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<p>This thesis is a summary of five papers with focus on adsorption processes of various monocarboxylates and aminocarboxylates at the water/goethite interface. Interaction of organic acids at the water/mineral interfaces are of importance in biogeochemical processes, since such processes have potential to alter mobility and bioavailability of the acids and metal ions.</p><p>In order to determine the coordination chemistry of acetate, benzoate, cyclohexanecarboxylate, sarcosine, MIDA (methyliminediacetic acid), EDDA (ethylenediamine-N,N’-diacetic acid) and EDTA (ethylenediamine-N,N’-tetraacetic acid) upon adsorption to the goethite (alpha-FeOOH) surface, a combination of quantitative measurements with attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) was utilized.</p><p>Over the pH range studied here (pH 3- 9) all ligands, except for sarcosine, have been found to form surface complexes with goethite. In general, theses were characterized as outer sphere surface complexes i.e. with no direct interaction with surface Fe(III) metal ions. Furthermore, two types of different outer-sphere complexes were identified, the solvent-surface hydration-separated ion pair, and hydration-shared ion pair. For the monocarboxylate surface complexes distinction between these two could be made. At high pH values the solvent-surface hydration-separated ion pair was the predominating complex, while at low pH the surface complex is stabilized through the formation of strong hydrogen bonds with the goethite surface. However, it was not possible to clearly separate between the two outer-sphere complexes for coordination of the aminocarboxylates with the surface of goethite. Additionally, EDDA also formed an inner-sphere surface complex at high pH values. The EDDA molecule was suggested to coordinate to the surface by forming a five membered ring with an iron at the goethite surface, through the amine and carboxylate groups.</p><p>Contrary to the other ligands studied, EDTA significantly induced dissolution of goethite. Some of the dissolved iron, in the form of the highly stable FeEDTA- solution complex, was indicated to re-adsorb to the mineral surface as a ternary complex. Similar ternary surface complexes were also found in the Ga(III)EDTA/goethite system, and quantitative and spectroscopic studies on adsorption of Ga(III) in presence and absence of EDTA showed that EDTA considerably effects speciation of gallium at goethite surface.</p><p>The collective results in this thesis show that the affinity of these ligands for the surface of goethite is primarily governed by their chemical composition and structure, and especially important are the types, numbers and relative position of functional groups within the molecular structure.</p>

As feature sizes in semiconductor devices become smaller and newer materials are incorporated, current methods for photoresist and post plasma etch residue removal face several challenges. A cleaning process should be environmentally benign, compatible with dielectric materials and copper, and provide residue removal from narrow and high aspect ratio features. In this work, sub-critical CO2 based mixtures have been developed to remove the etch residues; these mixtures satisfy the above requirements and can potentially replace the two step residue removal process currently used in the integrated circuit (IC) industry. Based on the chemical nature of the residue being removed, additives or co-solvents to CO2 have been identified that can remove the residues without damaging the dielectric layers. Using the phase behavior of these additives as a guide, the composition of the co-solvent was altered to achieve a single liquid phase at moderate pressures without compromising cleaning ability. The extent of residue removal has been analyzed primarily by x-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM). Various techniques such as attenuated total reflection - Fourier transform infrared (ATR-FTIR) spectroscopy, angle-resolved XPS (ARXPS), and interferometry were used to probe the interaction of cleaning fluids with residues. Model films of photoresists and plasma deposited residues were used to assist in understanding the mechanism of residue removal. From these studies, it was concluded that residue removal takes place primarily by attack of the interface between the residue and the substrate; a solvent rinse then lifts these residues from the wafer. It has been shown that transport of the additives to the interface is enhanced in the presence of CO2. From positronium annihilation lifetime spectroscopy (PALS) studies on a porous dielectric film, it has been shown that these high pressure fluids do not cause significant changes to the pore sizes or the bonding structure of the film. Hence, this method can be used to remove post etch residues from low-k dielectric films.

