Hydrophobic interactions guide important molecular self-assembly processes such as protein folding. On the macroscale, hydrophobic interactions consist of the aggregation of "oil-like" objects in water by minimizing the interfacial energy. However, the hydration mechanism of small hydrophobic molecules on the nanoscale (~1 nm) differs fundamentally from its macroscopic counterpart. Theoretical studies over the last two decades have pointed to an intricate dependence of molecular hydration mechanisms on the length scale. The microscopic-to-macroscopic cross-over length scale is critically important to hydrophobic interactions in polymers, proteins and other macromolecules. Accurate experimental determination of hydration mechanisms and their interaction strengths are needed to understand protein folding. This thesis reports the development of experimental and analytical techniques that allow for direct measurements of hydrophobic interactions in a single molecule. Using single molecule force spectroscopy, the mechanical unfolding of a single hydrophobic homopolymer was identified and modeled. Two experiments examined how hydrophobicity at the molecular scale differ from the macroscopic scale. The first experiment identifies macroscopic interfacial tension as a critical parameter governing the molecular hydrophobic hydration strength. This experiment shows that the solvent conditions affect the microscopic and macroscopic hydrophobic strengths in similar ways, consistent with theoretical predictions. The second experiment probes the hydrophobic size effect by studying how the size of a non-polar side-chain affects the thermal signatures of hydration. Our experimental results reveal a cross-over length scale of approximately 1 nm that bridges the transition from entropically driven microscopic hydration mechanism to enthalpically driven macroscopic hydration mechanism. These results indicate that hydrophobic interactions at the molecular scale differ from macroscopic scale, pointing to potential ways to improve our understanding and predictions of molecular interactions. The system established in this thesis forms the foundation for further investigation of polymer hydrophobicity.

abstract: All-dielectric self-supporting (ADSS) fiber optic cables are used for data transfer by the utilities. They are installed along high voltage transmission lines. Dry band arcing, a phenomenon which is observed in outdoor insulators, is also observed in ADSS cables. The heat developed during dry band arcing damages the ADSS cables' outer sheath. A method is presented here to rate the cable sheath using the power developed during dry band arcing. Because of the small diameter of ADSS cables, mechanical vibration is induced in ADSS cable. In order to avoid damage, vibration dampers known as spiral vibration dampers (SVD) are used over these ADSS cables. These dampers are installed near the armor rods, where the presence of leakage current and dry band activity is more. The effect of dampers on dry band activity is investigated by conducting experiments on ADSS cable and dampers. Observations made from the experiments suggest that the hydrophobicity of the cable and damper play a key role in stabilizing dry band arcs. Hydrophobic-ity of the samples have been compared. The importance of hydrophobicity of the samples is further illustrated with the help of simulation results. The results indi-cate that the electric field increases at the edges of water strip. The dry band arc-ing phenomenon could thus be correlated to the hydrophobicity of the outer sur-face of cable and damper. / Dissertation/Thesis / M.S. Electrical Engineering 2011

