Female sexual arousal refers to one’s feelings of sexual excitement and pleasure and has both physiological (i.e., objective) and psychological (i.e., subjective) components. It is an important, yet difficult phenomenon to investigate. As a result, many instruments have been used in an attempt to accurately measure female arousal; however, there are problems associated with each. Furthermore, the relationship between the subjective and physiological indicators of sexual arousal appears to be influenced by the instrument used to measure physiological sexual arousal. Specifically, instruments measuring physiological arousal internally (i.e., vaginal photoplethysmography) typically yield lower correlations between measures of physiological and subjective sexual arousal than instruments examining the external genitals (i.e., labial thermistor, thermal imager), which indirectly measure blood flow. Alternatively, laser Doppler imaging (LDI) is a direct measure of external genital blood flow but has only been used in one previous study that did not assess the relationship between physiological and subjective sexual arousal. The aims of the current study were to investigate the usefulness of LDI for assessing genital blood flow in women in response to erotic visual stimuli, and to explore the relationship between physiological and subjective indicators of sexual arousal. In addition, the role of psychosocial variables in predicting physiological and subjective sexual arousal was also examined. Eighty sexually healthy women completed a psychosocial interview and questionnaires. Participants also watched three 15-minute films during LDI scanning: two nature films (measuring acclimatization and baseline blood flow levels) and one randomly assigned experimental film (erotic, anxiety, humor, or neutral). They were asked to rate their level of subjective sexual arousal throughout and following the third film. Results indicated that LDI was able to differentiate the erotic condition from the three non-erotic conditions, and that physiological and subjective sexual arousal were significantly correlated. Although the psychosocial variables did not significantly predict either component of sexual arousal, specific variables moderated the association. Psychological, sexual, and social variables, along with genital sensations, played significant roles in the relationship between subjective and physiological sexual arousal. These findings suggest that LDI is a useful instrument for measuring female sexual arousal, and that sexual arousal is a complex process that requires further empirical investigation. / Thesis (Ph.D, Psychology) -- Queen's University, 2009-08-27 10:09:26.355

L'émergence de disciplines post-génomiques, telles que la protéomique et la métabolomique, requiert le développement d'outils analytiques toujours plus performants afin de déterminer, respectivement, l'ensemble des peptides et protéines et des composés organiques de faible masse moléculaire présents dans un milieu biologique. En raison de sa sensibilité, spécificité et rapidité d'acquisition des données, la désorption/ionisation laser assistée par une matrice (MALDI) constitue une des méthodes d'ionisation majeure en spectrométrie de masse (MS) permettant d'envisager les analyses de ces composés. Cependant, elle présente des limitations pour la détection de petites molécules (<700 Da) due à la présence des ions de matrice dans les basses masses du spectre. Dans ce contexte, le potentiel de différentes techniques LDI alternatives a été évalué dans le cadre de la détection de peptides synthétiques de compositions et de tailles variées. Dans le cadre de cette thèse, de nouvelles stratégies analytiques LDI-MS et LDI-MS/MS basées sur l'utilisation de matrices inertes ont été développées. Pour ce faire, des substrats, à base de silice et de titane présentant différentes structurations, ont été utilisés pour assister la désorption/ionisation sans ajout de matrice organique. L'optimisation des méthodologies a été réalisée, puis l'évaluation de la sensibilité et de la reproductibilité des techniques a ensuite été appréciée. Les problématiques de discrimination spectrale dans le cas d'analyses de mélanges de peptides synthétiques et ou issus de digestats trypsiques de protéines ont été abordées afin de valider ces méthodologies LDI pour des applications en protéomique. Les performances des méthodes ont été comparées à celles obtenues dans des stratégies LDI assistées par des matrices organiques (MALDI) pour des échantillons de peptides synthétiques seuls et en mélange ainsi que de quatre digestats trypsiques issus du Cytochrome C (12 kDa), de la β-Caséine (24 kDa), de l'albumine de sérum bovin (BSA, 66 kDa) et du fibrinogène (340 kDa). Un second aspect a consisté en l'analyse de peptide en spectrométrie de masse en tandem. Pour cela, des expériences de dissociation de peptides en fragmentation basse et haute énergie respectivement sur des appareillages de type ESI-QqTOF et MALDI-TOF/TOF ont été menées. Les résultats obtenus ont contribué à une meilleure compréhension du séquençage peptidique et ont démontré des comportements particuliers propres à certaines séquences observés quelles que soient les méthodes d'activation vibrationnelle employées. La présence de résidus basiques, à partir du moment où ils ne se trouvent pas en position C-terminale, a été déterminante pour déclencher des voies de fragmentation en compétition avec les dissociations bx-yn attendues. Ces comportements doivent être impérativement pris en compte par les logiciels de séquençage. / The advent of proteomics and metabolomics require the development of highly efficient analytical tool in order to detect and identify peptides and proteins as well as small organic compounds present in biological media. Due to its sensitivity, specificity and speed of data acquisition, Matrix-Assisted Laser Desorption/Ionization constitutes one of the major ionization methods in mass spectrometry suitable for the analyses of biomolecules. However the sensitive detection of low molecular weight compounds (<700 Da) is most of the time troublesome, being hampered by the production of matrix ions in the low mass range. In that case, the potency of various alternative LDI techniques based on inert ionization promoting substrates was evaluated for the detection of synthetic peptides presenting wide sequence diversity. Silicon and titanium based materials exhibiting different physico-chemical properties were probed for LDI-MS and LDI-MS/MS analyses of the designed model peptides. These methods, which were devoted of the use of any organic matrix, were optimized through a large set of experiments, taking particular attention to detection sensitivity and reproducibility. Spectral discrimination was another matter of concern, especially in the case of peptide mixture analyses which is encountered in proteomics for tryptic digest elucidation. The performances of the design LDI methods were compared with the original MALDI technique for peptide detection and sequencing from various samples i.e. pure and mixed synthetic peptides, and four tryptic digests issued from Cytochrome C (12 kDa), β-Casein (24 kDa), Bovin serum albumin (BSA, 66 kDa) and fibrinogen (340 kDa). A second research topic dealing with peptide sequencing by MS/MS technologies was pursued in order to contribute to the knowledge of the fragmentation rules. Vibrational activation methods through various mass analyzer configurations (MALDI-TOF/TOF, ESI-QqTOF) were investigated. Specific dissociation behaviors were extracted from the recorded MS/MS data sets. The presence of basic residues, provided that they are not located at the peptide C-terminal end, triggered specific backbone fragmentation in competition to the expected bx-yn pathway. This was found to be a critical issue to be considered by sequencing softwares.