Although the effects of diabetes on bone mineral content has been studied, little is known about the structural alterations in collagen, maturation of apatite crystals and carbonate content in diabetic bone. The first part of this study aimed to investigate the mineral and organic properties of cortical, trabecular and growth plate regions of rat femur tissues in type I diabetes using FTIR microspectroscopy and Vickers microhardness test. A decrease in mineral content (degree of mineralization), decrease in microhardness, increase in carbonate content, increase in size and maturation of hydroxyapetite crystals, which are the implications of increased osteoporosis, were observed in diabetic bone. In addition, a decreased carbonate substitution into bone apatite and an increase in labile type carbonate was observed in diabetic bone. There was a decrease in the level of crosslinking of collagen in cortical and trabecular regions of diabetic femurs, implying a decrease in bone collagen quality that may contribute to bone fragility. Recent evidence implies that intramyocellular lipid accumulation is directly correlated with insulin resistance, a key parameter in the generation of obesity. The second part of this study is mainly focused on the determination of the structural and compositional characterization of macromolecules of longissimus dorsi and quadriceps muscles of Berlin fat mouse inbred (BFMI) lines using ATR-FTIR spectroscopy and FTIR microspectroscopic imaging, together with the quantification of fiber specific distribution of lipids in these muscles by the use of confocal microscopy. The study groups included 10 weeks old standard breeding diet fed (juvenile) and 20 weeks old high fat diet fed control and BFMI lines. The results revealed the loss of unsaturation in lipids, increased triglyceride content, increased amount of lipids having shorter chain length, increased lipid peroxidation and fiber specific accumulation of lipids in type IIa and intermediate fibers in skeletal muscles of both 10 weeks old and 20 weeks old BFMI lines, emphasizing their obese phenotype. However, the alterations were more prominent in skeletal muscles of 20 weeks old high fat diet fed BFMI lines, displaying a more severe obesity phenotype. The results of the characterization revealed that BFMI860 and BFMI861 lines are convenient models for the study of spontaneous obesity and studies to enlighten the genetic basis of obesity.

The dissertation work focuses on the whole route of material development starting from the investigations of properties of the initial (raw) HBPs to their applications. Each research step is given in a separate chapter to enhance attention to various aspects of the aim of the work. Thus, every chapter is started with an introduction. After that, the methods applied and experimental procedure are described. Next part tries to give the comprehensive description of the results obtained. At the end of the chapter, the main points are summarized. The Chapter 1 gives the theoretical description of the main experimental techniques used in this work. In Chapter 2 the chemical (chemical composition, purity, typical structure elements) and physical (glass transition temperature, the temperature of the maximum decomposition, the thermal stability at the high temperatures, molar mass, polydispersity and possible aggregation in solution) properties examined by different techniques of polymer analysis are described. The Chapter 3 is divided into three separate parts: In Chapter 3.1 the description of the formation and modification of inter- and intramolecular hydrogen bonds of hydroxyl terminated HBP is presented to reveal the information of hydroxyl groups re- and/or association due to the high temperatures applied. In Chapter 3.2 the nature of the solid-liquid interface of HBP thin films have been studied by different surface sensitive techniques with respect to further protein adsorption investigations. In Chapter 3.3 the strategy for the fabrication of surface attached carboxyl terminated HBP using &amp;quot;grafting to&amp;quot; technique is developed. The Chapter 4 consists of two parts: The first (theoretic) part outlines the basic principles of protein chemistry, factors influencing on the protein molecule stability in aqueous medium, the mechanism of protein adsorption and forces involved in the adsorption process. In the second part the combination of different in situ techniques was applied to obtain a comprehensive description of complex adsorption processes of protein molecules on different polymer surfaces.

Alzheimer’s disease (AD) is the most common cause of senile dementia worldwide. AD is a neurodegenerative disorder characterized by the loss of memory and language skill, collapse of the cognitive function, and distortion of social behavior. As of today, the onset mechanisms of AD and cure are unknown; however, three hallmarks are commonly encountered: extra and intracellular accumulation of amyloid beta (A!) peptide plaques, formation of intracellular neurofibrillary tangles, and inevitable neuronal death. Hypothetically, a possible scenario provoking or involved in the onset of AD is a cascade effect that starts with an imbalance in the production and clearance of Aß peptide that consequently leads to its accumulation, formation of tau protein tangles and neuronal death. This work studied and characterized the mechanisms governing A! peptide aggregation and the effects of using anti-Aß monoclonal antibodies to modify this process. These mechanisms play an important role in the formation of AD plaques and are critical in the search for therapies involving Aß peptide plaque clearance. Yet, antibody-based therapies for plaque clearance are not well understood, adding to the existing concerns about side effects in humans, hence there is a necessity of knowledge in this matter. In this work different Nterminus, C-terminus, and Mid-domain antibodies were used against Aß peptide species (monomers, oligomers, and fibrils) to probe peptide aggregates modification and disruption. Additionally, construction of a soft supported lipid bilayer membrane was proposed to study the adhesion mechanisms of Aß peptide and interactions with antibodies, mimicking the neuronal cell surface. The main characterization techniques used in this work were: atomic force microscopy (AFM) and transmission electron microscopy that allowed the physical exploration and visualization of the different processes of aggregation in terms of adhesion, size evolution, and distribution of the peptide; and attenuated total reflectance Fourier spectroscopy (ATR/FTIR) which allowed monitoring the change of secondary structures for the peptide during the processes studied. It is endeavored that this work will help to elucidate the effects attributed to the molecular interactions between A! peptide species and antibodies to target Aß plaque’s clearance in the brain of AD patients. Ultimately, this study provides novel information critical for the formulation of effective therapies to prevent and treat AD with less collateral effects. It also represents a contribution to the basic scientific knowledge regarding peptide-antibody interactions with application to other diseases related to protein misfolding.

