L'objectif de cette recherche est d’explorer de nouvelles voies dans le domaine de la détection de gaz en ajustant finement la nature chimique, la texture et la morphologie de la couche active pour concevoir de nouveaux capteurs de gaz sélectifs. Ainsi, l’obtention de matériau présentant une haute sélectivité vis-à-vis des gaz constitue un enjeu majeur dans le domaine des capteurs de gaz. Notre approche est basée sur la conception de précurseurs moléculaires uniques - les alcynylorganoétains - qui contiennent toutes les fonctionnalités requises pour obtenir des matériaux hybrides stables par le procédé sol-gel, ces matériaux permettant une détection sélective des gaz nocifs / toxiques. Puis, les propriétés de détection de gaz de ces matériaux ont été comparées à celles de nanoparticules de dioxyde d'étain (SnO2) synthétisées à pression autogène. Une série de matériaux fonctionnels à base d'organooxoétains a été déposé sous forme de films minces films par le procédé d’enduction centrifuge puis ces films ont été caractérisés par des mesures de XRD, FT-IR, RAMAN, AFM, SEM, TEM, sorption d’azote et TGA-DTA. Les études de détection de gaz montrent que l'un des oxydes d'organoétain hybride présente une réponse sélective de détection de gaz tels que le CO, H2, l'éthanol, l'acétone et le NO2, tandis que les nanoparticules SnO2 conduisent à une détection non sélective des m^mes gaz dans les mêmes conditions. Ainsi, la meilleure sélectivité vis-à-vis du CO (à 100 et 200 ppm), de H2 (à 100, 200 et 400 ppm) et de NO2 (à 1, 2, 4 et 8 ppm) a été obtenue à 100 ° C pour le matériau hybride organostannique tandis que ce matériau ne conduisait à aucune réponse avec l’éthanol et l’acétone. Par ailleurs, les films de SnO2 nanoparticulaire sont sensibles à tous les gaz testés à de faibles concentrations (CO: 10 ~ 100 ppm, NO2: 0,5 à 4 ppm, H2: 100 à 800 ppm, acétone: 25 à 200 ppm, éthanol : 10 ~ 100 ppm) sur une plage de température comprise entre 200 et 400 °C. En outre, la sélectivité des matériaux SnO2 vis-à-vis de NO2 (entre 0,5 à 4 ppm) peut être optimisée en contrôlent bien la température de détection. Enfin, les matériaux à base d’organoétains et de dioxyde d’étain présentent une capacité de détection de gaz très élevée à de faibles concentrations en gaz. Ces résultats ont permis de développer une classe de matériaux entièrement nouvelle pour la détection sélective de gaz ainsi offrent la possibilité d'intégrer une fonctionnalité organique dans les oxydes métalliques capables de détecter les gaz. / The ultimate objective of this research is to draw new prospects in the gas sensing field by finely tuning the chemical nature, the texture and the morphology of the active layer to develop new type selective gas sensors. High gas selectivity has been a challenging issue during the past decades in the gas sensing area. Our approach is based on the design of molecular single precursors – alkynylorganotins which contain suitable functionalities required to obtain stable hybrid materials by the sol-gel method exhibiting selective gas detection towards harmful/toxic gases. Their gas sensing properties have been compared with those of tin dioxide (SnO2) nanoparticles synthesized by the hydrothermal route. A series of functional organooxotin-based materials have been processed as films by the spin or drop coating method and characterized by XRD, FT-IR, RAMAN, AFM, SEM, TEM, N2 sorption and TGA-DTA measurements. Gas sensing studies show that one of the hybrid organotin oxides exhibits an outstanding selective gas sensing response towards various gases, such as CO, H2, ethanol, acetone and NO2 whereas SnO2 nanoparticles present non-selective gas sensing ability under the same experimental condition. Thus, the best gas selectivity toward CO (at 100 and 200 ppm), H2 (at 100, 200 and 400 ppm) and NO2 (at 1, 2, 4 and 8 ppm) was achieved at 100 °C for the hybrid organooxotin-based film, however, it showed no response to ethanol/acetone at the same working temperature. On the other hand, the nanoparticulate SnO2 films prepared are sensitive to all the gases tested at low concentrations (CO: 10~100 ppm; NO2: 0.5~4 ppm; H2: 100~800 ppm; acetone: 25~200 ppm; ethanol: 10~100 ppm) in an operating temperature range from 200 to 400 °C. Moreover, the selectivity of SnO2 materials towards NO2 (between 0.5 ~ 4 ppm) can be optimized by well-manipulating the sensing temperatures. Finally, both organooxotin-based and tin oxide-based materials display superior gas sensing ability at low gas concentrations which opens a fully new class of gas sensing materials as well as a new possibility to integrate organic functionality in gas sensing metal oxides.

