hostility has been found to be a risk factor for cardiovascular disease. One proposed pathway between hostility and cardiovascular disease is an increase in cardiovascular reactivity among hostile individuals when faced with challenging, competitive situations, in which interpersonal stressors are present. A potential situation that may elicit this exaggerated reactivity is found in cardiac rehabilitation exercise programs. Such factors may be competition and feedback regarding their performance. This study sought to find out how hostile individuals would respond physiologically, behaviorally, and affectively when presented with negative and positive performance feedback, while exercising in a challenging, competitive setting. It was found that the three groups (positive feedback, negative feedback, no feedback) did not differ on physiological reactivity, exercise behavior, or affect as a result of the type of feedback they received. Limitations of the study are discussed and improvements for future studies are suggested.

Obesity is a growing problem in the United States. Research into the causes, treatment, and prevention of obesity is vital. One past study examined four eating behaviors in relation to obesity: eating beyond satiety, snacking, night eating, and feeling hungry within three hours of eating. Only eating beyond satiety was associated with obesity. The present study examined these same eating behaviors while correcting some of the flaws of the previous study. Using a cross-sectional design, university undergraduates reported on the frequency of the above-named eating behaviors. Current weight and height were collected. Multiple regression analyses determined that eating beyond satiety and hunger predicted body mass index (BMI). Race/ethnicity moderated the relationship between hunger and BMI. These findings have important implications for obesity treatment as well as suggesting important avenues for future research.

Smoking is now the leading cause of preventable death and disease in women. Understanding women's motivations to smoke is important in developing effective cessation and relapse prevention programs. Women, more so than men, appear to associate their smoking behavior to issues of weight. Although a general relationship between weight concerns and smoking has been found among women, a causal relationship had not been demonstrated. This study tested whether activation of negative body image cognitions would produce greater urges to smoke and whether the relationship would be moderated by trait body dissatisfaction and mediated by state body dissatisfaction. A randomized 2 X 2 crossed factorial, within-subjects design (body image cues X smoking cues) was conducted with 62 female college smokers. The body image manipulation comprised an image of either a thin model or a neutral object, and the smoking manipulation comprised an image of either a smoking cue or a neutral object. Participants completed pre-intervention measures assessing smoking history and body image dissatisfaction. Urge to smoke, mood state, and weight and appearance satisfaction were assessed during the experiment. It was hypothesized that main effects on reported urge to smoke would be found for both manipulations, with body dissatisfaction moderating the body image manipulation. Results indicated that both smoking cues and thin model images increased reported urges to smoke. Additionally, in the absence of smoking cues, the effect of the body image manipulation was moderated by baseline body dissatisfaction, with those women with greater body dissatisfaction reacting more strongly to the thin model image. The effect on smoking urges by the body image manipulation was partially mediated by both state measures of affect and body satisfaction. Thus,this study is the first to demonstrate through an experimental design that the presentation of images portraying thin women increased smoking urge, which is consistent with a causal influence of body image affecting their smoking motivation.