Conselho Nacional de Desenvolvimento Científico e Tecnológico / In this work we use the Density Functional Theory (DFT) to analyze the influence of a water environment in the interaction between amino acids and a semiconductor carbon nanotube (CNT). To the study of the interaction in vacuum we use both an ab initio and a parameterized tight-binding method. To the study of the same interactions in water we performed finite temperature (300 K) molecular dynamics calculations, using the parameterized tight-binding method. The selected amino acids have different hydrophobicity and polarity indexes. Our study shows that for the neutral amino acids, a direct relationship between the variation in the bonding distances and the hydrophobicity indexes when changing from vacuum to water environments, with the hydrophobic (hydrophilic) amino acids getting nearer (farther) of the carbon nanotube. The change in the binding energies, when going from the vacuum to the water environments, shows an inverse relationship with the polarity, with the amino acids that have more polar (nonpolar) side chains showing lower (greater) variations in the binding energies. We also analyze the variations in the binding energies in vacuum and water for the neutral and zwitterionic forms of glicine. We show that the zwitterionic form is more stable in the polar environment of water, whereas the neutral form is more stable in vacuum. / Neste trabalho utilizamos a teoria do funcional da densidade (DFT) para analisar a influência de um meio solvente, a água, na interação de aminoácidos com um nanotubo de carbono (CNT) semicondutor. Para o estudo das interações no vácuo utilizamos tanto um método ab-initio quanto um método tight binding parametrizado. Os estudos destas mesmas interações (CNT-aminoácidos) no meio aquoso foram realizados empregando o método de dinâmica molecular a uma temperatura de 300 K usando o método tight binding parametrizado. Os aminoácidos selecionados para o estudo tinham diferentes valores de índice de hidrofobicidade e de polaridade. Nossos resultados mostram que para a forma neutra destes aminoácidos, há uma relação direta entre a variação da distância da ligação, do vácuo em relação a água, e o índice de hidrofobicidade com os aminoácidos mais hidrofóbicos (hidrofílicos) se aproximando (afastando) do nanotubo de carbono. A variação da energia de ligação, quando se passa do vácuo para o ambiente aquoso, apresenta uma relação inversa com a polaridade, com os aminoácidos que possuem a cadeia lateral mais polares (menos polares) apresentado os menores (maiores) variações na energia de ligação. Analisamos ainda as variações na energia de ligação no vácuo e na água para o aminoácido glicina em relação as suas possíveis formas elétricas: neutra e como íon dipolar (zwiteri onica). Mostramos que a forma zwiteriônica é mais estável no ambiente polar da água, enquanto a forma neutra apresenta maior estabilidade no vácuo.

O microrganismo gram-negativo Aggregatibacter actinomycetemcomitans, fortemente associado a quadros de periodontite agressiva, coloniza a cavidade oral, aderindo e invadindo as células epiteliais e participando da formação de biofilme nas superfícies do hospedeiro. A. actinomycetemcomitans expressa Aae, uma proteína de superfície, relacionada com a adesão às células epiteliais. Este estudo avaliou o papel de Aae na adesão a outros substratos tais como proteínas extracelulares colagenosas e não-colagenosas, hidroxiapatita recoberta por saliva (SHA) e na formação de biofilme. Um mutante nulo em aae foi construído e o fenótipo comparado com o da linhagem selvagem (VT1169). O mutante nulo exibiu significativa redução na adesão às células epiteliais e a SHA, na formação de biofilme, além de apresentar-se menos hidrofóbico que a linhagem parental. A capacidade de adesão ao colágeno V e a fibronectina foi fracamente afetada pela interrupção do gene aae. Entretanto, o mutante nulo em aae exibiu uma capacidade diminuída na adesão à laminina e colágenos I, III e IV. Estes dados sugerem que Aae desempenha um importante papel na colonização da cavidade oral, não somente promovendo sua adesão às células epiteliais, mas também a outros substratos. / The gram-negative organism Aggregatibacter actinomycetemcomitans, associated with aggressive periodontitis, colonizes the oral cavity by binding to and invading epithelial cells and by participating in biofilms formed in host surfaces. A. actinomycetemcomitans express Aae, a surface protein, implicated in the adhesion to epithelial cells. This study evaluated the role of Aae in adhesion to other substrates such as collagen and non-collagen extracellular matrix proteins and saliva coated hydroxyapatite (SHA) and in biofilm formation. A null mutant in aae was constructed and its behavior was compared with the wild type strain VT1169. The null mutant exhibited a decreased ability to bind to epithelial cells and to SHA, formed less biofilm and was less hydrophobic than the parental strain. The abilities to bind to collagen V and fibronectin were very poorly affected by aae interruption. However, the null aae mutant exhibited a decreased ability to adhere to laminin, collagen I, III and IV. These data suggest that Aae may play an important role in the colonization of the oral cavity by A. actinomycetemcomitans, not only by promoting its adhesion to epithelial cells, but by mediating adhesion to other substrates.