Studies that have investigated college choice factors for high-achieving students repeatedly cite academic reputation as one of the top indicators of choice but have not indicated why some high-achieving students choose to attend universities with a less prestigious reputation than the more highly prestigious options available to them. The purpose of this study was to examine whether differences exist between traditional-aged high achieving students who choose to attend higher-tiered universities and their peers who choose to attend lower-tiered universities. Independent variables were selected based upon Hossler and Gallagher's (1987) three-stage model and previous research findings in the literature and grouped according to: (1) students' individual and family characteristics, including ethnicity, gender, parents' education level, and family income; (2) institutional characteristics, including financial considerations and academic reputation; and (3) the influence of others, including parents, relatives, teachers and counselors. The sample was drawn from the 97 universities which administered the CIRP Freshman Survey in 2004. Data were used for students who were attending their first choice college located more than 100 miles from home. Data were used from students who had received scores at or above 660 on the SAT Verbal, and scores at or above 670 on the SAT Math. For students who did not report scores for both SAT verbal and SAT math, the researcher accepted data from students reporting an ACT composite score of 30 or higher. In addition, in order for their data to be used, students were required to have an A or A+ average in high school. Results were reported as (1) frequencies and descriptive statistics, (2) a correlation matrix, and (3) multiple regression models. The study found the availability of financial aid to be the most important factor in predicting whether students will attend a higher-tiered or lower-tiered university. Although college costs and academic reputation were found to be significant predictors of the tier level of university attended, they were of secondary importance compared with the attention to financial aid by high achieving students.

This dissertation involves the study of epitaxial behavior of one-dimensional nanomaterials like single-walled carbon nanotubes and Indium Arsenide nanowires grown on metallic catalyst surfaces. It has been previously observed in our novel microplasma based CVD growth of SWCNTs on Ni-Fe bimetallic nanoparticles that changes in the metal catalyst composition was accompanied by variations in the average metal-metal bond lengths of the nanoparticle and that in turn, affected nanotube chirality distributions. In this dissertation, we have developed a very simplistic model of the metal catalyst in order to explain the nanotube growth of specific nanotube chiralities on various Ni-Fe catalyst surfaces. The metal catalyst model is a two-dimensional flat surface with varying metal-metal bond lengths and comprising of constituent metal atoms. The effect of the composition change was modeled as a change in the bond length of the model catalyst surface and density functional theory based calculations were used to study specific nanotube caps. Our results indicated that nanotube caps like (8,4) and (6,5) show enhanced binding with increased metal-metal bond lengths in the nanoparticle in excellent agreement with the experimental observations. Later, we used this epitaxial nucleation model and combined with a previously proposed chirality-dependent growth rate model to explore better catalysts that will preferentially grow an enhanced chirality distribution of metallic nanotubes. From our DFT calculations and other geometrical considerations for nanotube growth, we demonstrated that the pure Ni0.5Cu0.5 metal nanoparticles and its lattice-strained surfaces can serve as a promising catalyst for enhanced growth of metallic nanotubes. Finally, we extended this model of epitaxial growth to study the growth of,andoriented nanowires on gold metal nanoparticles where a faster growth rate ofnanowires was previously observed in experiments on shaped nanoparticles than that on spherical nanoparticles. The DFT calculations indicated an enhanced growth selectivity of theoriented nanowires on the Au(111) surfaces. However, the DFT results also show that theandNWs will preferentially grow on the Au(100) surface than on the Au(100) surface. The epitaxial model based DFT calculations of nanotube and nanowire growth on metal catalyst surfaces presented in this dissertation, provide a deep insight into their epitaxial growth mechansims and, can be easily exploited to layout better design principles of synthesizing catalysts that helps in growing these one-dimensional nanomaterials with desired material properties.