Ce travail a eu pour objectif d’améliorer notre compréhension des processus de formation et d’évolution des aérosols organiques secondaires (AOS) en étudiant les réactions susceptibles d’expliquer la présence d’espèces « mixtes » organosoufrées observées récemment dans l’aérosol atmosphérique. Les composés organiques volatils et en particulier les monoterpènes ont été identifiés comme étant des précurseurs potentiellement importants d’organosulfates dans l’atmosphère. Cependant, les mécanismes de formation de ces derniers ne sont pas encore bien compris. Seule une étude au niveau moléculaire et ciblée sur une réaction multiphasique unique, peut donner accès à des mécanismes réactionnels détaillés. Ainsi, les réactions entre l’α-pinène et quatre produits d’oxydation associés (α-pinène oxyde, myrténal, isopinocamphéol et pinanediol), avec des particules modèles de sulfate d’ammonium ont été étudiées individuellement dans le but de documenter la formation d’organosulfates. L’effet de l’humidité relative et celui de l’acidité des particules sur ces réactions ont été étudiés. La quantification en ligne des composés organiques volatils a été effectuée à l’aide d’un spectromètre de masse à transfert protonique. L’identification des structures moléculaires des organosulfates, formés en phase particulaire, a été effectuée par chromatographie liquide couplée à la spectrométrie de masse en tandem. Deux approches complémentaires, impliquant des expériences en réacteur quasi-statique et en chambre de simulation atmosphérique, ont permis de mettre en évidence la formation d’organosulfates mais également de proposer des mécanismes réactionnels pour l’ensemble des composés oxydés étudiés. / This work deals with the formation and aging processes of secondary organic aerosol (SOA). More precisely, the objective was to document organosulfate formation, recently identified in ambient aerosol. Volatile organic compounds (VOCs) such as monoterpenes have been recognized as potentially important precursors of organosulfates in the atmosphere. However, organosulfate formation is not yet well understood. Reliable chemical mechanisms can only be accessible when studying individual reactions at the molecular level. In this work, organosulfate formation was studied for the reactions of α-pinene and associated oxidized species (α-pinene oxide, myrtenal, isopinocampheol and pinanediol) with acidified ammonium sulfate particles. On-line quantification of VOCs was carried out using proton-transfer-reaction mass spectrometry. Identification of products in the particulate phase has been performed using liquid chromatography coupled with tandem mass spectrometry. Experiments from quasi-static reactor and atmospheric simulation chamber experiments are compared and discussed, allowing to propose chemical mechanisms explaining organosulfate formation for the heterogeneous reactions of interest.

Ce travail vise à étudier l’hydratation et les propriétés des ciments brushitiques à base de wollastonite dans la perspective d’une application au traitement et au conditionnement de déchets radioactifs de faible ou moyenne activité acides et/ou contaminés en strontium. Une étude des processus conduisant à la prise et au durcissement d’un ciment commercial est d’abord menée. L’influence de la composition de la solution de gâchage sur les réactions mises en jeu est ensuite précisée. Enfin, une première évaluation du potentiel de ce matériau pour la décontamination ou l’immobilisation d’effluents aqueux contaminés en strontium est réalisée.Les pâtes de ciment brushitique à base de wollastonite sont préparées à partir de wollastonite broyée et d’une solution d’acide phosphorique concentrée contenant des cations métalliques (Zn2+ et Al3+) ainsi que du borax. La wollastonite réagit selon un processus de dissolution/précipitation qui conduit à la formation de brushite, de silice amorphe et d’un aluminophosphate de calcium et de zinc amorphe dont la structure a été caractérisée par RMN-MAS du 31P et 27Al. La précipitation de brushite est précédée par la formation transitoire de phosphate monocalcique monohydraté. La simulation thermodynamique à l’aide d’un code de spéciation géochimique de la réaction de la wollastonite avec une solution d’acide phosphorique reproduit bien la séquence de précipitation des phases cristallines observée expérimentalement.Il apparaît que la concentration optimale de l’acide phosphorique dans la solution de gâchage est comprise entre 9 et 10 mol.L-1. Le bore retarde la prise du ciment tandis que le zinc l’accélère. L’ajout d’aluminium, qui permet la précipitation massive d’aluminophosphate de calcium amorphe, s’avère nécessaire pour obtenir un matériau avec de bonnes performances mécaniques. Une étude de surfaces de réponses par plan d’expériences, suivie d’une optimisation multicritères, a permis d’identifier un domaine de compositions de solutions de gâchage conduisant à un matériau possédant les propriétés recherchées (en terme de temps de prise, auto-échauffement et résistance mécanique) pour une matrice de conditionnement de déchets.Une étude cristallographique montre par ailleurs que la brushite peut incorporer au moins 30 % (mol/mol) de strontium en substitution du calcium dans sa structure. Des