A study of biosorption of cobalt metal by Pseudomonas Aerguinosa gram-negative bacterial strain is presented. The present study is carried out to determine the optimum conditions of cobalt biosorption at ultra-low concentration (ppb range) in aqueous solutions. The receptiveness of cobalt metal on the extracellular surface of bacterial strain was examined by varying the pH, Initial concentration of metal and treatment time. Experimental data showed that effect of pH and treatment time is prevalent in biosorption of cobalt and by increasing both these parameters resulted in the efficient sorption of cobalt on the extracellular surface of Pseudomonas Aerguinosa. In some cases, higher initial concentration of cobalt resulted in higher metal removal. However, there is no clear relationship is obtained between efficiency of biosorption and initial concentration of cobalt.

Direct numerical simulations (DNS) of an initially quiescent coupled air-water interface driven by an air flow with free stream speed of 5 m/s have been conducted. The DNS solves a scalar advection-diffusion equation for dissolved gas (or scalar) concentration in order to determine the impact of the water-side turbulence on scalar (mass) transfer from the air side to the water side and subsequent vertical transport in the water column. Two simulations are compared: one with a freely deforming interface and a second one with a flat interface. In the first simulation, the deforming interface evolves in the form of gravity-capillary waves generating aqueous Langmuir turbulence characterized by small-scale (centimeter-scale) Langmuir cells (LCs). The second simulation is characterized by pure shear-driven turbulence in the absence of LCs as the interface is intentionally held flat. It is concluded that the Langmuir turbulence serves to enhance vertical transport of the scalar in the water side and in the process increases scalar transfer efficiency relative to the shear-dominated turbulence in the flat interface case. Furthermore, transition to Langmuir turbulence was observed to be accompanied by a spike in scalar flux via molecular diffusion across the interface characterized by an order of magnitude increase. Such episodic flux increases, if linked to gusts and overall unsteadiness in the wind field, are expected to be an important contributor in determining the long-term average of the air-sea gas fluxes. The effectiveness of popular transfer velocity models, namely the small eddy model and the surface divergence model, in predicting this spike is evaluated via the DNS. In addition to LCs, DNS reveals that the water side turbulence is characterized by smaller, shear-driven turbulent eddies at the surface embedded within the LCs. LES with momentum equation augmented with the well-known Craik-Leibovich (C-L) vortex force is used to understand the roles of the wave and shear-driven LCs (i.e. the Langmuir turbulence) and the smaller shear-driven eddies (i.e. the shear turbulence) in determining molecular diffusive scalar flux from the air side to the water side and vertical scalar transport beneath. The C-L force consists of the cross product between the Stokes drift velocity (induced by the interfacial waves) and the flow vorticity. It is observed that Stokes drift shear intensifies the smaller eddies (with respect to purely wind-driven flow, i.e. without wave effects) leading to enhanced diffusive scalar flux at the air-water interface. LC leads to increased vertical scalar transport at depths below the interface and thus greater scalar transfer efficiency.

