Any center planning to install a Gamma Knife radiosurgery unit has to provide for an efficient shielding of the treatment room, to protect the patient, the staff and the public, against undesired radiation. The shielding barrier design is controlled by national and international recommendations; the reference documents for gamma ray radiotherapy facilities are the National Council on Radiation Protection and Measurements (NCRP) reports 49 and 151. However, some facts highlighted in this thesis point out that NCRP methods are ill-adapted to the Gamma Knife. Spectroscopic measurements were performed around the Gamma Knife with a Germanium detector. They revealed that the radiation field contains few high energy photons, is highly anisotropic, and that the leakage level is much lower than the NCRP estimation. These observations led to the development of a new approach to determine the necessary shielding, based on the actual and directly measurable radiation field around the unit. This method would reduce the shielding oversizing induced by the unsuitability of the NCRP recommendations for the Gamma Knife.

<p>The work in this thesis deals with pre-clinical development of rapid in vivo ³¹P mag- netic resonance spectroscopy (MRS) techniques. Current MRI literature of ³¹P spec- troscopy presents evidence of increased concentrations of phosphomonoesters (PME), and phosphodiester (PDE) as well as inorganic phosphate concentrations in tumor tissue. Human breast cancer studies have demonstrated correlation between disease progression and both PME and PDE peaks. Furthermore, ³¹P MRS can be used to detect, grade tumours and monitor response to chemo and radiation therapy.<br />Tumor measurements are typically static (i.e. single measurement per scan). In other experiments, on muscle for example, dynamic measures are required the purpose of which is to assess temporal function and recovery. In all ³¹P acquisitions there are problems surrounding RF coil design, pulse sequence speed, localization and system calibration. The work presented here focused on improving all these aspects and provide easy and reliable work flow to use ³¹P MRS in a clinical setting.<br />One of the aspects of this thesis lies in designing and construction of an RF coil that is well suited for integration with a clinical MRI breast imaging and biopsy system. The designed coil was tuned for simultaneous operation at ³¹P (51.73 MHz) and ¹H (127.88MHz) Larmor frequencies. This design has advantages in the fact that complex pulse sequences with heteronuclear decoupling could be performed easily. The additional features of the coil design is that it is possible to swap it into the breast imaging system without moving the patient. Along with the designed coil, custom software was written to assist with transmit gain calibration of ³¹P RF pulses, to ensure maximum MR signal. The automated prescan ensures easy work flow and minimizes the operator variability and patient time inside the MR scanner.<br />Another aspect of this thesis deals with rapid pulse sequence development, to further speed up the ³¹P MRS data acquisition. Echo planar spectroscopic imaging (EPSI) with a fly–back gradient trajectory is currently one of the most reliable and robust techniques for speeding up chemical shift imaging (CSI) acquisitions. A ³¹P EPSI sequence was written to acquire spectroscopic imaging data at 1, 2 and 2.6 cm spatial resolution and spectral bandwidth of 3125 Hz. The sequence showed an ability to speed up data acquisition up to 16 times, where SNR permits.<br />Phantom studies were used to verify the double tuned coil and EPSI sequence en- suring proper and safe operation. In vivo measurements of an exercising muscle demonstrated the ability of ³¹P EPSI to play an important role in rapidly acquiring spatially localized ³¹P spectroscopic data.<br />With these preclinical developments in place a clinical trial is possible using ³¹P MRS rapidly and efficiently. Furthermore the increased usability of ³¹P MRS provided by the tools developed in this thesis can prove to be beneficial by integrating ³¹P MRS into existing clinical protocols.</p> / Doctor of Science (PhD)

<p> Under 248 nm laser flash photolysis, the photodecomposition of 1,3,4-trimethyl-1-phenyl-1-germacyclopent-3-ene (28) in dry, deoxygenated hexane solution at 23 °C leads to the prompt formation of two transient species: phenylmethylgermylene (29) and its Ge=Ge doubly bonded dimer, 1,2-dimethyl-1 ,2-diphenyldigemene (30). The formation of 29 proceeds in high chemical yield as shown by the results of steady state trapping experiments with methanol and isoprene. The transient assigned to 29 exhibits λmax = 490 nm and decays with second-order kinetics (τ ~ 2 μs). The second transient, which is formed from the latter, is assigned to digermene 30 and exhibits λmax = 420 nm and a lifetime, τ ~ 8 μs. The assignments are based on comparisons to the spectra of other simple germylenes, such as dimethyl-, diphenyl and dimesitylgermylene as well as on the pattern of reactivity with trapping reagents in solution at room temperature.</p> <p> Reactions studied include N-H, O-H and Sn-H insertion reactions, the [1+2] addition to isoprene and t-butylacetylene, and halogen atom abstraction from carbon tetrachloride.</p> <p> Absolute rate constants for quenching of 29 with the above mentioned scavengers were obtained by direct measurement of the germylene decay kinetics, over the concentration range where the formation of the digermene was more than 70% quenched. This ensures that the decay of 29 was dominated by the reaction with the trapping reagent.</p> <p> Absolute rate constants for reaction of the same reagents with 30 have also been determined for most of the scavengers studied. However, the digermene was found to be considerably less reactive than phenylmethylgermylene in all cases.</p> <p> The trends in spectroscopic properties and reactivity of simple germylenes in solution are discussed.</p> / Thesis / Master of Science (MSc)