essais de piégeage du strontium par une pâte de ciment broyée, menés en suspension diluée, conduisent à une isotherme de sorption de type S, témoignant de l’existence de plusieurs mécanismes de rétention. Enfin, un essai de lixiviation sur un monolithe contenant du strontium révèle le bon confinement de ce dernier, avec un coefficient de rétention Rd plus de 100 fois supérieur à celui obtenu avec une pâte de ciment Portland. / This work aims at studying the hydration process and the properties of wollastonite-based brushite cements. These binders may indeed offer new prospects for the treatment or conditioning of low- or intermediate- level radioactive wastes characterized by a strong acidity and/or a contamination by strontium. First, a study of the hydration process is carried out with a commercial cement. Then, the influence of the mixing solution composition on the setting and hardening process is determined. Finally, a first assessment of the potential of this material for the decontamination and immobilization of strontium-containing aqueous effluents is performed.Wollastonite-based brushite cement pastes are prepared by mixing ground wollastonite and a phosphoric acid solution containing metallic cations (Al3+ and Zn2+) and borax. Wollastonite reacts through a dissolution/precipitation process, which leads to the formation of brushite, amorphous silica and amorphous zinc and calcium aluminophosphate whose structure has been investigated by 31P and 27Al MAS-NMR. The brushite precipitation is preceded by the transient formation of monophosphate calcium monohydrate. The thermodynamic simulation of the wollastonite reaction with a phosphoric acid solution, using a geochemical speciation code, fairly well reproduces the precipitation sequence of crystalline phases observed experimentally.It appears that the optimum phosphoric acid concentration in the mixing solution is comprised between 9 and 10 mol.L-1. Boron retards the cement setting whereas zinc accelerates it. The addition of aluminium, which leads to the massive precipitation of amorphous calcium aluminophosphate, is proved to be necessary to obtain a material with high mechanical strength. Thanks to response surface methodology and multi-criteria optimization, a composition domain of the mixing solution is pointed out, leading to a material with good properties (in terms of setting time, self-heating and mechanical strength) for waste conditioning.A crystallographic study also shows that brushite is able to incorporate at least 30 % (mol/mol) of strontium in substitution for calcium in its structure. Strontium retention tests by a ground cement paste in diluted suspension lead to a type S sorption isotherm, meaning that several retention mechanisms are involved. Finally, a leaching experiment performed on a cement monolith containing strontium shows that this species is well confined within the cement matrix, with a retention coefficient at least two orders of magnitude higher than that of a Portland cement paste.

The purpose of the present study was to use a biopsychosocial approach to investigate the role of body image concerns and appearance-related evaluation stress in the relationship between adiposity and cardiovascular reactivity and recovery. Participants included 106 Caucasian female undergraduates at the University of South Florida. The laboratory procedure consisted of resting baseline, speech preparation and delivery, and recovery phases. Participants also completed a variety of body image questionnaires. To manipulate appearance-related evaluation stress, participants were randomly assigned to present their speech to a video camera or an audio recorder. Overall adiposity was measured as body mass index (BMI) and central adiposity was measured as waist-to-hip ratio (WHR). Greater adiposity was associated with more weight-related anxiety during the speech task, regardless of speech condition (BMI: r = .54, p < .001; WHR: r = .44, p < .001). Additionally, those in the video condition reported more weight-related anxiety (M = 9.28, SD = 7.74) during the speech task than those in the audio condition (M = 3.31, SD < 5.61; F(1,99) = 19.73, p < .001). Significant relationships between adiposity and CVR and recovery emerged for several outcome measures with central and overall adiposity predicting different CVR patterns (all ps < .05). There was no main effect of speech condition on CVR or recovery (all ps > .05). Significant interactions between adiposity and speech condition emerged for some of the outcome variables as well (all ps < .05). Additionally, body image concerns mediated the relationship between adiposity, speech condition, and CVR for SV and CO reactivity. The results suggest that adiposity may have a robust effect on physiological reactivity and recovery independent of psychological processes that co-occur. The results also suggest that those with high adiposity experience more weight-related anxiety during evaluation, even when the evaluation is not intended to induce body image concerns. Finally, the results suggest that body image concerns may act to suppress reactivity among those with high levels of weight-related anxiety. Implications and future directions for research are discussed.

