<p> This thesis provides examples ~f new solid supports for Matrix-Assisted Laser Desorption Ionization Time-of-Flight (MALDI-TOF) in two parts. </p> <p> Firstly, mesoporous and macroporous silicas were developed as new supports for the elimination of low mass interference signals in the mass spectrum. Due to the complexity of the system, a variety of factors were studied, such as sol gel morphology, matrix crystallization, polymeric molecular weight and concentration. It was observed that the mesoporous silicas and higher matrix crystallization were advantageous for optimal signal intensity and signal-to-background ratio. </p> <p> Secondly, due to the inconsistencies in the literature apropos the role of the matrix in MALDI process, we have developed chemically modified compounds and studied these as alternative MALDI matrices. It was concluded that for optimal free matrix performance, the phenolic groups were desirable while crystallization was not required. Moreover, a highly selective covalently linked silicon-based matrix was developed, which yielded a superior signal-to-background ratio at moderate signal intensities. A chemical nature of matrix and sol gel processing methodology used were the relevant factors to be considered when optimizing a tethered matrix. It was demonstrated that requirements for free and surface-bound matrices were different; hence, suggesting the drastic difference in their operating mechanisms during MALDI process. </p> / Thesis / Master of Science (MSc)

Achieving autonomous in complex natural environments has the potential to transform society by bringing the benefits of automation from the confines of the factory floor to the outdoors. There, it could benefit areas such as environmental monitoring and clean-up, precision agriculture, delivery of goods. A fundamental requirement for achieving these goals are sensors that can provide reliable support for navigation, e.g., a drone, in natural environments. In this thesis, sonar-based navigation has been investigated as an approach to parsimonious autonomous sensing for drones. Bats living in dense vegetation have demonstrated that autonomous navigation in a complex, natural environment based on two one-dimensional ultrasonic echo streams is feasible. Here, a biomimetic sonar head has been used to collect echo data from recreations of natural foliage in the lab under controlled conditions. This data was used to address the research question whether the grazing angle at which the sonar is looking at a surface can be estimated from the echoes -- despite the random three-dimensional nature of the scatter from the foliage. To investigate this, the echoes have been subjected to statistical analysis such as spectral coherence and cross-correlation. Most importantly, the foliage data was compared against predictions made by the Endura method (energy, duration, and range method) that has been devices for two-dimension random scatterers. The results of this analysis shows that -- despite their profoundly random nature -- echoes can be used to estimate the sonar grazing angle directly, i.e., without the need to resort to reconstructions of the foliage geometry. This opens the possibility of developing simple devices for navigation control in natural environments that can control the direction of motion at a very little computational cost. / Master of Science / Autonomously flying drones is a potential technology that could bring benefits to the society and improve the quality of life for humans[22]. Therefore, a study of autonomously flying in a natural environment is necessary, and this thesis will focus on drone that could recognize objects with different grazing angle and acoustic signal by collecting data from near foliage surface. For example, when a bush wall is in front of the drone, a on board computer could inform drone whether the drone airline will collide with the bush wall or the bush wall is safely out of drone’s path[5]. If on board computer reads that there will be a collision with bush wall, then drone needs to make decision (change direction or stop immediately) to avoid crush on to bush wall. A sonar based navigation system has been investigated as an approach to achieve autonomous sensing for drones, which is inspired by bats. Bats use their natural sonar system to navigate in cave or forest, hence, it is hardly to see bats slam into any obstacles while flying. Bats navigation behaviours could be reconstructed as a sonar based autonomy. Hence, this thesis is inspired by bats to determine if there is a computational way to illustrate that sonar based sensor could be a solution to achieve reactive autonomy by using different grazing angle of the surface’s acoustic signals.

No / This article reports on the use of comprehensive two-dimensional gas chromatography–time-of-flight mass spectrometry (GC × GC–TOFMS) for forensic geotaphonomy application. Gravesoil samples were collected at various depths and analyzed for their volatile organic compound (VOC) profile. A data processing procedure was developed to highlight potential candidate marker molecules related to the decomposition process that could be isolated from the soil matrix. Some 20 specific compounds were specifically found in the soil sample taken below the carcass and 34 other compounds were found at all depths of the gravesoil samples. The group of the 20 compounds consisted of ketones, nitriles, sulfurs, heterocyclic compounds, and benzene derivatives like aldehydes, alcohols, ketones, ethers and nitriles. The group of the 34 compounds consisted of methyl-branched alkane isomers including methyl-, dimethyl-, trimethyl-, tetramethyl-, and heptamethyl-isomers ranging from C12 to C16. A trend in the relative presence of these alkanes over the various layers of soils was observed, with an increase in the amount of the specific alkanes when coming from the carcass to the surface. Based on the specific presence of these methyl-branched alkanes in gravesoils, we created a processing method that applies a specific script to search raw data for characteristic mass spectral features related to recognizable mass fragmentation pattern. Such screening of soil samples for cadaveric decomposition signature was successfully applied on two gravesoil sites and clearly differentiates soils at proximity of buried decaying pig carcasses from control soils.

