Im Rahmen dieser Arbeit wurden neuartige, temperatursensitive Polymerbürsten mit terminaler Click-Funktionalität hergestellt, die nicht nur im Detail untersucht bzw. charakterisiert wurden, sondern deren Eigenschaften zusätzlich durch die polymeranaloge Umsetzung mit einem entsprechend modifizierten Fluoreszenzfarbstoff, Polymer oder mit superparamagnetischen Nanopartikeln erweitert werden konnten. Mittels kontrolliert radikalischer Polymerisation wurde mono- und bi-funktionalisiertes Poly(N-isopropylacrylamid) mit unterschiedlichen Endgruppen und Molekulargewichten synthetisiert und über das "grafting to"-Verfahren an eine Modeloberfläche angebunden. Die kovalente Anbindung der entsprechenden Komponenten erfolgte entweder durch die Kupfer-katalysierte oder thermisch induzierte Alkin-Azid-Cycloaddition. Neben den physiko-chemischen Eigenschaften wurde im Besonderen das temperaturabhängige Schaltverhalten dieser funktionellen Polymerbürsten in situ untersucht, wobei neben der spektroskopischen Ellipsometrie als Hauptmethode, zusätzlich Rasterkraftmikroskopie, UV/VIS- und Fluoreszenzspektroskopie, sowie Elektronenmikroskopie verwendet wurden. Im Fall der Farbstoff-modifizierten Polymerbürsten zeigte sich, dass nicht nur die Eigenschaften des Farbstoffs durch das Polymer beeinflussbar sind, sondern auch das Quellverhalten der Polymerbürsten durch den Farbstoff. Die mit Nanopartikeln modifizierten Polymerbürsten zeigten eine homogene Verteilung der Partikel auf der Oberfläche, sowie eine veränderte Schaltcharakteristik, die durch das Auftreten eine dynamischen Wechselwirkungszone zwischen den Polymerbürsten und den Nanopartikeln erklärt werden kann. Mit Hilfe der thermisch induzierten Azid-Alkin-Cycloaddition konnten erstmalig definierte Kettenverlängerungen an Polymerbürsten durchgeführt und gleichzeitig der Nachteil der limitierten Pfropfungsdichte der „grafting to“-Methode überwunden werden. Darüber hinaus konnte der temperaturinduzierte Schalteffekt nicht nur erhalten bleiben, sondern in Bezug auf die Schaltamplitude auch signifikant vergrößert werden und ergab ein sensitiveres, verbessertes Polymerbürstensystem.

The dissertation work focuses on the whole route of material development starting from the investigations of properties of the initial (raw) HBPs to their applications. Each research step is given in a separate chapter to enhance attention to various aspects of the aim of the work. Thus, every chapter is started with an introduction. After that, the methods applied and experimental procedure are described. Next part tries to give the comprehensive description of the results obtained. At the end of the chapter, the main points are summarized. The Chapter 1 gives the theoretical description of the main experimental techniques used in this work. In Chapter 2 the chemical (chemical composition, purity, typical structure elements) and physical (glass transition temperature, the temperature of the maximum decomposition, the thermal stability at the high temperatures, molar mass, polydispersity and possible aggregation in solution) properties examined by different techniques of polymer analysis are described. The Chapter 3 is divided into three separate parts: In Chapter 3.1 the description of the formation and modification of inter- and intramolecular hydrogen bonds of hydroxyl terminated HBP is presented to reveal the information of hydroxyl groups re- and/or association due to the high temperatures applied. In Chapter 3.2 the nature of the solid-liquid interface of HBP thin films have been studied by different surface sensitive techniques with respect to further protein adsorption investigations. In Chapter 3.3 the strategy for the fabrication of surface attached carboxyl terminated HBP using "grafting to" technique is developed. The Chapter 4 consists of two parts: The first (theoretic) part outlines the basic principles of protein chemistry, factors influencing on the protein molecule stability in aqueous medium, the mechanism of protein adsorption and forces involved in the adsorption process. In the second part the combination of different in situ techniques was applied to obtain a comprehensive description of complex adsorption processes of protein molecules on different polymer surfaces.