<p>Diamond and cubic boron nitride surfaces have extreme properties that can be exploited in novel tribological, electrochemical and electronic applications. Normally insulating diamond surfaces can exhibit high surface conductivities due to hydrogen termination and the nature of the surrounding atmosphere. Successful growth of cubic boron nitride thin films is hindered when harsh synthesis methods are used.</p><p>Three significant surface-related properties are addressed in this thesis using computational methods: (1) the structure, energy stability and reactivity of clean and differently terminated diamond surfaces, (2) the high surface conductivity of diamond, and (3) the adsorption-induced stability, reactivity and reconstruction of the cubic boron nitride (100) surface. Density Functional Theory (DFT) has been used at the GGA level under periodic boundary conditions to simulate the diamond and cubic boron nitride surfaces. </p><p>The diamond surface structures are shown to be insensitive to hydrogen desorption. Oxygen atoms bind in different positions and with different bond strengths. Hydroxyl groups experience both attractive hydrogen bonding and steric repulsions within the adsorbed species. The reconstruction of diamond (111)-1x1 is strongly dependent on the species adsorbed onto the surface. Electron transfer was observed from a diamond surface into a water-based adlayer, yielding a p-type doped surface, depending on the nature of the surface and the adlayer. The cubic boron nitride (100)-1x1 surface was shown to reconstruct into a 2x1 configuration on both the boron- and nitrogen-rich side through the formation of B-B bonds, as well as N–N dimer-induced surface relaxation. Hydrogen stabilized the (100)-1x1 surface, but the partial removal of hydrogen yielded non-reactive dimer formation on the surface. </p>

Les façades des nouveaux bâtiments et des bâtiments existants sont altérées par la pénétration de l'eau. Afin de protéger les bâtiments et surfaces exposées aux intempéries, des traitements contenant des agents hydrophobes doivent être appliqués. Les traitements utilisés à l’heure actuelle sont des traitements de surface qui se dégradent au cours du temps. L'agent hydrophobe, présent en surface, est soumis à des conditions très rudes telles que des rayonnements ultraviolets, de grandes variations de température, de l'abrasion ..., qui réduisent l’efficacité et la durabilité des traitements. La plupart des traitements aujourd'hui disponibles, fournisse une barrière efficace au passage de l’eau à court terme, mais doivent donc être réappliqués régulièrement. Le projet de recherche, présenté ici, traite de la mise en place d'un traitement de masse de matériaux cimentaires utilisés dans la protection de structures (joints, crépi ...). Ce traitement devrait offrir une protection à long terme, mais ne devrait pas modifier de manière significative les propriétés mécaniques des matériaux. Les avantages d'un traitement de masse sont évidents. Seule une petite partie de l'agent hydrophobe est exposée et dégradée par les conditions climatiques et l'abrasion de surface ne porte pas atteinte à l'intégrité du traitement. Une étude fondamentale a été menée afin d'étudier l'influence de l'incorporation d´agents à base de silicium sur les processus d'hydratation des ciments Portland et de comprendre leur mode d'action. Deux agents (alpha,omega dihydroxypolydimethylsiloxane et n-octyltriethoxysilane) et deux ciments Portland (ordinaire et blanc CEM I 42,5N) ont été choisis et étudiés. Trois modes d´introduction (liquides purs, émulsions et granules) ont été mis en œuvre et comparés. Le but est de déterminer les meilleures conditions pour obtenir un traitement efficace et durable tout en préservant les propriétés mécaniques. Les