Abstract Amorphous Selenium (a-Se) was first commercialized for use as a photoconductor in xerography during the middle of the twentieth century. Since then the hole transport properties of a-Se have been studied extensively, however the study of electron transport remains relatively limited. Flat panel digital X-ray detectors using a-Se as a photoconductor have been developed and are being used in mammographic screening. The charge transport properties of the photoconductor layer will in part determine the performance of the flat panel detector. X-ray absorption causes electron-hole pair generation in the bulk of the photoconductor, requiring both electrons and holes to drift across the sample and be collected. If these carriers are lost in the many localized trapping states as they cross the sample, they will not contribute to the image signal resulting in unnecessary radiation exposure to the patient. Eleven a-Se samples were deposited at the University of Saskatchewan varying in thickness from 13 μm to 501 μm. Pure a-Se was chosen to ensure uniformity across the thickness of the samples, that is, to ensure the composition of the film did not change across the thickness. Time of flight transient photoconductivity experiments (TOF) and interrupted field time of flight (IFTOF) measurements were performed to measure the electron drift mobility and lifetime respectively. The product of electron drift mobility μ and lifetime τ, hence the carrier range (μτ) at a given applied electric field. The electron range is an important parameter as this places limits on the practical thickness of the photoconducting layer in a detector. This study also includes an investigation into the effect of the definition of transit time on the calculated drift mobility and analysis of the dispersive transport properties of a-Se. It was observed that as sample thickness (L) increased, electron drift mobility (μ) decreased. In addition electron lifetime (τ) decreased dramatically in samples thinner than 50 μm. Electron range (μτ) was 2.26 × 〖10〗^(-6) cm^2/V in the 147μm sample and 5.46 × 〖10〗^(-8) cm^2/V in the 13 μm sample, a difference of almost two orders of magnitude. The comparison of the half current method and inflection point methods to calculate the transit time of the same TOF curve, shows that the calculated mobility can vary by as much as 24%. This illustrates clearly that it is important to use the same point on the TOF curve to define the transit time. Charge packet dispersion (spread) in the time domain in pure a-Se samples was proportional to L^m where L is the photoconductor thickness and m ~ 1.3, measured at both 1 V/μm and 4 V/μm.

Le couplage neuro-vasculaire est un domaine grandissant. Ce dernier étudie les effets de l’activité cérébrale sur le comportement du flux sanguin cérébral (cerebral blood flow, CBF) et sur le flux des vaisseaux sanguins. Avec l’aide de l’imagerie par résonance magnétique (IRM), il est possible d’obtenir des images comme les images pondérées par susceptibilité (susceptibility weighted imaging, SWI) pour voir les veines ou bien avec des images de temps de vol par angiographie (time-of-flight magnetic resonance angiography, TOF MRA) pour imager les artères. Ces images permettent d’avoir une représentation structurelle des vaisseaux dans le cerveau. Ce mémoire présente une méthode permettant la segmentation des vaisseaux sanguins à partir d’images structurelles afin d’en extraire les caractéristiques. En utilisant le masque de segmentation, il est possible de calculer le diamètre des vaisseaux ainsi que leur longueur. Avec l’aide de tels outils de segmentation automatique, nous avons conduit une étude permettant d’analyser le comportement des vaisseaux sanguins lors d’activités neuronales. Grâce à une stimulation visuelle, nous avons fait l’acquisition de deux images; la première dite au repos et la seconde avec stimulation. Nous avons pu comparer le diamètre dans chacune des images et ainsi obtenir la vasodilatation en millimètre, mais également en pourcentage, et cela pour chaque voxel. Nous avons également calculé la distance entre le site d’activation et un voxel pour observer l’amplitude de la vasodilatation en fonction de la distance. Tout ceci permet d’avoir une meilleure compréhension du système vasculaire du cerveau humain. / Abstract : The neurovascular coupling is a growing field; it studies the effects of cerebral activity on the behaviour of cerebral blood flow (CBF) and the blood vessels themselves. With the help of magnetic resonance imaging (MRI), it is possible to obtain images such as susceptibility weighted imaging (SWI) to see the veins or time-of-flight magnetic resonance angiography (TOF MRA) to visualize the arteries. These images allow having a structural representation of vessels in the brain. This thesis presents a method to segment blood vessels from structural images and extract their features. Using the segmentation mask, it is possible to calculate the diameter of the vessels as well as their length. With the help of such automatic segmentation tools, we conducted a study to analyze the behaviour of blood vessels during neuronal activities. Due to visual stimulation, we have acquired two images; one at rest and the other with stimulation. We compare the diameter in each of the images and obtain vasodilation in millimeters, but also as a percentage in each voxel. We also calculated the distance between the activation site and each voxel to see the magnitude of the vasodilation function of the distance. All this provides a better understanding of the vascular system of the human brain.