Nous savons que la grande majorité des étoiles WC9 produit de la poussière à base de carbone. Cette dernière doit se former dans des zones de très haute densité afin de survivre à l’environnement hostile qu’est celui du vent d’une étoile WR. Les étoiles WC appartenant à un système binaire WR + O produisent de la poussière quand les vents des deux étoiles entrent en collision et forment une zone de choc pouvant augmenter la densité du gaz d’un facteur 1000. Par contre, plusieurs étoiles WC9 n’ont, à ce jour, montré aucun signe de la présence d’un compagnon. Le but du projet est de tenter d’identifier un mécanisme alternatif responsable de la formation de poussière dans les étoiles WC9 n’appartenant pas à un système binaire. Nous présentons les résultats d’une campagne d’observation visant à caractériser la variabilité spectroscopique d’un échantillon de huit étoiles WC9 et une étoile WC8d. Nos résultats indiquent que la majorité des étoiles montrent des variations à grande échelle dans la raie d’émission C III 5696, soit à un niveau d’au moins 5% du flux de la raie et que les structures dans le vent ont une dispersion de vitesses de l’ordre de 150-300 km/s. De manière générale, les variations de vitesse radiales sont anti-corrélées avec le coefficient d’asymétrie de la raie, ce qui semble infirmer la présence d’un compagnon. Des observations en photométrie de l’étoile WR103 montrent une période de 9.1 ± 0.6 jours qui s’accorde avec les variations spectroscopiques et qui ne semble pas, de manière évidente, d’origine binaire. / We know that the majority of WC9 stars produces carbon-based dust. To survive in the hot and harsh environement that is the wind of a WR star, the dust grains must be formed in regions of very high density. We know that WC stars that are part of a WR + O system can produce dust at periastron passage where the collision of the two stellar winds is strong enough to produce shocks that compress the gas to densities up to a factor 103 higher than that of the WR star. However, so far, many WC9 stars have shown no signs of a companion. The goal of the current project is to identify a mechanism that could be responsible for the formation of dust in single WC9 stars. We present the results of an observing campaign which aimed to characterize the spectroscopic variability of eight WC9 stars and one WC8d star. Our results indicate that most stars show large scale variations of their C III 5696 emission line that reach at least 5% of the total line flux, and that the structures in the wind have a mean velocity dispersion of 150-300 km/s. In general, the radial velocity variations are anti-correlated with the skewness variations. This seems to indicate that the variations are not due to the presence of a companion. Photometric observations of WR 103 show a period of 9.1 ± 0.6 days that agrees with the spectroscopic variations and does not seem from binary origin.

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal

Mémoire numérisé par la Division de la gestion de documents et des archives de l'Université de Montréal

Prostate cancer is the most common malignancy afflicting Canadian men in 2011. Physicians use digital rectal exams (DRE), blood tests for prostate specific antigen (PSA) and transrectal ultrasound (TRUS)-guided biopsies for the initial diagnosis of prostate cancer. None of these tests detail the spatial extent of prostate cancer - information critical for using new therapies that can target cancerous prostate. With an MRI technique called proton magnetic resonance spectroscopic imaging (1H-MRSI), biochemical analysis of the entire prostate can be done without the need for biopsy, providing detailed information beyond the non-specific changes in hardness felt by an experienced urologist in a DRE, the presence of PSA in blood, or the “blind-guidance” of TRUS-guided biopsy. A hindrance to acquiring high quality 1H-MRSI data comes from signal originating from fatty tissue surrounding prostate that tends to mask or distort signal from within the prostate, thus reducing the overall clinical usefulness of 1H-MRSI data. This thesis has three major areas of focus: 1) The development of an optimized 1H-MRSI technique, called conformal voxel magnetic resonance spectroscopy (CV-MRS), to deal the with removal of unwanted lipid contaminating artifacts at short and long echo times. 2) An in vivo human study to test the CV-MRS technique, including healthy volunteers and cancer patients scheduled for radical prostatectomy or radiation therapy. 3) A study to determine the efficacy of using the 1H-MRSI data for optimized radiation treatment planning using modern delivery techniques like intensity modulated radiation treatment. Data collected from the study using the optimized CV-MRS method show significantly reduced lipid contamination resulting in high quality spectra throughout the prostate. Combining the CV-MRS technique with spectral-spatial excitation further reduced lipid contamination and opened up the possibility of detecting metabolites with short T2 relaxation times. Results from the in vivo study were verified with post-histopathological data. Lastly, 1H-MRSI data was incorporated into the radiation treatment planning software and used to asses tumour control by escalating the radiation to prostate lesions that were identified by 1H-MRSI. In summary, this thesis demonstrates the clinical feasibility of using advanced spectroscopic imaging techniques for improved diagnosis and treatment of prostate cancer.