This work is concerned with the derivation of general analytical formulae for the matrix elements, in an M representation, of effective two-nucleon interaction. The anisotropic harmonic oscillator wave equation is solved in cylindrical coordinates and the subsequent wave functions used to find the desired matrix element expressions. Since these expressions are in a form conducive to rapid machine computation this representation is well suited for spectroscopic calculations for deformed nuclei. This is illustrated by the calculation of the relative Mng energies, by means of a limited Hartree—Fock method, of several nucleonic configurations in the 2s-ld shell. / Thesis / Master of Science (MS)

Mid-infrared spectroscopic imaging, which leverages the inherent vibrational contrast of chemical bonds, has been a powerful analytical tool for sample characterization. However, its use in studying living systems is limited by low spatial resolution and significant water absorption. Recently developed mid-infrared photothermal (MIP) microscopy addresses these limitations by probing the absorption-induced photothermal effect using visible light. MIP microscopy achieves sub-micrometer spatial resolution and reduces water background interference. Yet, the imaging speed of current MIP microscopy is constrained by the challenge of measuring a small modulation over the probe laser background. This low imaging throughput hinders the visualization of living dynamics, and the rich molecular information in the spectroscopic domain is obscured due to the slow acquisition process. This dissertation explores solutions for enhancing imaging speed and spectral throughput and extending MIP imaging into visualizing chemical dynamics in living systems. In the first part of the dissertation, the mid-infrared photothermal process is studied and modeled in the time, frequency, and spatial domains using heat transfer analysis. Photothermal dynamics imaging (PDI) is introduced with the ability to visualize nanosecond-scale thermodynamics in samples upon laser excitation. By capturing all higher-order harmonics, PDI achieves more than a four-fold improvement in signal-to-noise ratio compared to the lock-in method for detecting low-duty cycle photothermal signals. An imaging speed nearly two orders of magnitude faster than the lock-in counterpart has been reached. In addition, PDI captures the transient thermal field evolution, providing a tool to gauge the target’s physical properties and microenvironment. In the second part, a video-rate MIP microscope is introduced based on the PDI detection method. In the system, a synchronized IR and visible beam scanning scheme is developed, enabling photothermal detection with a single IR pulse at each pixel. Moreover, synchronized laser scanning allows uniform MIP imaging in a field of view over hundreds of micrometers while maintaining a high spatial resolution. This capability enabled the visualization of fast chemical dynamics inside living fungal cells, cancer cells, and living worms, providing an imaging platform for biology research. Having reached the speed limitation of single-pulse imaging, we further advanced the speed of spectroscopic imaging by moving beyond the conventional measurement of absorption contrast in the photothermal process. In the final part of this dissertation, we revisited the photothermal process from the perspective of energy deposition, discovering that the absorption coefficient is reflected in the slope of the heating process rather than its overall amplitude. We demonstrated mid-infrared energy deposition (MIRED) spectroscopy using a 32-channel quantum cascade laser array that emits a broadband pulse train in microseconds. With MIRED, we achieved hyperspectral mid-infrared imaging on a microsecond scale.

No / The use of Fourier-transform Raman spectroscopy for characterising lignocellulosics has increased significantly over the last twenty years. Here, an FT-Raman spectroscopic study of changes in the chemistry of waterlogged archaeological wood of Pinus sp. and Quercus sp. from a prehistoric assemblage recovered from northern Greece is presented. FT-Raman spectral features of biodeteriorated wood were associated with the depletion of lignin and/or carbohydrate polymers at various stages of deterioration. Spectra from the archaeological wood are presented alongside spectra of sound wood of the same taxa. A comparison of the relative changes in intensities of spectral bands associated with lignin and carbohydrates resulting from decay clearly indicated extensive deterioration of both the softwood and hardwood samples and the carbohydrates appear to be more deteriorated than the lignin. The biodeterioration of the archaeological timbers followed a pattern of initial preferential loss of carbohydrates causing significant loss of cellulose and hemicellulose, followed by the degradation of lignin.