Energy harvesting using rectennas for infrared radiation continues to be a challenge due to the lack of fast switching diodes capable of rectification at THz frequencies. Metal insulator metal diodes which may be used at 30 THz must show adequate nonlinearity for small signal rectification such as 30 mV. In a rectenna assembly, the voltage signal received as an output from a single nanoantenna can be as small as ~30µV. Thus, only a hybrid array of nanoantennas can be sufficient to provide a signal in the ~30mV range for the diode to be able to rectify around 30THz. A metal-insulator-metal diode with highly nonlinear I-V characteristics is required in order for such small signal rectification to be possible. Such diode fabrication was found to be faced with two major fabrication challenges. The first one being the lack of a precisely controlled deposition process to allow a pinhole free insulator deposition less than 3nm in thickness. Another major challenge is the deposition of a top metal contact on the underlying insulating thin film. As a part of this research study, most of the MIM diodes were fabricated using Langmuir Blodgett monolayers deposited on a thin Ni film that was sputter coated on a silicon wafer. UV induced polymerization of the Langmuir Blodgett thin film was used to allow intermolecular crosslinking. A metal top contact was sputtered onto the underlying Langmuir Blodgett film assembly. In addition to material characterization of all the individual films using IR, UV-VIS spectroscopy, electron microscopy and atomic force microscopy, the I-V characteristics, resistance, current density, rectification ratio and responsivity with respect to the bias voltage were also measured for the electrical characterization of these MIM diodes. Further improvement in the diode rectification ratio and responsivity was obtained with Langmuir Blodgett films grown by the use of horizontally oriented organic molecules, due to a smaller tunneling distance that could be achieved in this case. These long chain polymeric molecules exhibit a two-dimensional molecular assembly thereby reducing the tunneling distance between the metal electrodes on either side of the insulating layer. Rectification ratios as high as 450:1 at ±200mV were obtained for an MIM diode configuration of Ni-LB films of Arachidic Acid films-(Au/Pd). The bandwidth of the incident radiation that can be used by this rectenna assembly is limited to 9.5% of 30THz or ±1.5THz from the center frequency based on the antenna designs which were proposed for this research. This bandwidth constraint has led to research in the field of frequency selective emitters capable of providing a narrowband emission around 30THz. Several grating structures were fabricated in the form of Ni-Si periodic arrays, in a cleanroom environment using photolithography, sputtering and deep reactive ion etching. These frequency selective samples were characterized with the help of focusing optics, monochromators and HgCdTe detectors. The results obtained from the emission spectra were utilized to calibrate a simulation model with Computer Simulation Technology (CST) which uses numerous robust solving techniques, such as the finite element method, in order to obtain the optical parameters for the model. Thereafter, a thorough analysis of the different dimensional and material parameters was performed, to understand their dependence on the emissivity of the selective emitter. Further research on the frequency selectivity of the periodic nano-disk or nano-hole array led to the temperature dependence of the simulated spectra, because the material parameters, such as refractive index or drude model collision frequency, vary with temperature. Thus, the design of frequency selective absorbers/emitters was found to be significantly affected with temperature range of operation of these structures.

La formation de H2 dans le milieu interstellaire, à partir de deux atomes H, est une question essentielle en astrophysique. Cette réaction exothermique qui a lieu à la surface d'un grain de poussière interstellaire est la première étape d'une suite de réactions primordiales pour la physico-chimie. Dans les nuages diffus et les régions de photodissociation, on invoque pour mécanisme de formation une réaction de catalyse hétérogène Eley Rideal, un des atomes étant chimisorbé. Les grains sont principalement carbonés et constitués notamment de graphite. Les travaux théoriques antérieurs effectués en géométrie réduite n'ont pas permis d'expliquer la formation de H2 dans les états rovibrationnels observés (v<5). Pour prendre en compte les degrés de liberté de tous les atomes, nous avons conçu à partir du potentiel de Brenner, un nouveau potentiel pour modéliser le système graphène-H-H avec lequel nous avons réalisé une étude de dynamique moléculaire classique de la formation de H2. Cette étude a été effectuée pour des énergies de collision d'atomes H incidents de 0.015eV à 0.2eV et pour des surfaces à 0, 10 et 30K. Un des résultats principaux est que la section efficace de réaction est directement reliée à l'allure du potentiel que voit l'atome H incident. De plus, il a été mis en évidence que la distribution rovibrationnelle obtenue en autorisant la relaxation de la surface correspond mieux à celle observée par les astrophysiciens (v < 6), la surface absorbant ~25% de l'énergie disponible. Des travaux étudiant l'influence de la présence d'un atome H supplémentaire sur la surface ou d'une possible structure poreuse des grains, sur la formation de H2, sont présentés en annexe.