In the context of transistor size miniaturization the motivation of this work was focused on the fabrication process of planar double gate devices. We proposed in this work three process flows based on the use of buried mask which could allow the fabrication of self-aligned planar double gate transistors. The novel concept of buried mask consists into modifying the etch rate of a buried polysilicon or oxide layer. This etch rate modification being defined by ion implantation, etch stop or scacrificial zones aligned with the implantation mask can thus be fabricated. This technique solve the alignment of the front and back gate. Ion implantation causes damages to the implanted target, and is used to dope semiconductor material. If the implanted atoms have a small radii they can induce stress to the implanted lattice. These three consequences of ion implantation, damage, doping and stress are used to modify the etch rate of oxide and polysilicon. High etching selectivity are reached, which allow the fabrication of a localized buried sacrificial or etch stop zone, called buried mask. The definition of the buried mask being done by ion implantation, it opens the possibility to fabricate a buried mask aligned with the implantation mask. Although some more work has to be invested to fabricate planar double gate MOS using buried mask in polysilicon, this concept of buried mask, which could also be called anisotropic wet and vapor etching, is foreseen as a very promising technique in MEMS micromachining and for bio sensor applications.

The processes influencing larval fish survival in the low-latitude open ocean are poorly understood, especially with regard to feeding. As part of a large-scale study that included two years of monthly sampling in the Straits of Florida (SOF), the objectives of this dissertation were to elucidate the larval fish feeding behaviors and strategies of 1) istiophorid billfishes, 2) tunas, and 3) coral reef fishes, while also 4) characterizing the feeding environment, synthesizing the dominant trophic pathways to fish larvae, and reviewing the literature for evidence of latitudinal distinctions in larval fish trophodynamics. Larval billfishes exhibited highly selective feeding, and their diets were numerically dominated (90%) by two genera of crustaceans, Farranula copepods and Evadne cladocerans. These prey were consumed throughout early larval ontogeny, from first-feeding through piscivorous lengths (> 5 mm), until piscivory became exclusive near 12 mm. High feeding incidence (0.94) and rapid digestion (~3.5 hrs) suggests frequent and successful feeding by billfish larvae. For tunas, nearly all larvae examined (>98%) contained prey. Thunnus spp. exhibited a mixed diet, while skipjack, little tunny, and Auxis spp. nearly exclusively consumed appendicularians. All four tuna taxa co-occurred in the western SOF where prey was more abundant, while in the central and eastern SOF (where prey availability was lower), only Thunnus spp. and skipjack were present. Additionally, these two taxa exhibited significantly different vertical distributions. Estimates of predatory impact indicated the potential for depletion of resources in the absence of the spatial and dietary niches of larval tunas. Coral reef fish families examined included Serranidae, Lutjanidae, Mullidae, Pomacentridae, Labridae, Scaridae, and Acanthuridae. Feeding incidences were high (0.94 to 1.0) for all taxa except scarids (0.04), and diets were narrow and predator-specific. Cluster analysis yielded clear groupings based on the selective feeding exhibited by the taxa, while within taxa, canonical correspondence analysis illustrated the change in diet with a variety of variables. The physical and biological environment varied markedly across the SOF, largely influenced by the Florida Current. Characteristics examined included thermocline depth, fluorescence, and abundances of total plankton and copepod nauplii. The feeding ecologies of the 21 taxa of fish larvae in this work were synthesized into qualitative and quantitative webs that illustrate the variable trophodynamic strategies of larvae in the SOF and the levels of community reliance upon zooplankton prey types. A review of 170 investigations on larval fish feeding revealed notable distinctions between high- and low-latitude regions, highlighting the substantial variability across environments in the role of larval fishes within the planktonic food web.