Land uses dominated by human activity can have a significant effect on ecological processes. In Florida, oxygen depletion is the most common impairment in lake, stream, and coastal water bodies. The continual growth and development in Florida, along with a conversion to more human intense land uses warrants study and discussion on impacts to dissolved oxygen regimes along a gradient of human disturbance. This research study is designed to identify observable trends in dissolved oxygen regimes along a gradient of increasing human intensity. Twenty-six stations in the Tampa Bay area were selected to represent lotic systems in west-central Florida. Data was collected quarterly, during four-day deployments, using a deployable data sonde. Grab samples for nutrients and chlorophyll-a provided antecedent data to explain observed trends. Physical components of streams, such as channelization were also taken into account. Biological integrity of streams was assessed to identify if altered dissolved oxygen regimes as a result of human land use significantly affect the health of the systems. Analysis included the use of Spearman rank order correlations to identify patterns. Dissolved oxygen regimes were correlated with the Landscape Development Intensity Index (LDI). Nutrients, primary productivity, and physical alteration to the streambed play a significant role in understanding how land use affects dissolved oxygen regimes. Results indicate the intensity of human land use has a significant effect on dissolved oxygen regimes and has significant policy implications for Florida's Total Maximum Daily Load (TMDL) program. Diel variation in oxygen measurements may be a more appropriate indicator of impairment and stream biological integrity.

No description available.

No description available.

No description available.

