Flavin adenine dinucleotide (FAD) is a coenzyme that participates in the redox process of flavoenzymes. Attempts to characterize the catalytic pathways of these enzymes have relied in part on the use of FAD chemical models. The efforts described in this dissertation focus on the chemical model approach to investigate the mechanism of the monoamine oxidase (MAO) catalyzed oxidation of the cyclic tertiary allylamine 1-methyl-4-(2-methyl-1H-pyrrol-2-yl)-1,2,3,6-tetrahydropyridine (TMMP), which is a close analog of the parkinsonian-inducing designer drug 1-methyl-4-phenyl-1,2,3,6-tetrahydropyridine (MPTP). MAO-B catalyzes the conversion of MPTP and its derivatives into active neurotoxins in the brain that subsequently mediate neurogenerative processes that mimic the events leading to idiopathic Parkinson\'s disease. Monoamine oxidase inhibitors are currently used to treat early stages of Parkinson\'s disease. Two FAD chemical models are examined in this project: 5-ethyl-3-methyllumiflavinium perchlorate (5Et3MLF+ClO4-) and 3-methyllumiflavin (3MLF). The flavinium salt 5Et3MLF+ClO4- is an activated form of 3MLF. These FAD chemical models have been used to examine the MAO catalyzed oxidation. MAO-B is expressed in the brain and is known to be involved in the conversion of TMMP into the neurotoxic metabolite 1-methyl-4-phenyl pyridnium (MMP+). MAO-B is responsible for the alpha-carbon oxidation of TMMP to yield 1-methyl-4-(2-methylpyrrol-2-yl)-2,3-dihydropyridinium (DHP+), which then undergoes a second 2-electron oxidation to MMP+. Previous findings demonstrated that 3MLF and 5Et3MLF+ClO4- promoted the oxidation reaction of primary and secondary amines but not tertiary amines. However, the cyclic tertiary allylamine TMMP has not been examined experimentally. Therefore, the alpha-carbon oxidation of TMMP in the presence of the FAD chemical models is reported in this dissertation. The effect of dioxygen and water on the activity of these FAD models is also investigated. / Ph. D.

In the first part of this study, frictional and normal forces in aqueous solutions were measured between a glass particle and oligopeptide films grafted from a glass plate. Homopeptide molecules consisting of 11 monomers of different amino acids were each "grafted from" an oxidized silicon wafer using microwave-assisted solid phase peptide synthesis. Oligopeptides increased the magnitude of friction compared to a bare hydrophilic silicon wafer. Friction was a strong function of the nature of the monomer unit and was lower for hydrophilic films. There was a strong adhesion and therefore friction between surfaces of opposite charges. Changes in adhesion and friction depended on the hydrophobicity and electrostatic forces: hydrophobic films and oppositely charged films produced high friction, whereas hydrophilic and like-charges produced low friction. Friction was lower in phosphate buffered saline than in pure water due to the screening of the double layer attraction for oppositely charged surfaces and additional lubrication by hydrated salt ions. We also investigated antimicrobial action of poly (allyl amine) (PA) when covalently bonded to glass. Glass surfaces were prepared by a two-step procedure where the glass was first functionalized with epoxide groups using 3-glycidoxypropyltrimethoxy silane (GOPTS) and then exposed to PA to bind via reaction of a fraction of its amine groups. Antibacterial properties of these coatings were evaluated by spraying aqueous suspensions of bacteria on the functionalized glass slides, incubating them under agar, and counting the number of surviving cell colonies. The PA film displayed strong anti-microbial activity against both Gram-positive and Gram-negative bacteria. Films that were prepared by allowing the PA to self assemble onto the solid via electrostatic interactions were ineffective antimicrobials. Such films had an insufficient positive charge and did not extend far from the solid. Thus we found that antimicrobial activity was correlated with a combination of the ability of the polymer chain to extend into solution and a positive surface potential. / Ph. D.

New vigorous regulations have been established for decreasing the allowable formaldehyde emissions from nonstructural wood based composites. Two main sources of formaldehyde emission in non-structural wood based composites are adhesive and wood. Adhesives are quite well known and great efforts have been conducted to decrease their formaldehyde content; however formaldehyde emission from wood has received little attention and it is not completely understood. Wood-borne formaldehyde emission exists in a complex equilibrium in wood matrix. The reaction between formaldehyde and wood hydroxyl groups/water can hinder the complete formaldehyde extraction. In order to have a complete formaldehyde extraction, a stronger nucleophile than hydroxyl and water groups is needed. In this study cross-linked poly (allylamine) (PAA) beads were synthesized and used as a strong nucleophile to extract all the biogenic and synthetic free-formaldehyde within the woody matrix of never-heated and heat-treated Virginia pines; the results were compared to simple water extraction. A new formaldehyde capturing device was also developed using a serum bottle. Results showed that there was no advantage of using PAA beads over simple water extraction for extracting woody matrix free-formaldehyde. This means that simple water extraction can extract all the free-formaldehyde from the woody matrix. It was also found that thermal treatment resulted in generating more wood-borne formaldehyde. The other important finding was the new developed formaldehyde capturing device. The device was very promising for detecting wood-borne formaldehyde from very small pieces of wood (5-70 mg) and can be very useful in future studies. / Master of Science

No description available.