résultats d'absorption d'eau par capillarité et de perméabilité à la vapeur d’eau sont prometteurs et les essais mécaniques sur mortiers n’ont pas montré de diminutions significatives des résistances mécaniques. La microstructure et la progression de l'hydratation des matrices cimentaires adjuvantées et de référence, ont été caractérisées par calorimétrie à conduction, par calorimétrie différentielle à balayage couplée à la thermogravimétrie, par spectroscopie infra-rouge, par diffraction des rayons X, par porosimétrie au mercure, et par microscopie électronique à balayage. La durabilité des matériaux adjuvantés a été étudiée afin de montrer la pertinence des traitements ainsi que l'évaluation de la progression de l'hydratation. Les performances hydrofuges ainsi que l’évolution de la microstructure, à l’issue des différents vieillissements artificiels et naturels, ont été déterminées. Les mortiers mis en œuvre ont été soumis à des vieillissements artificiels simulant des conditions proches de celles rencontrées en pratique (tels que des cycles rayonnements UV, pluie, sel, gel/dégel…). Une amélioration de la durabilité des mortiers adjuvantés a été observée. Les résultats sont très encourageants et confirment l'intérêt d’un tel traitement dans la masse. /Protection of cement-based materials means above all, moisture protection because water is primarily responsible for inducing damaging physical and chemical processes in building materials. In most cases, water repellents are applied either directly during the construction or insulation process; or as a post-treatment of the exposed surfaces in order to protect the buildings from further decay. A new way is to develop a bulk treatment for cement-based materials which should provide a long term protection without modifying the mechanical properties of the cementitious materials. The advantages of a bulk treatment are obvious i.e. only a small part of the hydrophobic agent is exposed and degraded by the UV. In addition, surface abrasion does not affect the integrity of the treatment. A fundamental study was initiated to investigate the influence of the incorporation of two active silicon-based agents (already used as post-building treatments) on the hydration processes of Portland cements and to understand the involved mechanisms of interaction. Two agents (alpha,omega dihydroxypolydimethylsiloxane and n-octyltriethoxysilane) and two Portland cements (Ordinary and White Portland Cement CEM I 42,5N) were chosen and studied. Three incorporation modes (pure liquids, water emulsions and granules) were investigated. The effects of the three modes were compared. The aim was to determine the best conditions for an efficient and sustainable treatment preserving the mechanical properties of the materials. The results of capillary water penetration and water vapor permeability are promising and are not accompanied by a significant decrease of the mechanical performances The microstructure and progression of hydration of admixtured cement pastes were characterized by conduction calorimetry, differential scanning calorimetry, thermo-gravimetry, infra-red spectroscopy, X-ray diffraction, mercury intrusion porosimetry, and scanning electron microscopy. In addition, the durability of water-repellent additives and of the admixtured cement was studied in order to show the relevance of the treatments as well as the assessment of the progression of hydration and the type of products that were developed. Mortar specimens were submitted to artificial ageing cycles such as freeze-thaw cycles, ultraviolet cycles and rain-sun cycles. The general trend is an improvement of the durability of admixtured mortars. The results are very encouraging and confirm the interest of the bulk mortar treatment.