Over the last decades organic light-emitting diodes (OLEDs) and organic solar cells (OSCs) have gained considerable attention as efficient, flexible, lightweight, and potentially low-cost technology for lighting and display applications or as a renewable energy source, respectively. However, achieving long-term stability remains challenging. Revealing and understanding aging processes is therefore of great interest. This work presents fundamental investigations to understand and circumvent organic device degradation. In the first part, single materials used in organic devices were investigated. By tailoring an attenuated total reflection infrared (ATR-IR) spectrometer to the specific needs and subsequent measurements, it is shown that the tris(8-hydroxyquinoline)aluminum (Alq3) molecule, a well known fluorescent green emitter, degrades during air exposure by the formation of carbonyl groups. By using a laser desorption/ionization time of flight mass spectrometer (LDI-TOF-MS) it was shown that a,w-bis-(dicyanovinylen)-sexithiophen (DCV6T-Bu4), a well known small-molecule material which is used as part of the active layer, reacts with oxygen during ultraviolet (UV) irradiation. By using climate boxes and a sun simulator the impact of dry and humid air as well as sunlight on C60, a widely-used acceptor molecule in organic solar cells, was investigated. The breaking of the C60 cage to C58 and C56 and the further reaction of these components with oxygen as well as the dimerization of C58 and C56 molecules were found. The degradation products such as C58O increase with air exposure time but they are independent of the humidity level of the ambient air as well as sunlight irradiation. Subsequent annealing leads to a decrease of the C58O concentration. Many efficient n-dopants are prone to degradation in air, due to the low ionization potentials, thereby limiting the processing conditions. It was found that the air exposure of the highly efficient n-dopant tetrakis(1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidinato)ditungsten(II) (W2(hpp)4) leads to oxidation reactions of the molecule to [W(hpp)2 + O] and other degradation products. The decay constant of W2(hpp)4 and the matching mean growth time of the [W(hpp)2 + O] degradation as well as a second very quick degradation of the dopant could be determined. The two decay constants can be explained by the assumption that W2(hpp)4 molecules, which are involved in the charge transfer, do degrade slower due to the fact that the charge transfer leads to a downshift of the energy levels of the W2(hpp)4 molecule. Apart from the properties of the organic materials, other effects such as the impact of different purification systems on the material purity as well as the dependence of material purity on the OLED lifetime has been investigated. No correlations between the purification grade and the amount of impurities were found. OLEDs which contain N,N\'-di(naphthalen-1-yl)-N,N\'-diphenyl-benzidine (alpha-NPD) purified in a vertically interlaced stainless steel sublimation systems shows slightly higher external quantum efficiencies compared to tube-based vacuum sublimation systems. The devices which contain alpha-NPD purified by a sublimation system have an extended lifetime. Finally, the impact of residual gases during device fabrication on OLED lifetime and electrical characteristics was investigated. It was found that water vapor introduces an additional series resistance to the OLED, while the other gases do not influence the electric characteristics. The presence of nitrogen or oxygen impacts the lifetime of the OLEDs by the same amount. Nitrogen is non-reactive, this leads to the conclusion that the influence of nitrogen and oxygen on the OLED lifetime is of non-chemical nature, such as changes in the morphology of the organic layers. Water vapor introduces an additional, even faster degradation process within the first hours of OLED operation. As major sources of device degradation, the dimerization of 4,7-diphenyl-1,10-phenanthroline (BPhen) as well as the complexation reaction of alpha-NPD with a bis(1-phenylisoquinoline)iridium(III) (Ir(piq)2) fragment was identified.