Les tubes polymères, de PDMS ou de PVC, sont des matériaux hydrophobes polyvalents et peu couteux. Ils sont très largement utilisés dans l'industrie pour transférer des fluides plus ou moins complexes tels que de l'eau potable, des émulsions (e.g lait), des suspensions (e.g café), ou encore des solutions de molécules actives (e.g médicament). La plupart de ces applications mettent en jeux des écoulements intermittents répétés de liquide qui peuvent contaminer le matériau. Cette étude a pour but de mieux comprendre comment ces écoulements de fluides complexes entraînent la contamination des tubes. Nous étudions expérimentalement et théoriquement les régimes d'un segment de liquide de faible viscosité s'écoulant dans un tube en conditions de mouillage partiel. Deux processus sont en compétition : à cause de la vitesse élevée du segment de liquide, un film de liquide se forme à l'arrière du segment, alors qu'à cause de des conditions de mouillage partiel le film de liquide démouille. Nous montrons qu'au-delà de la limite en vitesse correspondant à la transition de mouillage dynamique qui est bien inférieure à la prédiction de Cox-Voinov, un régime précédemment inconnu avec un film épais, dont l'épaisseur dépend de la vitesse, est obtenu bien avant la formation classique d'un film de Landau-Levich-Derjaguin. Nos simulations numériques sont en partie en accord avec nos observations. / Polymer tubes, made of PDMS or PVC, are versatile, low cost, hydrophobic materials. They are heavily used in industry for transferring more or less complex fluids such as drinkable water, emulsions (e.g milk), suspensions (e.g coffee), or solution of active molecules (e.g pharmaceutics). Most of these applications involve repeated, intermittent flow of liquids which can lead to unwanted contamination. This study aims at better understanding the mechanisms of contamination for intermittent flow. We experimentally and theoretically investigate the flow regimes of low viscosity liquid slugs flowing down a vertical tube under partial wetting condition. Two processes are in competition: because of the large slug velocity, a liquid film tends to be created at the back of the slug whereas because of the partial wetting condition, the liquid film dewets. We investigate how this competition controls film deposition in hydrophobic tubes. We show that above the threshold velocity for dynamic wetting which is much lower than predicted by Cox-Voinov, a previously unknown regime is found where we observe a velocity dependent thick film well before the classical Landau-Levich-Derjaguin regime.

Nanocrystalline diamond (NCD) films possess great mechanical properties (low friction coefficient, high hardness etc.), chemical properties (e.g. low corrosivity or chemical inertness) and good biocompatibility. This makes them perspective materials for protective coatings of medical implants and devices. As bacteria biofilms are often very resistant to antibacterial treatment, materials with anti-bacterial or at least anti-adhesive properties are needed. The interaction of NCD films with bacteria has not been properly examined yet. The aim of this thesis was to introduce and optimize the methods for routine bacterial biofilm cultivation and analysis, use them to investigate the ability of NCD films to inhibit the attachment and biofilm formation of Escherichia coli and correlate it with the NCD surface hydrophobicity. The materials used for the study were hydrogenated NCD (hydrophobic), oxidized NCD (hydrophilic) and uncoated glass. For bacterial biofilm growth, cultivation in six-well plates and continuous cultivation in CDC Bioreactor was used. Several methods were tested for quantitative biofilm detachment and analysis. The putative anti-bacterial properties of NCD material were not confirmed in this work. Higher bacterial attachment to NCD films in comparison to the uncoated glass was...