Les stents coronariens sont des dispositifs médicaux, généralement fabriqués en acier inoxydable 316L, utilisés pour traiter des maladies cardiovasculaires comme l’athérosclérose. Les stents recouverts ou à relargage contrôlé de médicaments sont des solutions prometteuses pour réduire les phénomènes de resténose. Ce travail a pour objectif le développement d’un procédé plasma basse pression capable de déposer une couche de polymère permettant de protéger la surface des stents contre l’agressivité du milieu physiologique. L’allylamine est choisie comme précurseur moléculaire pour assurer un taux élevé de fonctions amines primaires. Ces fonctions pourront être utilisées, successivement, pour l’immobilisation de molécules bioactives afin d’augmenter la biocompatibilité des stents. Les dépôts sont effectués sur des substrats d’acier inoxydable 316L en utilisant un réacteur plasma basse pression (70 kHz). Les différentes techniques d’analyse de surface utilisées (angle de contact, XPS, FTIR-ATR) montrent que les variations de puissance de la décharge et du temps de traitement ne modifient pas significativement la composition chimique de surface des dépôts. Cependant, grâce à une technique de dérivation chimique nous avons mis en évidence une meilleure sélectivité vis-à-vis des fonctions amines primaires pour les couches déposées à faibles valeurs de puissance. En effet, des analyses in-situ de la phase plasmagène (spectrométrie de masse, spectroscopie d’émission optique) révèlent qu’une augmentation de la puissance de la décharge conduit à l’augmentation de son caractère énergétique et, ainsi, à l’augmentation du taux de fragmentation du précurseur. La stabilité des revêtements au lavage dans l’eau de-ionisée a été aussi évaluée. Les dépôts obtenus pour une puissance de la décharge de 2W présentent le meilleur compromis entre rétention des fonctions amines primaires et stabilité. Enfin, nous avons évalué les propriétés d’adhérence des couches après déformation plastique en utilisant le « small punch test », permettant de reproduire les conditions qu’on retrouve lorsque les stents sont déployés dans les artères. Les dépôts présentent des propriétés adéquates de cohésion et d’adhérence au substrat pour répondre à la déformation sans se fissurer et/ou délaminer. Ces résultats montrent que les couches d’allylamine déposées par procédé plasma basse pression présentent des caractéristiques prometteuses afin d’être utilisées comme revêtement performant pour les stents coronariens. / Coronary stents are metallic devices, mainly made of 316L stainless steel (316L SS) used for the treatment of cardiovascular disease such as atherosclerosis. In order to reduce the restenosis rate of bare metal stents, coated stents and drug eluting stents were developed. The aim of this study is to develop a process to isolate metallic surface from the biological environment by depositing a thin plasma polymerized allylamine (PPAA) film on the metallic surface. Allylamine has been chosen as molecular precursor to insure high retention of primary amino groups which can be used, afterwards, to graft biomolecules to improve the biocompatibility of the devices. PPAA films were deposited on flat electropolished 316L SS samples in a low pressure plasma reactor (70 kHz). The different surface analytical methods (water contact angle, XPS, FTIR-ATR) showed that surface chemical composition of the coatings was not significantly influenced by variation of plasma power discharge and treatment time. However, chemical derivatization has shown that high selectivity towards primary amino-groups could be obtained using low discharge power values. In fact, in-situ diagnostic analysis of the plasma discharge, performed by mass spectrometry and optical emission spectroscopy, revealed the increase of the energetic character of the discharge as a function of discharge power that leads to higher fragmentation of the precursor. The coating stability in de-ionised (D.I.) water has been also investigated. We have found an optimum of stability for films deposited at a power of 2 W. For this optimized condition, we have the best trade-off between selectivity and stability upon immersion in D.I. water. In order to mimic stent expansion conditions, a “small punch test” has been used to investigate the adhesive properties of the coating. According to XPS analysis, no significative modification of the chemical composition of the coating was induced by plastic deformation. No cracks, delamination or failures of the coating were observed by FE-SEM indicating that the coating presents sufficient interfacial adhesion and cohesion to resist to plastic deformation. For these reasons, PPAA films presents promising features to be applied as a coating for coronary stents.