Je définis tout d'abord les polynômes vectoriels orthogonaux relativement à une matrice r x s de mesures ou de poids et je rappelle les propriétés habituelles : la récurrence à r+s+1 termes, le théorème de Shohat-Favard ou l'égalité de Christoffel-Darboux. Ces polynômes permettent, par l'utilisation d'approximants de Padé, de caractériser l'ensemble résolvant de l'opérateur aux différences associé aux récurrences. Cette caractérisation a déjà été donnée par Duren mais la démonstration utilisée ici est novatrice. Je définis ensuite des fonctions homographiques sur l'ensemble des matrices $r\times s$. J'uniformise ainsi tous les cas connus de fractions continues: scalaire, vectoriel ou matriciel. Elles permettent aussi de démontrer un théorème d'accélération de convergence de fractions continues matricielles, généralisation d'un théorème similaire pour les fractions généralisées donné par de Bruin et Jacobsen. J'utilise alors les polynômes vectoriels pour calculer les coefficients de récurrence d'autres polynômes par l'algorithme de Chebyshev modifié vectoriel, généralisation du cas scalaire pour lequel nous démontrons des critères de stabilité. Finalement, l'algorithme de Chebyshev modifié est utilisé pour étudier l'évolution temporelle du système dynamique semi-infini de Toda-Langmuir. Dans ce système, les particules sont sur le semi-axe réel et elles interagissent suivant une loi exponentielle décroissante. L'approche utilisée pour résoudre le problème est, encore une fois, innovante. En effet, j'étudie seulement les n premières particules et je m'intéresse à l'erreur commise sur l'évolution lorsque l'on tronque le système à N>>n quantités c'est-à-dire que l'on travaille avec un système fini. Je présente l'étude théorique de l'erreur, où je réutilise nos résultats sur la stabilité de l'algorithme de Chebyshev modifié, ainsi que des exemples numériques.

L'objectif de cette thèse est de contrôler les propriétés optiques des nanoparticules d'or greffées de polymère en modulant les propriétés structurales de la couche protectrice de polymères. Des nanoparticules greffées de polymères thermosensibles avec une large gamme de masse molaire et différents degrés d'hydrophobicité sont synthétisées par la méthode de " grafting-to ". La DNPA est utilisée pour caractériser les propriétés structurales de la couche protectrice de polymère. Les spectres d'absorption sont modélisés en utilisant la théorie de Mie. Nous démontrons que la sensibilité de la SPR à la propriété diélectrique du solvant diminue progressivement avec la fraction volumique de la couche de polymère jusqu'à devenir quasi-nulle; dans ce dernier cas de figure, la SPR est dite " gelée " par la couche de polymère. Un déplacement significatif de la bande de SPR vers le rouge est induit (un changement de couleur se produit) dû à une transition de collapse de la couche de polymère avec la température. La gamme de température pour induire ce déplacement dépend du degré d'hydrophobicité du polymère et de la salinité. Une partie important de cette thèse est également consacrée aux propriétés des nanoparticules d'or greffées de polymères à l'interface air-eau. La technique de Langmuir est utilisée pour former des films minces dont la distance entre particule est contrôlée par la compression, la longueur des chaînes du polymère greffé et la température. Les propriétés structurales des films minces sont étudiées en déterminant la conformation de la couche de polymère greffée et l'organisation du cœur de l'or par la réflectivité de neutron et de X, respectivement. Les mesures de réflectivité nous permettent également d'évaluer et d'améliorer la stabilité des films minces pour un meilleur control de la distance entre particule, aspect important pour l'optimisation de la SPR. Enfin, les propriétés optiques des nanoparticules d'or à l'interface sont mesurées par des mesures de transmission.

Langmuir monolayers can be employed as simple model systems to study interactions at surfaces. Such investigations are important to fields ranging from biology to materials science. Herein, several aspects of these films and their associated water structure have been examined with vibrational sum frequency spectroscopy (VSFS). This second order nonlinear optical spectroscopy is particularly well suited for simultaneous investigations of the monolayer and the associated water structure with unprecedented surface specificity. The structures of these systems were altered through the control of experimental parameters including monolayer pressure, subphase temperature, pH and ionic content. Thermodynamic information about structural changes in a fatty amine monolayer's hydrophobic region was obtained by observation of the pressure and temperature dependence of the monolayer's solid to liquid phase transition. Further studies used the coordination of divalent cations to acid monolayers to perturb the water layers nearest to the film which enabled a better understanding of the water related VSFS features from these hydrophilic interfaces. Information from both the monolayer and water structure was then combined in order to examine the role of water in mediating ion-biomaterial interactions, often expressed in terms of the Hofmeister series.