Les lichens, organismes symbiotiques associant un champignon et un partenaire photosynthétique (algue verte et/ou cyanobactérie), sont caractérisés par la biosynthèse de métabolites secondaires uniques dotés de bioactivités variées. Pour valoriser au mieux cette ressource privilégiée, des méthodes innovantes de spectrométrie de masse ont été développées dans le but de minimiser la préparation de l’échantillon et la durée des analyses. Deux techniques de spectrométrie de masse ont été évaluées en ce sens : le DART-MS et le LDI-MS. L’apport de chacune de ces deux méthodes a pu être établi sur un large panel de lichens, représentant une part importante de l’espace chimique couvert par ces organismes. Il a été démontré que des profils chimiques complets pouvaient être obtenus respectivement à partir de thalles lichéniques et d’extraits acétoniques totaux. Compte tenu de la très large utilisation de la CCM pour l’analyse chimique de lichens, les possibilités offertes par le couplage de la CCM à l’ionisation electrospray ont également été explorées. Une seconde partie de ces travaux avait pour but de cartographier la distribution des métabolites secondaires au sein du thalle lichénique. À ces fins, des analyses d’imagerie LDI ont été réalisées sur une coupe transversale d’un lichen crustacé modèle : Ophioparma ventosa. Ce lichen a été étudié en phytochimie pour identifier six napthopyranones à partir des apothécies dont quatre nouvelles structures. Les principaux métabolites de ce lichen ont pu être imagés par LDI-MSI avec une résolution spatiale de 50 μm environ. Une corrélation entre la distribution des molécules et leur rôle écologique présumé permet d’avancer des hypothèses d’écologie chimique. Des approches conjointes reliant histolocalisation et étude génétique des partenaires de la symbiose ont été entreprises. La recherche des gènes de la biosynthèse de la mycosporine sérinol chez les symbiontes isolés de Lichina pygmaea par microdissection capture laser a été initiée en ce sens. D’autres approches innovantes comme l’analyse cristallographique par diffraction de poudre par les rayons X sont également abordées dans ce document articulé autour de six publications issues de ce travail et de deux articles en cours de soumission. / Lichens are self-sustaining symbiotic partnerships comprising a fungus associated with a green alga and/or a cyanobacteria. This consortium produces unique secondary metabolites that are endowed with various biological activities. To harness this privileged chemodiversity, innovative mass spectrometry techniques were developed in the course of this study to accelerate the dereplicative holdup through both a minimal sample preparation and a decrease of the time of analysis. Two approaches were considered during this work: DART-MS and LDI-MS and their adequacy for lichen dereplication was assessed on a vast array of samples encompassing a wide range of metabolites. Both of them facilitated complete chemical profiles, respectively from unprocessed lichen material and crude acetone extracts. Since TLC still enjoys a wide-spread popularity among lichenologists, the advantages offered by TLC-ESI-MS hyphenation were evaluated as well. A second part of this manuscript focused on the histolocalization of lichen metabolites. For this purpose, LDI mass spectrometry imaging studies were undertaken on the crustose lichen Ophioparma ventosa. The phytochemical investigation of this species afforded the isolation of six naphthopyranones from its apothecia, four of them being new molecules. LDI-MSI revealed the distribution patterns of all the main metabolites of this lichen, reaching a spatial resolution of 50 μm. Most interestingly, the distribution pattern of imaged metabolites within the thallus is highly organized and is related to their ecological relevance. Joint strategies combining histolocalization and genetic investigation of lichen symbionts separated using laser capture microdissection were also considered. As such, an investigation of the biosynthesis of mycosporine serinol within Lichina pygmaea dissociated symbionts was initiated. Further analytical strategies such as X-ray powder diffraction are introduced in this thesis that contains six publications and two drafts to be submitted.

Digital filters having sharp transition band play a vital role in modern digital signal processing (DSP) applications. Emerging technologies require digital filters to be both computationally efficient in software/hardware realizations. This thesis is concerned with the design and structural-level optimization of sharp transition band digital filters employing the well known frequency response masking (FRM) approach. Unlike the conventional finite impulse response (FIR) based FRM approach, the FRM technique used in this thesis incorporates infinite impulse response (IIR) digital interpolation subfilters, thereby reducing the overall filter order that results in a reduction of hardware complexity. Two realization methods are discussed in this thesis, namely, the bilinear-lossless-discrete-integrators (bilinear-LDI) digital filter design technique, and the lattice wave digital filter (lattice WDF) digital filter design technique. Diversity controlled (DC) genetic algorithm (GA) is employed to optimize both types of IIR based FRM digital filters over the efficient canonical signed digit (CSD) multiplier coefficient space. DCGAs represent FRM digital filters by a binary chromosome and proceed from a population pool of candidate chromosomes to future generations in order to arrive at the desired FRM digital filter satisfying the design specifications. A novel cost-function is used that allows the DCGA to simultaneously optimize both the amplitude-frequency and group-delay frequency response. A fast convergence speed has been observed. / Communications

Estimation of elastic anisotropy, which is usually caused by rock fabrics and mineral orientation, has an important role in exploration seismology and better understanding of crustal seismic reflections. If not properly taken care of during processing steps, it may lead to wrong interpretation or distorted seismic image. In this thesis, a state-of-the-art under the development Laser Doppler Interferometer (LDI) device is used to measure phase velocities on the surface of rock samples from a major deformation zone (Österbybruk Deformation Zone) in the Bergslagen region of eastern Sweden. Then, a general inversion code is deployed to invert measured phase velocities to obtain full elastic stiffness tensors of two samples from the major deformation zone in the study area. At the end, results are used to correct for the anisotropy effects using three dimensionless Tsvankin's parameters and a non-hyperbolic moveout equation. The resulting stacked section shows partial reflection improvement of the deformation zone compared with the isotropic processing section. This suggests that rock anisotropy may also contribute to the generation of reflections from the deformation zones in the study area but requires further investigations.