ν Octantis is a spectroscopic binary with a semi-major axis and period of 2.55 AU and 2.9 years, respectively. Ramm et al. (2009) discovered a 52 ms^(-1) radial-velocity (RV) perturbation with a period of 417 days in this system. All evidence, both photometric and spectroscopic, suggests the perturbation is the result of a 2.5 MJ planet orbiting the primary star. However, when assuming a “normal” prograde coplanar orbit, celestial mechanics predicts this orbit is unstable, contradicting the observed stability. Simulations by Eberle and Cuntz (2010) showed a retrograde orbit for the planet to be stable for at least 10^7 years. In this thesis, we performed a 10^8 -yr simulation of the retrograde orbit, and found it remained stable. Simulations over a range of planetary semi-major axes, eccentricities, and primary/secondary masses showed that stable retrograde orbits are not possible past a semi-major axis of 1.315 +/- 0.092 AU . Therefore, planetary retrograde orbits are most likely inherently more stable than prograde orbits owing to the absence of stability at known mean-motion resonances. Eccentricity simulations showed that the period of the planet's dominant eccentricity variation is related to the planet's semi-major axis by a second order exponential. However, retrograde orbits tend to have longer eccentricity periods than prograde orbits at the same semi-major axis. There is also evidence that this eccentricity period is connected to the orbital stability. By fitting a keplerian to both Ramm et al. (2009) and current radial velocities, the period of the ν Octantis binary was determined to be 1050.04 +/- 0.02 days with an eccentricity of 0.2359 +/- 0.001 . The planetary orbital solution for just the data reduced in this thesis gave a period of 416.9 +/- 2.1 days and an eccentricity of 0.099 +/- 0.015 , with an RMS scatter of 9.6 ms^(-1). Therefore, the orbital elements are within 1σ of the Ramm et al. (2009) elements. Assuming a retrograde coplanar orbit about the primary star then the planet has a mass of M_pl = 2.3 M_J and a semi-major axis of a_pl = 1.21 +/- 0.09 AU.