Herein are presented collective studies of amino acid-based surfactants, also known as lipoamino acids, at liquid interfaces. Chapter III describes an investigation of domain morphology of N-Stearoylglutamic acid (N-SGA) Langmuir monolayers at the air/water interface by epifluorescence microscopy. Anisotropic feather-like domains were observed in L-enantiomeric monolayers while symmetric circular domains were found in racemic N-SGA monolayers. At a surface pressure of 30 mN/m the enantiomeric domains melted at 31 ??C while the racemic domains melted at 27 ??C. This result is exactly opposite to the behavior found in bulk crystals where the racemate melts at a higher temperature. These results were explained in terms of different molecular packing and hydrogen bonding between bulk crystals and two-dimensional thin films for enantiomeric and racemic compounds. Chapter IV summarizes the investigations of hydrogen bonding in N-acyl amino acid monolayers by vibrational sum-frequency spectroscopy (VSFS). The intermolecular hydrogen bonding interaction between the adjacent molecules through amide-amide groups in N-stearoylalanine (N-SA) is characterized by an NH stretch peak at 3311 cm-1. This is the first time that the amide NH stretching signals have been detected with the VSFS technique. A similar peak was detected at 3341 cm-1on N-SGA monolayer. The higher frequency indicates that the H-bond strength is weaker due to the larger size of the glutamic acid residue. The NH stretch mode can thus be used as a fingerprint of hydrogen bonding among amide-amide groups. A peak at 3050 cm-1 due to hydrogen bonding among carboxyl groups was also resolved from the VSFS spectra. Molecular models of intermolecular hydrogen bonding were proposed.

The interactions between peptides and lipids are of fundamental importance in the functioning of numerous membrane-mediated biochemical processes including antimicrobial peptide action, hormone-receptor interactions, drug bioavailability across the blood-brain barrier and viral fusion processes. Alteration of peptide structure could be a cause of many diseases.<br> Biological membranes are complex systems, therefore simplified models may be introduced in order to understand processes occurring in nature. The lipid monolayers at the air/water interface are suitable model systems to mimic biological membranes since many parameters can be easily controlled. In the present work the lipid monolayers were used as a model membrane and their interactions with two different peptides B18 and Amyloid beta (1-40) peptide were investigated.<br> B18 is a synthetic peptide that binds to lipid membranes that leads to the membrane fusion. It was demonstrated that it adopts different structures in the aqueous solutions and in the membrane interior. It is unstructured in solutions and forms alpha-helix at the air/water interface or in the membrane bound state. The peptide has affinity to the negatively charged lipids and even can fold into beta-sheet structure in the vicinity of charged membranes at high peptide to lipid ratio. It was elucidated that in the absence of electrostatic interactions B18 does not influence on the lipid structure, whereas it provides partial liquidization of the negatively charged lipids. The understanding of mechanism of the peptide action in model system may help to develop the new type of antimicrobial peptides as well as it can shed light on the general mechanisms of peptide/membrane binding.