For this project, we investigate different methods of adding location-based security to a WLAN network. A literature review is done toconfirm the current state-of-the-art on the subject, and we scrutinizethe available methods based on practicality, security, and simplicity.We then further delve into a few specific methods with good prop-erties based on the prior review, to confirm if these are suitable fora proof-of-principle implementation. Finally, if a suitable method isfound, we develop the proof-of-principle to show that the system canwork in practice.

L’identification des micro-organismes reposait jusqu’à présent sur l’étude des caractères culturaux et biochimiques de chaque espèce. Depuis quelques années, la spectrométrie de masse de type Matrix Assisted Laser Desorption/Ionization Time Of Flight (MALDI-TOF) s’est développée dans les laboratoires de microbiologie clinique. Cette nouvelle technologie permet de réaliser très rapidement et à moindre coût un diagnostic d’espèce sur des colonies de bactéries ou de champignons isolées sur des milieux de culture solides.Dans un premier temps, nous avons montré que cette technologie permet de réaliser une identification des germes isolés en milieu liquide, comme les flacons d’hémoculture au cours des bactériémies par exemple. Ce dépistage se fait directement à partir du flacon positif, sans attendre l’isolement des colonies sur milieu solide. Ce diagnostic disponible dès le premier jour permet d’adapter l’antibiothérapie au phénotype de résistance habituel de l’espèce.Dans un deuxième temps, nous avons cherché à identifier la nature des biomarqueurs utilisés pour l’identification des espèces bactériennes, en prenant comme exemple la bactérie pathogène Neisseria meningitidis. La comparaison du génome et du protéome des souches entièrement séquencées a permis de mettre en évidence la nature exacte des protéines impliquées dans le diagnostic d’espèce. Par ailleurs, les protéines ribosomales étant majoritaires et pouvant servir d’outil épidémiologique, nous avons constaté que la mise en évidence de leurs variations sur le spectre de masse rend la différenciation de souches au sein d’une même espèce possible, en adaptant la méthode d’analyse. Enfin, nous avons présenté des résultats préliminaires encourageants sur l’exploitation du caractère constant de certaines protéines ribosomales visibles directement sur le spectre de masse, permettant de différencier des espèces très proches, comme Streptococcus pneumoniae et Streptococcus mitis. / Until now, bacterial and fungal identification has been based on biochemical characterization of microorganisms. The Matrix-Assisted Laser Desorption/Ionization Time of Flight Spectrometry (MALDI-TOF MS) has recently been developed in clinical microbiology laboratories. This new technology allows a rapid, accurate and less expensive identification of bacterial and fungal colonies grown on agar media. First, we have shown that the direct identification of bacteria grown in liquid media such as blood cultures was possible, without waiting for a subculture on solid media. Since the diagnosis is available on the first day, the presumptive antimicrobial treatment can be rapidly adapted according to the usual resistance phenotype of the microorganism. We have then searched to identify the biomarkers used for the identification of bacteria, using Neisseria meningitidis as a model. Comparing the genome and the proteome of sequenced strains allowed us to identify the ribosomal proteins as thoses involved in the MALDI-TOF MS diagnosis. Ribosomal proteins are very abundant and are very often used as epidemiological tools : their variations on the bacteria mass spectrum allows an intra-species differentiation of several strains. Finally we present encouraging preliminary results based on the detection of consistent ribosomal proteins directly visible on the mass spectrum that lead to the accurate identification of some very close species such as Streptococcus pneumoniae and Streptococcus mitis.