Prostate cancer is the most common malignancy afflicting Canadian men in 2011. Physicians use digital rectal exams (DRE), blood tests for prostate specific antigen (PSA) and transrectal ultrasound (TRUS)-guided biopsies for the initial diagnosis of prostate cancer. None of these tests detail the spatial extent of prostate cancer - information critical for using new therapies that can target cancerous prostate. With an MRI technique called proton magnetic resonance spectroscopic imaging (1H-MRSI), biochemical analysis of the entire prostate can be done without the need for biopsy, providing detailed information beyond the non-specific changes in hardness felt by an experienced urologist in a DRE, the presence of PSA in blood, or the “blind-guidance” of TRUS-guided biopsy. A hindrance to acquiring high quality 1H-MRSI data comes from signal originating from fatty tissue surrounding prostate that tends to mask or distort signal from within the prostate, thus reducing the overall clinical usefulness of 1H-MRSI data. This thesis has three major areas of focus: 1) The development of an optimized 1H-MRSI technique, called conformal voxel magnetic resonance spectroscopy (CV-MRS), to deal the with removal of unwanted lipid contaminating artifacts at short and long echo times. 2) An in vivo human study to test the CV-MRS technique, including healthy volunteers and cancer patients scheduled for radical prostatectomy or radiation therapy. 3) A study to determine the efficacy of using the 1H-MRSI data for optimized radiation treatment planning using modern delivery techniques like intensity modulated radiation treatment. Data collected from the study using the optimized CV-MRS method show significantly reduced lipid contamination resulting in high quality spectra throughout the prostate. Combining the CV-MRS technique with spectral-spatial excitation further reduced lipid contamination and opened up the possibility of detecting metabolites with short T2 relaxation times. Results from the in vivo study were verified with post-histopathological data. Lastly, 1H-MRSI data was incorporated into the radiation treatment planning software and used to asses tumour control by escalating the radiation to prostate lesions that were identified by 1H-MRSI. In summary, this thesis demonstrates the clinical feasibility of using advanced spectroscopic imaging techniques for improved diagnosis and treatment of prostate cancer.

[Special characters cannot be displayed. Please see the pdf version of the Abstract for an accurate reproduction.] We studied the circumstellar discs, the initial mass function (IMF), mass distribution, binarity and the fundamental properties of the [special character] 9 Myr-old pre-main sequence (PMS) [special character] Chamaeleontis cluster. Using JHKL colour-colour and colour-excess diagrams, we found the circumstellar disc fraction to be [special character] 0.60 among the late-type members. Four stars with [special character] (K - L) > 0.4 were identified as experiencing ongoing accretion which was later confirmed by high-resolution spectroscopic study. Quantitative analysis of the H[special character] profiles found accretion in these four stars at rates comparable to that of two members of the similarly-aged TW Hydrae Association (TWA); rates 1 - 3 orders of magnitude lower than in younger classical T Tauri stars. Together these results suggest that, while the mass accretion rate decreases with age, PMS stars can retain their inner discs for [special character] 10 Myr. An optical photometric survey spanning 1.3 ?? 1.3 pc added two low-mass stars to the cluster inventory. Together with other recent surveys the population is likely to be significantly complete for primaries with masses M > 0.15M[special character]. The cluster now consists of 18 primaries and 9 confirmed and candidate secondaries, with [special character] 2-4 times higher multiplicity than seen in field dwarfs. The cluster IMF is consistent with that of rich young clusters and field stars. By extending the IMF to lower masses, we predict 20-29 low-mass stars and brown dwarfs may remain undiscovered. From study of the cluster???s spatial and mass distribution, we find the [special character] Cha cluster has significant mass segregation, with > 50 per cent of the stellar mass residing within the central 0.17 pc. Lastly we classified members of the cluster with low-resolution spectra, providing information about the fundamental properties of the PMS stars by comparison to standard dwarfs. Broadband VRI colours and pseudocontinuum indices derived for the cluster stars are indistinguishable from dwarfs at visual and red wavelengths. This suggests the temperature sequence for the PMS [special character] Cha cluster is similar to that of the dwarf sequence. Narrow-band spectral indices for the [special character] Cha cluster possibly indicate higher metallicity and strongly indicate lower surface gravity than the dwarf indices.

An Ultraviolet to Visible (UV-Vis) spectroscopic analysis based on fuzzy logic approach has been developed for furan content measurement in transformer oil. Following the successful identification and quantification of furan derivatives in transformer oil by ASTM D5837 standard, the new approach is able to approximate the furan content more conveniently and economically. As furan concentration level would determine the absorption intensity in UV-Vis spectral range, the fuzzy logic software model developed would exploit this characteristic to aggregate the furans content level in transformer oil. The UV-Vis spectral response at other ambient temperature is also studied. The proposed technique provides a convenient alternative to conventional method of furan measurement by High Performance Liquid Chromatography (HPLC) or Gas Chromatography Mass Spectrometry (GC/MS) in ASTM D5837 Standard.