Evolution of enzymes with novel functional properties has gained much attention in recent years. Naturally evolved enzymes are adapted to work in living cells under physiological conditions, circumstances that are not always available for industrial processes calling for novel and better catalysts. Furthermore, altering enzyme function also affords insight into how enzymes work and how natural evolution operates. Previous investigations have explored catalytic properties in the directed evolution of mutant libraries with high sequence variation. Before this study was initiated, functional analysis of mutant libraries was, to a large extent, restricted to uni- or bivariate methods. Consequently, there was a need to apply multivariate data analysis (MVA) techniques in this context. Directed evolution was approached by DNA shuffling of glutathione transferases (GSTs) in this thesis. GSTs are multifarious enzymes that have detoxication of both exo- and endogenous compounds as their primary function. They catalyze the nucleophilic attack by the tripeptide glutathione on many different electrophilic substrates. Several multivariate analysis tools, e.g. principal component (PC), hierarchical cluster, and K-means cluster analyses, were applied to large mutant libraries assayed with a battery of GST substrates. By this approach, evolvable units (quasi-species) fit for further evolution were identified. It was clear that different substrates undergoing different kinds of chemical transformation can group together in a multi-dimensional substrate-activity space, thus being responsible for a certain quasi-species cluster. Furthermore, the importance of the chemical environment, or substrate matrix, in enzyme evolution was recognized. Diverging substrate selectivity profiles among homologous enzymes acting on substrates performing the same kind of chemistry were identified by MVA. Important structure-function activity relationships with the prodrug azathioprine were elucidated by segment analysis of a shuffled GST mutant library. Together, these results illustrate important methods applied to molecular enzyme evolution.

The kinetic mechanism of an α/β hydrolase fold epoxide hydrolase from potato, StEH1, has been studied with the aims of explaining the underlying causes for enantio- and regioselectivity, both being important for product purity. Further effort has been laid upon understanding the causes of a hysteretic behavior discovered in the measurements leading to Paper I. The enantioselectivity was investigated with substrates differing only in substituent size at one carbon of the oxirane ring structure. In catalysis with trans-stilbene oxide and styrene oxide, enantioselectivity is the result of differences in alkylation rates. In pre-steady state measurement with trans-2-methylstyrene oxide (2-MeSO), a rate-limiting step involving slow transitions, referred to as hysteresis, was discovered. With this substrate enantioselectivity is proposed to be a consequence of the catalytic rate of (1R,2R)-enantiomer being more influenced by the hysteretic behavior than was the rate of the other enantiomer. In steady-state measurements with (1R,2R)-2-MeSO, at different temperatures and pH, hysteretic cooperativity was displayed. It can be concluded that this behavior is dependent on the relationship between kcat and the rate of transition between two Michaelis complexes. From the differences in pH dependence of kcat/KM in formation of the two diols resulting from low regioselectivity in catalysis of (1R,2R)-2-MeSO, it is suggested that hysteresis is a result of the substrates placed in different conformational modes within the active site cavity. Regioselectivity is proposed to be the result of specific interactions between the catalytically important Tyr and the substrate, with a link between KM-values and degree of regioselectivity. Furthermore, the hysteretic kinetic model proposed can explain hysteresis, cooperativity and regioselectivity resulting from StEH1 catalyzed hydrolysis of (1R,2R)-2-MeSO.