Detta examensarbete fokuserar på utveckling och utvärdering av en ny metod för att räkna dubbelriktade personflöden inomhus med hjälp av Ultrasonic Time-of-Flight teknik. Projektets huvudsyfte är att skapa en kostnadseffektiv, strömsnål och integritetsvänlig lösning som är i linje med lagar som GDPR. Studien börjar med en kort genomgång av tillgängliga tekniker för personflödesmätning, men det blir tydligt att dessa tekniker brister i kraven för den önskade tekniken. Mot denna bakgrund framstår Ultrasonic Time-of-Flight som en lovande kandidat på grund av sin förmåga att detektera objekt och rörelseriktningar utan att samla in personligt identifierbar information. För att realisera detta projekt har ett utvecklingskit baserat på sensorn CH201 från Chirp Microsystems använts. Sensorns låga strömförbrukning och förmåga att mäta avstånd i ett brett synfält är det som är lovande i tekniken. Ett akustiskt hölje optimerar sensorernas synfält och minimerar störningar. Experimentdelen av arbetet inkluderar uppbyggnaden av en testmiljö där sensorernas förmåga att korrekt räkna individer och bestämma deras rörelseriktning testas. Resultaten från dessa tester visar på hög noggrannhet i detektering av enskilda individer som passerar, men har lägre noggrannhet då flera personer passerar samtidigt. Vidare diskuteras potentialen för att vidareutveckla systemet för att även kunna hantera större personflöden och mer komplexa scenarion, som flera personer som rör sig bredvid varandra i olika riktningar. En kritisk granskning av systemets prestanda under längre tidsperioder och i olika miljöer föreslås som framtida forskningsarbete för att ytterligare validera och förbättra tekniken. Sammanfattningsvis demonstrerar detta arbete potentialen hos tekniken som en säker och integritetsvänlig lösning för effektiv övervakning av personflöden. Med ytterligare utveckling och anpassning förväntas tekniken kunna uppfylla en ännu högre noggrannhet. / This thesis focuses on the development and evaluation of a new method for measuring bidirectional indoor people flows using Ultrasonic Time-of-Flight technology. The main purpose of the project is to create a cost-effective, low-power, and privacy-friendly solution that complies with laws like the GDPR. It begins with a short review of existing techniques for measuring people flow, concluding that these technologies do not support the goal of the new technology. Ultrasonic Time-of-Flight emerges as a promising candidate due to its ability to detect objects and directions of movement without collecting personally identifiable information. To realize this project, a development kit based on the CH201 sensor from ChirpMicrosystems has been used. The sensor’s low power consumption and ability to measure distances in a wide field of view are what made the technology promising. An acoustic enclosure optimizes the sensors’ field of view and minimizes interference. The experimental part of the work includes the construction of a test environment where the sensors’ ability to accurately count individuals and determine their direction of movement is tested. The results from these tests show high accuracy in detecting individual passersby but encounter more problems with multiple individuals simultaneously. Further discussions will explore the potential for developing the system to manage larger crowds and more complex scenarios, such as multiple people moving side by side in different directions. A critical review of the system’s performance over longer periods and in different environments is proposed as future research work to further validate and improve the technology. In conclusion, this work demonstrates the potential of the technology as a secure and privacy-friendly solution for effective monitoring of people flows. With further development and adaptation, the technology is expected to offer significantly better accuracy.

Capillary electrochromatography (CEC) is a rapidly developing liquid chromatographic technique in which electroosmotic flow (EOF) is used to propel mobile phase through the chromatographic column. The use of EOF results in reduced band dispersion when compared with pressurised flow, but narrow capillaries are required to avoid dispersion due to heating that arises from the required application of high electrical potentials. Measurement of UV absorbance in these narrow capillaries is therefore relatively insensitive, demanding improved detection methods. This work presents an alternative strategy that is based on the combination of ion trap accumulation with time-of-flight mass spectrometry. Electrospray is most often used to transfer analytes from solution to the gas phase, concomitant with ionisation, when interfacing CEC to mass spectrometry. The small volumetric flow rates encountered in CEC, however, raise the possibility of other types of interface being effective. The work presented here describes the development of a novel interface in which a pulsed IR laser is used to vaporise chromatographic eluent, followed by ionisation using a pulsed UV laser. Vaporisation and ionisation both occur within the ion trap to remove the possibility of transmission losses. Ionisation laser wavelength is varied to impart a degree of selectivity. The presence of vaporised solvent and analyte ions inside the trap offers the possibility of performing ion-molecule chemistry. In developing this instrument, the electrochromatographic column was separated from the interface by an electrically grounded junction and a transfer capillary. To preserve chromatographic efficiency, the fluid dynamics of this junction between the column and the transfer capillary were investigated both computationally and experimentally. Simulations of the fluid dynamics of the junction are presented. In order to test the interface without the intermittent, chromatographic, delivery of analyte, a continuous leak inlet was employed. The performance of the instrument was evaluated with polycyclic aromatic hydrocarbons because they are important environmental pollutants and because they are amenable to laser ionisation at 266 nm. Expressed as a number of theoretical plates per metre, an average chromatographic efficiency of 95,000 was obtained with a test mixture that consisted of acenaphthene, biphenyl, fluorene, naphthalene and phenanthrene. Furthermore, using the leak inlet, naphthalene was detected as a 100 nM solution in acetonitrile.