Le sujet de cette thèse concerne les applications hautes températures, où les moteurs doivent être capables de fonctionner à 400°C pendant 2 heures, selon la norme en vigueur. Il convient dans ce type d'applications de disposer de matériaux assez stables pour que leurs propriétés isolantes restent inchangées, ce qui est le cas du fil émaillé PolyImide (PI). Ce fil émaillé pose néanmoins des problèmes économiques et de fournisseurs, d'où la nécessité de trouver d'autres alternatives. Ce travail de thèse a eu pour but de mettre au point et valider des techniques d'analyses (ATG / ATM / ATR-FTIR / DRS) adaptées au fil émaillé, et ce jusqu'à 400°C. Le PEI présente des propriétés insuffisantes pour ce type d'application car il se dégrade avant 350°C et perd ses propriétés d'isolation électrique. Le PAI est un matériau qui ne se dégrade que peu avant 400°C, et présente des caractéristiques électriques (propriétés diélectriques et de conduction) déjà plus proche du PolyImide. Nous avons pu établir la comparaison de deux PAI dont l'un est conventionnel et l'autre est un nanocomposite à base d'alumine. Ce dernier PAI est plus stable en température mais ne semble pas avoir de propriétés électriques très supérieures. Pour confronter les résultats expérimentaux obtenus dans des conditions particulières aux conditions réelles d'utilisation, des moteurs avec ces fils émaillés ont été fabriqués. Les moteurs équipés des fils PEI/PAI (fil standard) et PAI sont défaillants après 40 minutes au lieu de 2h, contrairement aux moteurs équipés de fil PI. La dégradation du PEI et le fluage du PAI, caractérisé au-delà de sa Tg (280°C), peuvent être la cause des dysfonctionnements de ces moteurs

Les biosenseurs sont des dispositifs analytiques utilisés pour la détection de reconnaissance moléculaire. Ils consistent en un élément biologique immobilisé en contact intime avec un transducteur approprié qui convertit un signal biochimique en un signal électrique quantifiable. Leur principe est basé sur la reconnaissance d'une ou plusieurs molécules d'intérêt en solution (le ligand), par un composant biologique (le récepteur) étroitement lié au substrat transducteur. Le senseur réagit aux interactions récepteur-ligand et produit un signal mesurable, généralement proportionnel à la concentration du ligand fixé. Les biosenseurs sont déjà utilisés dans beaucoup de domaines différents, notamment dans le domaine médical (diagnostique et thérapeutique), le contrôle de l’environnement, et l’analyse et le monitoring de processus biotechnologiques. <p><p>La recherche concerne la mise au point d’un nouveau type de biosenseurs polyvalents à haute performance. Ces senseurs utilisent un élément de transduction optique dont la surface a été fonctionnalisée en vue de permettre la détection sélective d'interactions récepteur-ligand ainsi que le dosage des molécules fixées aux récepteurs. La technique utilisée pour la détection et le dosage est celle de la Spectroscopie ATR-FTIR (Spectroscopie Infra Rouge à Transformée de Fourrier en Réflexion Total Atténuée). Le système permet la détection directe, en temps réel, et sans marquage des molécules ciblées. La spectroscopie ATR-FTIR fournit une analyse des molécules sur base de leur empreinte spectrale infra rouge (IR) caractéristique, ce qui offre une mine d'informations pour identifier les ligands. Ce nouveau système de biosenseur, appelé BIA-ATR (Biospecific Interaction Analysis – Attenuated Total Reflection) est original et offre des avantages majeurs par rapport à la plus part des biosenseurs commercialement disponibles. Il fournit à l’utilisateur le spectre IR entier du ligand étudié, permettant non seulement le dosage quantitatif de ce dernier, mais aussi d’identifier sa nature intrinsèque. Un autre avantage est sa grande sensibilité ;le senseur BIA-ATR peut détecter la fixation de petites molécules et dans certains cas, aussi les réactions chimiques associées. <p><p>Le potentiel de cette nouvelle technologie de senseur est évalué dans ce travail par son application à plusieurs systèmes d’intérêt biologique et médical :la détection de protéines en milieux complexes, appliquée à la détection du Facteur VIII de coagulation du sang impliqué dans l’hémophilie de type A ;la fixation d’une petite molécule, le phosphate (phosphorylation), sur l’ATPase gastrique, un récepteur protéique de grande taille responsable de la sécrétion d’acide dans l’estomac et la détection et dosage d’un antibiotique, la vancomycine, utilisé en soins intensifs hospitaliers dans les cas d’infections bactériennes sévères à Staphylocoques dorés.<p> / Doctorat en Sciences / info:eu-repo/semantics/nonPublished