<br> The other studied peptide - Amyloid beta (1-40) peptide, which is the major component of amyloid plaques found in the brain of patients with Alzheimer's disease. Normally the peptide is soluble and is not toxic. During aging or as a result of the disease it aggregates and shows a pronounced neurotoxicity. The peptide aggregation involves the conformational transition from a random coil or alpha-helix to beta-sheets. Recently it was demonstrated that the membrane can play a crucial role for the peptide aggregation and even more the peptide can cause the change in the cell membranes that leads to a neuron death. In the present studies the structure of the membrane bound Amyloid beta peptide was elucidated. It was found that the peptide adopts the beta-sheet structure at the air/water interface or being adsorbed on lipid monolayers, while it can form alpha-helical structure in the presence of the negatively charged vesicles. The difference between the monolayer system and the bulk system with vesicles is the peptide to lipid ratio. The peptide adopts the helical structure at low peptide to lipid ratio and folds into beta-sheet at high ratio. Apparently, Abeta peptide accumulation in the brain is concentration driven. Increasing concentration leads to a change in the lipid to peptide ratio that induces the beta-sheet formation. The negatively charged lipids can act as seeds in the plaque formation, the peptide accumulates on the membrane and when the peptide to lipid ratio increases it the peptide forms toxic beta-sheet containing aggregates. / Wechselwirkungen zwischen Peptiden und Lipiden sind von grundlegender Bedeutung für die Funktion vieler Membran-vermittelter biochemischer Prozesse wie der Wirkung von antimikrobiellen Peptiden, Hormon-Rezeptor Wechselwirkungen, Bioverfügbarkeit von Arzneistoffen durch die Blut-Hirn-Schranke und viraler Fusionsprozesse. Veränderungen in der Peptidstruktur können die Ursache für viele Erkrankungen sein.<br> Biologische Membranen sind für grundlegende physikalisch-chemische Untersuchungen von Naturprozessen zu komplexe Systeme, so dass vereinfachte Modelle für solche Studien eingesetzt werden. Eine Lipidmonoschicht an der Wasser/Luft Grenzfläche ist ein geeignetes Modellsystem für eine Membranoberfläche. Viele physikalisch-chemischen Parameter können auf einfache Weise gezielt verändert werden. In der vorliegenden Arbeit wurden Lipidmonoschichten genutzt, um Wechselwirkungen mit zwei unterschiedlichen Peptiden (B18 and Amyloid Beta (1-40) Peptid) zu untersuchen.<br> B18 ist ein oberflächenaktives synthetisches Peptid, das an Lipidmembranen bindet und zu Membranfusion führt. Es kann verschiedene Sekundärstrukturen ausbilden. So ist B18 in wässrigen Lösungen ungeordnet und bildet eine alpha-helikale Struktur an der Wasser/Luft Grenzfläche. Das Peptid hat eine große Affinität zu negativ geladenen Lipiden und kann in der Nähe von geladenen Membranoberflächen bei einem großen Peptid/Lipid Verhältnis eine Beta-Faltblatt Struktur ausbilden. Beim Fehlen elektrostatischer Wechselwirkungen hat B18 keinen Einfluss auf die Lipidstruktur. Es wirkt jedoch strukturabbauend auf anionische Lipide. Das Verständnis der Peptidwirkungen in Modellsystemen kann helfen, generelle Mechanismen von Peptide-Membran Wechselwirkungen zu verstehen und zur Entwicklung neuer antimikrobieller Peptide beizutragen.<br> Amyloid Beta (1-40) Peptid ist die Hauptkomponente von Amyloid-Plaque, das im Gehirn von Alzheimer Patienten gefunden wird. Normalerweise ist das Peptid löslich und nicht toxisch. Hohe Neurotoxizität wird bei Peptidaggregation, die eine Strukturumwandlung von ungeordnet oder alpha-helikal zu Beta-Faltblatt nach sich zieht, beobachtet. In der vorliegenden Arbeit wurde die Struktur des Membran-gebundenen Amyloid Beta (1-40) Peptids untersucht. Es zeigte sich, dass das Peptid nach Adsorption an die Wasser/Luft Grenzfläche oder an Lipidmonoschichten eine Beta-Faltblatt Struktur ausbildet. Eine alpha-helikale Sekundärstruktur wird nur bei Anwesenheit negativ geladenen Lipidvesikel gefunden. Der entscheidende Unterschied zwischen den Monoschicht- und Vesikel-Systemen ist das Peptid/Lipid Verhältnis. Die alpha-helikale Struktur wird nur bei kleinem Peptid/Lipid Verhältnis beobachtet, während bei großem eine Beta-Faltblatt Struktur auftritt. Steigende Konzentration an Amyloid Beta (1-40) Peptid führt zum Anstieg des Peptid/Lipid Verhältnisses und damit zur Ausbildung der Beta-Faltblatt Struktur. Negativ geladene Lipide können somit als Keimpunkte für die Plaquebildung fungieren.