A promising new approach for studying cold ion-molecule chemical reactions is the combination of laser- or sympathetically-cooled trapped ions and slow-moving molecules from a cold molecule source, such as a quadrupole velocity selector or a Stark decelerator. Previous reaction studies using trapped atomic ions and slow molecules from a quadrupole velocity selector were able to reach average collision energies as low as 1 K. However, the guided molecules had an approximately room temperature rotational energy distribution, so the reactions studied were not truly cold. Thus, a new molecular source for producing translationally and rotationally cold molecules utilizing buffer gas cooling and quadrupole velocity selection was constructed by K. Twyman and characterized for use in cold reaction studies. This new source of cold molecules is referred to as the buffer gas guide. A new ion trap has been designed and built for use with the existing buffer gas guide. The new ion trap apparatus is compact and mechanically compatible with this new guide. It uses a linear Paul ion trap with cylindrical electrodes to trap ions. Two optical axes (one axial and one radial) enable efficient cooling of small ion crystals. A field-free time-of-flight tube and ion detection assembly are also incorporated into the apparatus. A new technique for determining the mass and quantity of trapped ions has also been developed, termed digital ion trap mass spectrometry. The new technique uses a digital RF waveform to trap ions before ejecting the ions radially from the trap using an ejection pulse applied to the trap electrodes. The ions are then detected after free flight along a time-of-flight tube. This technique was characterized by ejecting crystals of various sizes and compositions: Ca^&plus; only, Ca^&plus;/CaF^&plus;, Ca^&plus;/CaOH^&plus;/CaOD^&plus;, and Ca^&plus;/NH^&plus;<sub style='position: relative; left: -.6em;'>3</sub> /NH^&plus;<sub style='position: relative; left: -.6em;'>4</sub> /H₃O^&plus;. A linear relationship between the number of ions ejected (determined by comparing experimental and simulated crystal images) and the integral of the time-of-flight peak was observed for Ca^&plus; and Ca^&plus;/CaF^&plus;. All mass peaks were resolved. Simulations of the trapped ions and their trajectories through the time-of-flight tube were also performed, and excellent agreement between the simulated and experimental mass resolution was observed. Progress towards combining the buffer gas guide with the previously independent ion trap is also presented. It is anticipated that the combined buffer gas guide ion trap apparatus will enable the study of ion-molecule reactions at low temperatures with translationally and rotationally cold molecules. It is anticipated that the new digital ion trap mass spectrometry technique will simplify the study of reactions when multiple product ions whose masses are separated by only 1 AMU are formed. A new ion trap has been designed and built for use with the existing buffer gas guide. The new ion trap apparatus is compact and mechanically compatible with this new guide. It uses a linear Paul ion trap with cylindrical electrodes to trap ions. Two optical axes (one axial and one radial) enable efficient cooling of small ion crystals. A field-free time-of-flight tube and ion detection assembly are also incorporated into the apparatus. A new technique for determining the mass and quantity of trapped ions has also been developed, termed digital ion trap mass spectrometry. The new technique uses a digital RF waveform to trap ions before ejecting the ions radially from the trap using an ejection pulse applied to the trap electrodes. The ions are then detected after free flight along a time-of-flight tube. This technique was characterized by ejecting crystals of various sizes and compositions: Ca+ only, Ca+/CaF+, Ca+/CaOH+/CaOD+, and Ca+/NH+3/NH+4/H3O+. A linear relationship between the number of ions ejected (determined by comparing experimental and simulated crystal images) and the integral of the time-of-flight peak was observed for Ca+ and Ca+/CaF+. All mass peaks were resolved. Simulations of the trapped ions and their trajectories through the time-of-flight tube were also performed, and excellent agreement between the simulated and experimental mass resolution was observed. Progress towards combining the buffer gas guide with the previously independent ion trap is also presented. It is anticipated that the combined buffer gas guide ion trap apparatus will enable the study of ion-molecule reactions at low temperatures with translationally and rotationally cold molecules. It is anticipated that the new digital ion trap mass spectrometry technique will simplify the study of reactions when multiple product ions whose masses are separated by only 1 AMU are formed.