The work leading to this thesis has provided additional information and novel knowledge concerning structure-function relationship in the potato epoxide hydrolase. Epoxide hydrolases are enzymes catalyzing the hydrolysis of epoxides to yield the corresponding vicinal diols. The reaction mechanism proceeds via a nucleophilic attack resulting in a covalent alkylenzyme intermediate, which in turn is attacked by a base-activated water molecule, followed by product release. Epoxides and diols are precursors in the production of chiral compounds and the use of epoxide hydrolases as biocatalysts is growing. The promising biocatalyst StEH1, a plant epoxide hydrolase from potato, has been investigated in this thesis. In paper I the active site residue Glu35, was established to be important for the formation of the alkylenzyme intermediate, activating the nucleophile for attack by facilitated proton release through a hydrogen bond network. Glu35 is also important during the hydrolytic half reaction by optimally orienting the hydrolytic water molecule, aiding in the important dual function of the histidine base. Glu35 makes it possible for the histidine to work as both an acid and a base. In paper II a putative proton wire composed of five water molecules lining a protein tunnel was proposed to facilitate effective proton transfer from the exterior to the active site, aiding in protonation of the alkylenzyme intermediate. The protein tunnel is also proposed to stabilize plant epoxide hydrolases via hydrogen bonds between water molecules and protein. Enzyme variants with modified enantiospecificity for the substrate (2,3-epoxypropyl)benzene have been constructed by in vitro evolution using the CASTing approach. Residues lining the active site pocket were targeted for mutagenesis. From the second generation libraries a quadruple enzyme variant, W106L/L109Y/V141K/I155V, displayed a radical shift in enantioselectivity. The wild-type enzyme favored the S-enantiomer with a ratio of 2:1, whereas the quadruple variant showed a 15:1 preference for the R-enantiomer.

This thesis is about protein profiling in blood-derived samples using suspension bead ar- rays built with protein affinity reagents, and the evaluation of binding characteristics and potential disease relation of such profiles. A central aim of the presented work was to discover and verify disease associated protein profiles in blood-derived samples such as serum or plasma. This was based on immobiliz- ing antigens or antibodies on color-coded beads for a multiplexed analysis. This concept generally allow for a dual multiplexing because hundreds of samples can be screened for hundreds of proteins in a miniaturized and parallelized fashion. At first, protein antigens were used to study humoral immune responses in cattle suffering from a mycoplasma infec- tion (Paper I). Here, the most immunogenic of the applied antigens were identified based on reactivity profiles from the infected cattle, and were combined into an antigen cocktail to serve as a diagnostic assay in a standard ELISA set-up. Next, antibodies and their em- ployment in assays with directly labeled human samples was initiated. This procedure was applied in a study of kidney disorders where screening of plasma resulted in the discovery of a biomarker candidate, fibulin-1 (Paper II). In parallel to the disease related applica- tions, systematic evaluations of the protein profiles were conducted. Protein profiles from 2,300 antibodies were classified on the bases of binding properties in relation to sample heating and stringent washing (Paper III). With a particular focus on heat dependent de- tectability, a method was developed to visualize those proteins that were captured to the beads in an immunoassay by using Western blotting (Paper IV). In conclusion, this thesis presents examples of the possibilities of comparative plasma profiling enabled by protein bead arrays. / <p>QC 20130208</p>

As the number of cancer survivors continues to rise, there is an increasing need for psychological research to better understand and help individuals cope with their cancer journey. According to Socioemotional Selectivity theory (SST), shortened time perspective and mortality awareness heighten the importance of social and emotional goals. In the present analysis, SST is applied to the unmet needs of cancer survivors. This is done to provide a better understanding of the association between unmet needs of cancer survivors and the impact of such needs on the survivors' psychological well-being, especially in the case of survivor’s awareness of his/her mortality. In keeping with SST theory, we anticipated that for those with higher mortality awareness (e.g., recurrence of cancer, older age, greater mortality ratio), high unmet social and emotional needs, above else, will be associated with lower psychological well-being. Partial support was found for these hypotheses and results are discussed in terms of their contribution to a better understanding of the nature of psychological well-being of cancer survivors.