I den här avhandlingen har vi studerat hur man kan göra nya tensider. En tensid är en speciell molekyl som har förmågan att lösa sig i både vatten och olja. Man kan göra följande experiment hemma: Fyll en glasburk till hälften med vatten och tillsätt en droppe matolja. Oljan bildar en droppe ovanpå vattnet, därför att vatten och olja inte är blandbara. Vatten är polärt och olja är opolärt. Om man rör om med en sked kommer oljedroppen förvisso att dela upp sig i mindre droppar, men så snart man slutar att röra kommer dessa att lägga sig på vattenytan igen. Sätt nu en droppe diskmedel till blandningen och rör om. Nu sprider sig oljedropparna mycket bättre i vattnet, och de lägger sig heller inte på vattenytan lika fort när man slutar att röra. Det här beror på att diskmedel innehåller en tensid, som har en polär och en opolär del. Den polära delen passar ihop med det polära vattnet, medan den opolära delen passar ihop med den opolära oljan. På så vis kan tensiden hjälpa till att lösa upp opolära ämnen i polära vätskor. Den aktiva delen av ett läkemedel består ofta av opolära ämnen, vilka inte löser sig i polära vätskor såsom vatten. Eftersom kroppen består till stor del av vatten måste man ändå försöka få läkemedlet vattenlösligt, för att möjliggöra transport via blodet till problemområdet. Det kan man uppnå genom att tillsätta tensider. Om läkemedel-tensidblandningen ska ges till djur eller människor får inte tensiden orsaka någon skada i kroppen. Vi har försökt framställa tensider som ska kunna användas för att just lösa läkemedel i vatten. För att kunna framställa nya tensider måste man ha kunskap i organisk syntes. Det betyder att man måste veta hur man från små intermediat (”byggstenar”) successivt kan bygga upp nya molekyler som har de önskvärda egenskaperna. Genom olika typer av organisk syntes har vi byggt upp tre nya tensidtyper, vars egenskaper vi studerat med olika mätningar. Ingen av dessa tensider lämpade sig som tillsats till läkemedel, men vårt arbete har givit mycket ny kunskap om hur framtida tensidmolkyler kan tillverkas och vilka egenskaper de får. / This thesis deals with the synthesis and characterization of new polyhydroxy surfactants. The first part describes the synthesis of three new surfactant classes, and the second part concerns the surface chemical characterization of the synthesized surfactants. A stereodivergent route for preparation of hydrophilic head groups was developed, that featured consecutive stereoselective dihydroxylations of a diene. This method provided in total four different polyhydroxylated head groups. These surfactant head groups were natural and unnatural sugar analogues, and were used for the coupling with two different hydrophobic tail groups. Another approach took advantage of a metathesis reaction and provided a polyhydroxylated compound that was coupled to 12-hydroxy stearic acid The third class of surfactants contained an amide linkage between the hydrophilic and the hydrophobic parts. The hydrophilic part consisted of two glucose units, and 12-hydroxy stearic acid was used as the hydrophobic part. The hydroxy moiety in the tail group was further functionalized as aliphatic esters, which provided in total four different surfactants. A selection of the surfactants was used to investigate the chiral discrimination in Langmuir monolayers at an air-water interface. The isotherms showed a remarkable difference in compressibility between diastereomeric surfactants and also a pronounced chiral discrimination between racemic and enantiomerically pure surfactants, favoring heterochiral discrimination. The monolayers were also investigated with Brewster angle microscopy (BAM) and grazing incidence X-ray diffraction (GIXD). It was not possible to observe any chirality dependent features from the BAM images, but the GIXD measurement supported the conclusion that heterochiral discrimination governed the intermolecular forces within the racemic monolayer. The third class of surfactants, containing an amide linkage between the glucose units and 12-hydroxy stearic acid was evaluated with respect to the CMC and the haemolytic activity. These surfactants were all haemolytic close to their respective CMC. / QC 20101015