Today’s market offers an ever-increasing range of cellulose pulps (derivative pulps) made fromvarious wood types through different delignification processes. Each pulp segment has its uniquecharacteristics, which makes it difficult for the producer of cellulose derivatives to choose the mostsuitable pulp for optimum processability and product quality. The objective of this study was toimprove knowledge of cellulose pulps and to describe how different pulp properties affectprocessability and quality in the production of viscose dope and cellulose ethers.Ten pulp samples were investigated, originating from both sulfite and sulfate processes, with highand low viscosities and with softwood and hardwood as raw material. The pulps were analyzed fortheir properties and then processed to viscose dope and a cellulose ether in two separate pilotfacilities. The intermediates in the viscose process as well as the quality of the viscose dope andcellulose ether were analyzed and the results correlated to pulp properties.Multivariate regression methods were applied to investigate the dominating physical and chemicalproperties of each pulp and pulp segment, and to study the use of spectroscopic analyses inpredicting pulp origin, concentration and composition of hemicelluloses as well as the content ofreducing end groups in cellulose. For the production of viscose dope, the models presented showedthe most important pulp properties for good cellulose reactivity and viscose filterability. In addition,the properties affecting gel formation, flocculation, degree of substitution and clarity in theproduction of cellulose ether were highlighted. The study also emphasized the need to supplementthe use of conventional analyses on pulps and viscose intermediates with other analytical methods,such as molecular weight distribution and carbohydrate analysis, to better predict the quality ofboth viscose dope and viscose fiber.The results of the present study could be useful to predict the origin and properties of new pulps, toreplace or supplement otherwise expensive pulp analyses, and to assess the impact of pulpproperties on the production of cellulose derivatives without extensive pilot-scale trials.

By using multidisciplinary analysis of CA inclusions in prostate glands of patients diagnosed with prostate cancer, we have revealed that their major components are the amyloid forms of S100A8 and S100A9 proteins associated with numerous inflammatory conditions and types of cancer. We have demonstrated that material closely resembling CA can be produced from S100A8/A9 in vitro and shows the characters of amyloids. This process is facilitated by calcium or zinc, both of which are abundant in ex vivo inclusions. These observations were supported by computational analysis of the S100A8/A9 calcium-dependent aggregation propensity profiles. We have found DNA and proteins from Escherichia coli in CA bodies, suggesting that their formation is likely to be associated with bacterial infection. CA inclusions were also accompanied by the activation of macrophages and by an increase in the concentration of S100A8/A9 in the surrounding tissues, indicating inflammatory reactions. These findings, taken together, suggest a link between bacterial infection, inflammation and amyloid deposition of pro-inflammatory proteins S100A8/A9 in the prostate gland, such that a self-perpetuating cycle can be triggered and may increase the risk of malignancy in the ageing prostate. We evaluated the autoimmune reactions to endocrine (insulin) and astrocytical (S100B) biomarkers in the blood sera of PD patients compared with healthy controls. Peripheral immune responses can be sensitive indicators of disease pathology. We found a statistically significant increase of the autoimmune responses to both antigens in patients compared with controls. Heterogeneity of the immune responses observed in patients may reflect the modulating effect of multiple variables associated with neurodegeneration and also changes in the basic mechanisms of individual autoimmune reactivity. We did not detect any pronounced immune reactions towards insulin amyloid fibrils and oligomers in patients, indicating that an amyloid-specific conformational epitope is not involved in immune recognition of this amyloid type. Immune reactions towards S100B and insulin may reflect the neurodegenerative brain damaging processes and impaired insulin homeostasis occurring in PD. Generated auto-antibodies towards the major amyloidogenic protein involved in PD Lewy bodies - a-synuclein and its amyloid oligomers and fibrils were measured in the blood sera of early and late PD patients and controls by using ELISA, Western blot and Biacore surface plasmon resonance analyses. We found significantly higher antibody levels towards monomeric a-synuclein in the blood sera of PD patients compared to controls, though the responses decreased with PD progression. There were no noticeable immune responses towards amyloid oligomers, but substantially increased levels of IgGs towards a-synuclein amyloid fibrils both in PD patients and controls, which subsided with the disease progression. Pooled IgGs from PD patients and controls interacted also with amyloid fibrils of Ab (1-40) and hen lysozyme, however the latter were recognized with lower affinity. This suggests that IgGs bind to amyloid conformational epitope, though displaying higher specificity towards human amyloid species associated with neurodegeneration. The findings suggest the protective role of autoimmunity in PD and therefore immune reactions towards PD major amyloid protein - a-synuclein can be used in treatment strategies and in diagnostics, especially in identifying early disease.