No

Hydrogen peroxide (H2O2) is extensively used in a broad range of industrial and medical applications, such as aseptic processing of food and pharmaceuticals, disinfection, water treatment plants, and decontamination of industrial effluents. H2O2 is believed to be responsible for chemical degradation of polymer membranes in Polymer-Electrolyte-Membrane (PEM) fuel cells. Therefore, a versatile H2O2 sensor that functions in different environments with different conditions is of practical importance in various fields. This dissertation presents the fabrication of a fiber-optic H2O2 sensing probe (optrode) and its H2O2 sensing behavior in different conditions. An H2O2 optrode is fabricated using chemical deposition of Prussian blue (PB) onto the tip of a multimode optical fiber. Sensing tests are performed in aqueous solutions at a constant pH and different concentrations of H2O2. Sensing features of the optrode (i.e. repeatability, durability, and reproducibility) are assessed by performing multiple sensing tests with several optrodes. The results show the prepared optrode is able to detect concentrations of H2O2 in aqueous solutions at a constant pH of 4 and the optrode features a repeatable and durable response at this condition. The functionality of optrodes at different pH values is further investigated by performing additional sensing experiments. These experiments are carried out in aqueous solutions with different concentrations of H2O2 at different pH values (i.e. pH 2-7). The sensor detects the presence of H2O2 at a range of pH values. Sensing behavior of optrodes toward detection and measurement of H2O2 concentrations is studied at the pH value corresponding to an operating PEM fuel cell (i.e. pH 2). The optrode is able to detect concentrations of H2O2 at this condition with a repeatable and durable response. The stability of PB films, prepared through different conditions, is investigated to address the stability of optrodes at elevated temperatures. PB films are first deposited onto the glass slides through three different chemical processes, and then at different synthesis temperatures. The PB films are left in Phosphate-Buffer-Solutions (PBS) with pH 2 and at elevated temperatures for a day. Finally, PB films are characterized using Fourier transform infrared spectroscopy (FTIR) to analyze their stability following PBS processing at operating temperatures and pH value corresponding to an operating PEM fuel cell (i.e. 80 °C and pH 2). The results of these experiments illustrate the PB films prepared through the single-source precursor (SSP) technique and at synthesis temperatures above 60 °C remain stable after the PBS processing. The proposed optrode shows reliable sensing behavior toward detection and measurement of H2O2 concentrations in aqueous solutions at different conditions. The prepared optrode has the potential for being developed and used in different industrial and medical fields, as well as an operating PEM fuel cell, to detect and measure H2O2 concentrations. / Graduate / 0794 / 0548 / 0485 / hakbarik@uvic.ca

Cette thèse s'inscrit dans le cadre de la mission spatiale Rosetta et porte sur les propriétés spectrophotométriques de la comète 67P/Churyumov-Gerasimenko à l’aide de l’instrument OSIRIS. Cet instrument est composé de deux caméras pour les observations du noyau et de la coma de la comète. Elles permettent d’acquérir des images avec des filtres qui opèrent dans la gamme du proche UV au proche IR. Dans un premier temps, j'ai analysé les courbes spectrophotométriques des taches claires qui sont apparues sur le noyau de la comète. Une étude comparative de celles-ci grâce aux données du spectro-imageur VIRTIS a ainsi permis de constater que les taches claires sont liées à la glace de H2O. Dans un second temps, j’ai entrepris une étude spectrophotométrique de la région Khonsu, qui a mis en évidence les variations saisonnières de la pente spectrale de différents terrains. Par la suite, j’ai élargi mon analyse des taches à tout le noyau de la comète. J’ai détecté plus de 50 taches claires dues à la présence de glace de H2O et j’ai produit une carte pour repérer leurs emplacements sur le noyau, afin d’étudier plus en détail leur répartition et leur évolution au cours de temps. Ceci m’a permis d’identifier quatre types de taches regroupés en fonction de leur morphologie et de constater qu'elles sont dues à différentes sources d'activité cométaire. / This thesis is based on the spectrophotometric properties of the comet 67P/Churyumov-Gerasimenko, using the OSIRIS instrument of Rosetta space mission. Composed of two scientific cameras to observe the nucleus and the coma of the comet, OSIRIS images are acquired with multiple filters, that span the near-UV to near-IR wavelength range. They were used to study the spectrophotometric curves of the exposed bright features that appeared on the surface of the cometary nucleus, leading to a comparative study, that was carried out in collaboration with the VIRTIS spectro-imager aboard Rosetta, that demonstrated, that these exposures are related to H2O ice, using its absorption band located at 2 microns. The thesis further details a spectrophotometric study of the Khonsu region in the southern latitudes of the comet, where the seasonal variation of the spectral slope of different types of terrains is explored. Finally, the results of an extended survey of exposed bright features are presented. More than 50 individual features are presented under four morphologies along with an albedo calculation, suggesting that different activity sources are responsible for their appearance on the nucleus.

