to the need of novel, more efficient, low-cost ionizing radiation detectors with new functionalities. Personal dosimetry would benefit from wearable detectors able to conform to the body surfaces. Traditional semiconductors used for ionizing radiation direct detectors offer high performance but they are intrinsically stiff, brittle and require high voltages to operate. Hybrid lead-halide perovskites emerged recently as a novel class of materials for ionizing radiation detection. They combine high absorption coefficient, solution processability and high charge transport capability, enabling efficient and low-cost detection. The deposition from solution allows the fabrication of thin-film flexible devices. In this thesis, I studied the detection properties of different types of hybrid perovskites, deposited from solution in thin-film form, and tested under X-rays, gamma-rays and protons beams. I developed the first ultraflexible X-ray detector with exceptional conformability. The effect of coupling organic layers with perovskites was studied at the nanoscale giving a direct demonstration of trap passivation effect at the grain boundaries. Different perovskite formulations were deposited and tested to improve the film stability. I report about the longest aging studies on perovskite X-ray detectors showing that the addition of starch in the precursors’ solution can improve the stability in time with only a 7% decrease in sensitivity after 630 days of storage in ambient conditions. 2D perovskites were also explored as direct detector for X-rays and gamma-rays. Detection of 511 keV photons by a thin-film device is here demonstrated and was validated for monitoring a radiotracer injection. At last, a new approach has been used: a 2D/3Dmixed perovskite thin-film demonstrated to reliably detect 5 MeV protons, envisioning wearable dose monitoring during proton/hadron therapy treatments.

Conceptual design of the integral measurement system of the radiation dose of the fuel elements for the ALFRED reactor.

Conceptual design of the integral measurement system of the radiation dose of the fuel elements for the ALFRED reactor.

Study of high-quality ALD gate dielectrics in radiation sensitive oxide field effect transistors

Radiation dosimetry is crucial in many fields, where the exposure of ionizing radiation must be precisely controlled to avoid health and environmental safety issues. Radiotherapy and radioprotection are two examples in which fast and reliable detectors are needed. Compact and large area wearable detectors are being developed to address real-life radiation dosimetry applications, their ideal properties include flexibility, lightness, and low-cost. This thesis contributed to the development of Radiation sensitive OXide Field Effect Transistors (ROXFETs), which are detectors able to provide fast and real-time radiation read out. ROXFETs are based on thin film transistors fabricated with high-mobility amorphous oxide semiconductor, making them compatible with large area, flexible, and low cost production over plastic substrates. The gate dielectric material has high dielectric constant and high atomic number, which results in high performances and high radiation sensitivity, respectively. The aim of this work was to establish a stable and reliable fabrication process for ROXFETs made with atomic layer deposited gate dielectric. A study on the effect of gate dielectric materials was performed, focusing the attention on the properties of the dielectric-semiconductor interface. Single and multi layer dielectric structures were compared during this work. Furthermore, the effect of annealing temperature was studied. The device performances were tested to understand the underlying physical processes. In this way, it was possible to determine a reliable fabrication procedure and an optimal structure for ROXFETs. An outstanding sensitivity of (65±3)V/Gy was measured in detectors with a bi-layer Ta₂O₅-Al₂O₃ gate dielectric with low temperature annealing performed at 180°C.

Dosimetric optimization of CT protocols for the preoperative planning of hip arthroplasty

Radiation dose in x-ray computed tomography (CT) has become a topic of great interest due to the increasing number of CT examinations performed worldwide. In fact, CT scans are responsible of significant doses delivered to the patients, much larger than the doses due to the most common radiographic procedures. This thesis work, carried out at the Laboratory of Medical Technology (LTM) of the Rizzoli Orthopaedic Institute (IOR, Bologna), focuses on two primary objectives: the dosimetric characterization of the tomograph present at the IOR and the optimization of the clinical protocol for hip arthroplasty. In particular, after having verified the reliability of the dose estimates provided by the system, we compared the estimates of the doses delivered to 10 patients undergoing CT examination for the pre-operative planning of hip replacement with the Diagnostic Reference Level (DRL) for an osseous pelvis examination. Out of 10 patients considered, only for 3 of them the doses were lower than the DRL. Therefore, the necessity to optimize the clinical protocol emerged. This optimization was investigated using a human femur from a cadaver. Quantitative analysis and comparison of 3D reconstructions were made, after having performed manual segmentation of the femur from different CT acquisitions. Dosimetric simulations of the CT acquisitions on the femur were also made and associated to the accuracy of the 3D reconstructions, to analyse the optimal combination of CT acquisition parameters. The study showed that protocol optimization both in terms of Hausdorff distance and in terms of effective dose (ED) to the patient may be realized simply by modifying the value of the pitch in the protocol, by choosing between 0.98 and 1.37.

Characterization of a prototype for cone beam breast computed tomography

The project aims to experiment the Cone Beam Breast Computed Tomography technique using a standard digital mammography system. The work is focused on the definition of a protocol of quality measurements for the pre-clinical evaluation of the machine. The paper is developed in two parts. The first is specifically concerned with the methods used to define the image quality and dosimetry aspects specific for digital mammography devices. A complete characterization of the system has been performed according to the applicable IEC standards to assure the performances of the equipment and define the quality levels. Due to the lack of a quality control protocol dedicated to CBBCT mammography scanner, a new equivalent test procedure has been proposed. The second part of the paper is focused on the evaluation, through quantitative and visual analyzes, of the CBCT exam feasibility in the hardware and software conditions currently proposed by IMS Giotto. The prototype was in fact developed differing from the technical choices of competing companies and developed for a different intended use. The main difference with respect to the existing breast CT scanners is the possibility of performing on the same system the CBBCT scanning but also all the mammographic techniques. In this thesis, we aim to assess whether, in the current setup, considering a dosimetric range very close to that used in the clinic, the tests produce results that can be considered acceptable or at least indicative of the feasibility of the entire project from a commercial point of view. For this purpose, the final reconstruction images, obtained by two previously developed software, are analyzed.