Drop coating deposition Raman (DCDR) spectroscopy is a special method of Raman spectroscopy, which is based on the evaporation of solvent from a drop of solution or suspension on a hydrophobic surface. This typically leads to the formation of ring-shaped drying pattern, often called as "coffee ring". As a result a preconcentration of a material and higher intensity of Raman signal in comparison with Raman scattering from solution is obtained. In this work several hydrophobic surfaces with different roughness and hydrophobicity were compared: a smooth substrate with polytetrafluorethylen (pPTFE) coating and nanorough substrates where surface hydrophobicity was formed by deposited cupper or argent nanoparticles with different concentration. It was shown that for DPPC liposome suspension stronger preconcentration is obtained by means of a nanorough substrate. When different nanorough substrate compared, no better improvement was acquired. As for the drying of drops at different temperatures (from 15řC to 60řC) deposited on the smooth pPTFE substrate and the substrate with argent nanoparticles, it was observed that Raman spectra did not reveal any spectral changes corresponding to phase transition of lipid. In case of drying at temperatures higher than a temperature of the phase transition, non-homogeneities...

This master's thesis project investigates the impact of hydrophobicity and topology on dry and wet macroscopic particle accumulation on surfaces. The report begins by outlining the challenges associated with this phenomenon and the existing theories and methods used to study it, including adhesion, surface engineering, the Lotus effect, and humidity. The method chapter presents the case study of grass accumulation for robotic lawn mowing application and describes experiments conducted to simulate the accumulation of grass during robotic lawn mowing. These experiments explore two different phenomena: the accumulation of grass that is already stuck to a surface and the process by which grass initially sticks to a surface. Experiments have been done to change the hydrophobicity level of certain specimens and investigate how hydrophobicity and humidity affect the stickiness of grass when already accumulated on a surface. In addition, experiments are conducted by throwing grass towards surfaces with different hydrophobicity and topology to determine the influence of these variables on accumulation. Finally, a physical field test is conducted. The findings indicate that hydrophobicity up to 108,2° water contact angle has a low impact on both static and dynamic grass accumulation. Increased hydrophobicity does not tend to decrease grass accumulation, even showing increased accumulation in some experiments. Humidity and the wetness of the grass are more important factors. Experiments have shown that a textured surface can decrease the accumulation, showing significant results in a controlled environment. However, these results did not transfer over in a significant way to a real robotic lawn mowing situation.

ACP interacts with diverse proteins in an unknown way. Possibly there is a similar mode of interaction between ACP and all ACP-binding proteins, the amphiphilic helix. The hydrophobicities of helices from 4 different ACPs were compared. Hydrophobic moment plots were prepared for ACP helices and those of many EF hand calcium-binding proteins. Both groups of proteins occupied the same region of the plot.

Superhydrophobic coatings (SHC) with excellent self-cleaning and corrosion resistance property is developed on magnetite coated AISI SAE 1020 steel by using a simple immersion method. Roughness measurement, scanning electron microscopy (SEM), atomic force microscopy (AFM), X-ray diffraction (XRD), contact angle measurement (CAM), energy dispersive spectroscopy (EDS), Fourier transform infrared spectroscopy (FTIR), potentiodynamic polarization test, electrochemical impedance spectroscopy (EIS), and qualitative characterization of self-cleaning behavior, antifouling property and durability of the coatings are assessed. A water contact angle as high as 152o on the coated surface with excellent self-cleaning and resistivity to corrosion and good longevity in atmospheric air is obtained. Self-cleaning test results prove that these surfaces can find applications in large scale production of engineering materials. Potentiodynamic polarization tests and EIS tests confirm that the superhydrophobic low carbon steel surfaces have better resistance to corrosion compared to bare steel and magnetite coated steel in 3.5% NaCl solution. But the longevity of the coated steel surfaces in 3.5% salt solution is limited, which is revealed by the immersion durability test. However, hydrophobic coatings (HC) have better stability in normal tap water, and it can stay unharmed up to 15 days. Finally, hydrophobic coatings on low carbon steel surface retains hydrophobic in open atmosphere for more than two months. Results of this investigation show surface roughness is a critical factor in manufacturing hydrophobic steel surfaces. Higher contact angles are obtained for rougher and more uniform surfaces. A linear mathematical relationship (y =6x+104; R2 = 0.93) is obtained between contact angle (y) and surface roughness (x).