[ES] Esta tesis se ha centrado en el modelado, diseño y demostración experimental de un sensor espectroscópico integrado basado en un AWG (del inglés Arrayed Waveguide Grating). El dispositivo ha sido diseñado y fabricado en una nueva plataforma de nitruro de silico (Si3N4) en oxido de silico (SiO2) desarrollada en España. El trabajo realizado en esta tesis se puede dividir en dos secciones principalmente. En la primera parte, se describe el panorama general de las plataformas de Si3N4 existentes y su estado del arte, junto con la descripción de los procesos de fabricación y caracterización de nuestra plataforma de Si3N4 con 300 nm de altura en la capa de guiado. En la segunda parte, se presenta el dispositivo bautizado como Integrated Optical Spectroscopic Sensor (IOSS). El IOSS consiste en un AWG cuyo conjunto de guías de onda está dividido en dos subgupos diseñados para replicar los canales del AWG. Las guías de uno de los subgrupos contienen ventanas de sensado, que están definidas por secciones en las que el núcleo de las guías está al descubierto y, por tanto, en contacto con el medio que las rodea. De esta manera, el sensado se lleva a cabo mediante la interacción del campo evanescente con la muestra depositada. Las guías del segundo subconjunto permanecen inalteradas. Por lo tanto, el dispositivo proporciona al mismo tiempo los espectros de sensado y de referencia. El modelo matemático del IOSS, su procedimiento de diseño y la prueba de concepto del sensor configurado para espectroscopía de absorción se describen en esta tesis. / [CAT] La present tesi s'ha centrat en el modelatge, disseny i demostració experimental d'un sensor espectroscòpic integrat basat en un AWG (de l'anglès Arrayed Waveguide Grating). El dispositiu ha sigut dissenyat i fabricat en una nova plataforma de nitrur de silici (Si3N4) en òxid de silici (SiO2) desenvolupada a Espanya. El treball realitzat en aquesta tesi es pot dividir en dues seccions principalment. En la primera part, es descriu el panorama general de les plataformes de Si3N4 existents i el seu estat de l'art, juntament amb la descripció dels processos de fabricació i caracterització de la nostra plataforma de Si3N4 amb 300 nm d'altura en la capa de guiat. En la segona part, es presenta el dispositiu batejat com Integrated Optical Spectroscopic Sensor (IOSS). El IOSS consisteix en un AWG en el que el seu conjunt de guies d'ona està dividit en dos subgrups dissenyats per a replicar els canals del AWG. Les guies d'un dels subgrups conté finestres de detecció, que estan definides per seccions en les quals el nucli de les guies d'ona està al descobert i en contacte amb el mitjà que li envolta. D'aquesta manera, la detecció es duu a terme mitjançant la interacció del camp evanescent amb la mostra depositada. Les guies del segon subconjunt romanen inalterades. Per tant, el dispositiu proporciona al mateix temps els espectres de detecció de referència. El model matemàtic del IOSS, el seu procediment de disseny i la prova de concepte del sensor configurat per a espectroscopia d'absorció es descriuen en aquesta tesi. / [EN] This thesis is focused on the model, design and experimental demonstration of an integrated spectroscopic sensor based on a modified Arrayed Waveguide Grating (AWG). The device has been designed and fabricated in a new silicon nitride (Si3N4) on silicon oxide (SiO2) platform developed in Spain. The work performed for this thesis can be then divided into two main sections. In the first part, an overview of the existing Si3N4 platforms and their state of art is described, alongside the report on the fabrication and characterization of our 300 nm guiding film height Si3N4 platform. On the second part, the device named Integrated Optical Spectroscopic Sensor (IOSS) is presented. The IOSS consists of an AWG which arrayed waveguides are divided into two sub-sets engineered to replicate the AWG channels. The waveguides of one of the sub-sets contain sensing windows, defined as waveguides sections which core is in contact with the surrounding media. Thus, the sensing is performed through evanescent field interaction with the sample deposited. The waveguides from the second sub-set remain isolated. Therefore, the device provides both sensing and reference spectra. The IOSS mathematical model, design procedure and proof of concept configured for absorption spectroscopy are reported in this thesis. / Micó Cabanes, G. (2020). Integrated Spectroscopic Sensor fabricated in a novel Si3N4 platform [Tesis doctoral]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/159381