The dissertation work focuses on the whole route of material development starting from the investigations of properties of the initial (raw) HBPs to their applications. Each research step is given in a separate chapter to enhance attention to various aspects of the aim of the work. Thus, every chapter is started with an introduction. After that, the methods applied and experimental procedure are described. Next part tries to give the comprehensive description of the results obtained. At the end of the chapter, the main points are summarized. The Chapter 1 gives the theoretical description of the main experimental techniques used in this work. In Chapter 2 the chemical (chemical composition, purity, typical structure elements) and physical (glass transition temperature, the temperature of the maximum decomposition, the thermal stability at the high temperatures, molar mass, polydispersity and possible aggregation in solution) properties examined by different techniques of polymer analysis are described. The Chapter 3 is divided into three separate parts: In Chapter 3.1 the description of the formation and modification of inter- and intramolecular hydrogen bonds of hydroxyl terminated HBP is presented to reveal the information of hydroxyl groups re- and/or association due to the high temperatures applied. In Chapter 3.2 the nature of the solid-liquid interface of HBP thin films have been studied by different surface sensitive techniques with respect to further protein adsorption investigations. In Chapter 3.3 the strategy for the fabrication of surface attached carboxyl terminated HBP using &amp;quot;grafting to&amp;quot; technique is developed. The Chapter 4 consists of two parts: The first (theoretic) part outlines the basic principles of protein chemistry, factors influencing on the protein molecule stability in aqueous medium, the mechanism of protein adsorption and forces involved in the adsorption process. In the second part the combination of different in situ techniques was applied to obtain a comprehensive description of complex adsorption processes of protein molecules on different polymer surfaces.

Effects of sodium sulfate (Na2SO4) particle deposition on the atmospheric corrosion of copper (Cu) metal and a Cu-based alloy (Cu5Al5Zn) used in architectural applications were investigated at laboratory conditions compared with effects induced by sodium chloride (NaCl) and to some extent ammonium sulfate (NH4)2SO4 induced corrosion. Pre-deposited surfaces were exposed to repeated wet/dry conditions in a climatic chamber and the formation of corrosion products were assessed using light optical microscopy (LOM), scanning electron microscopy with elemental analysis (SEM/EDS), Fourier transform infrared techniques (FTIR microscopy) and cathodic reduction (CR). Na2SO4 induced corrosion resulted in corrosion cells locally over the surface on both Cu and Cu5Al5Zn, of increased oxygen content in the anodic area of the cells (center of pre-deposited area). The main corrosion products formed on Cu metal are basic copper sulfates and cuprite (Cu2O), while basic sulfates (copper and/or zinc) and Cu2O were the main corrosion products formed on Cu5Al5Zn. A combined deposition of Na2SO4 + NaCl was carried out on the Cu5Al5Zn alloy using two different deposition methods to investigate the possible interplay from a corrosion initiation perspective between the two salt particles. For short time exposed Cu5Al5Zn (1 cycle), two different corrosion cells formed, mainly induced by Na2SO4 and NaCl. Corrosion products formed in anodic areas of a Na2SO4 induced corrosion cell were similar to findings observed for Cu5Al5Zn pre-deposited with Na2SO4 only, whereas peripheral cathodic areas primarily were affected by NaCl dissolution and predominantly composed of Cu2O that was the main corrosion product with small amount of hydroxides and carbonates of the NaCl induced corrosion cells. After relatively longer exposure periods (2 and 6 wet/dry cycles), NaCl dominated the corrosion of the entire surface with the formation of more Cu2O, hydroxides and carbonates. Cathodic reduction findings revealed a negative interplay on corrosion for the mixed salt after short time exposures (1 and 2 cycles), whereas a slight synergistic effect was evident after a longer exposure period (6 cycles), compared with corrosion induced by single salts.