Poly(ethylene-co-acrylic acid) random copolymers : amphiphilic properties and self-assembly in aqueous medium

Les travaux de recherche présentés ici avaient pour objectif principal la synthèse de copolymères statistiques à base d’éthylène et d’acide acrylique (AA). Pour cela, la déprotection des groupements esters d’un copolymère statistique précurseur, le poly(éthylène-co-(tert-butyl)acrylate), a été effectuée par hydrolyse à l’aide d’iodure de triméthylsilyle. La synthèse de ce précurseur est réalisée par polymérisation catalytique en présence d’un système à base de Palladium (Pd). Le deuxième objectif a été d’étudier et de caractériser des polymères synthétisés à l’état solide et en suspension colloïdale. Plusieurs copolymères précurseurs comprenant différents pourcentages molaires en tert-butyl acrylate (4 à 12% molaires) ont été synthétisés avec succès, puis déprotégés par hydrolyse pour obtenir des poly(éthylène-coacide acrylique) (pE-co-AA) avec différentes compositions. Seuls les copolymères comprenant 10% molaire ou plus de AA sont solubles dans le Tétrahydrofurane (THF) et uniquement dans ce solvant. De telles solutions peuvent être dialysées dans l’eau, ce qui conduit à un échange lent entre cette dernière et le THF, et l’autoassemblage du copolymère dans l’eau peut ensuite être étudié. C’est ainsi qu’ont pu être observées des nanoparticules stables dans le temps dont le comportement est sensible au pH et à la température. Les polymères synthétisés ont été caractérisés par Résonance Magnétique Nucléaire (RMN) ainsi que par spectroscopie Infra-Rouge (IR), avant et après déprotection. Les pourcentages molaires d’AA ont été déterminés par combinaison des résultats de RMN et ii de titrages conductimètriques. A l’état solide, les échantillons ont été analysés par Calorimétrie différentielle à balayage (DSC) et par Diffraction des rayons X. Les solutions colloïdales des polymères pE-co-AA ont été caractérisées par Diffusion dynamique de la lumière et par la DSC-haute sensibilité. De la microscopie électronique à transmission (TEM) a permis de visualiser la forme et la taille des nanoparticules.

Défauts et diffusion dans le silicium amorphe

Nous avons observé une augmentation ‘’transient’’du taux de cristallisation interfacique de l’a-Si lorsqu’on réimplante du Si à proximité de l’interface amorphe/cristal. Après amorphisation et traitement thermique à 650°C pendant 5s de la couche a-Si crée par implantation ionique, une partie a été réimplantée. Les défauts produits par auto-réimplantation à 0.7MeV se trouvent à (302±9) nm de l’interface initiale. Cela nous a permis d’étudier d’avantage la variation initiale de la vitesse SPE (Épitaxie en phase solide). Avec des recuit identiques de 4h à 500°C, nous avons déterminé les positions successives des interfaces et en déduit les taux de cristallisation SPE. La cristallisation débute à l’interface et continue graduellement vers la surface. Après le premier recuit, (252±11) nm s’est recristallisé dans la zone réimplantée soit un avancement SPE de 1.26x10^18at./cm2. Cette valeur est environ 1.50 fois plus importante que celle dans l’état relaxé. Nous suggérons que la présence de défauts à proximité de l’interface a stimulé la vitesse initiale. Avec le nombre de recuit, l’écart entre les vitesses diminue, les deux régions se cristallisent presque à la même vitesse. Les mesures Raman prises avant le SPE et après chaque recuit ont permis de quantifier l’état de relaxation de l’a-Si et le transfert de l’état dé-relaxé à relaxé.

Self adhesion of short Kevlar fibre -thermoplastic polyurethane composite

The self adhesion behaviour of thermoplastic polyurethane (TPU) in itself and its composite with short Kevlar fibre with respect to contact time, temperature, pressure, and fibre loading has been studied. The adhesion strength showed two linear increments of different slopes with respect to the square root of time: with temperature and pressure of contact, the adhesion strength was improved. The maximum strength was obtained with 20 phr of short fibre in only one of the mating substrates in the peel test sample. The duration for wetting and diffusion was shifted to longer time intervals with fibres loaded in both the substrates.

Influence of the solvent on the self-assembly of a modified amyloid beta peptide fragment. II. NMR and computer simulation investigation

The conformation of a model peptide AAKLVFF based on a fragment of the amyloid beta peptide A beta 16-20, KLVFF, is investigated in methanol and water via solution NMR experiments and Molecular dynamics computer simulations. In previous work, we have shown that AAKLVFF forms peptide nanotubes in methanol and twisted fibrils in water. Chemical shift measurements were used to investigate the solubility of the peptide as a function of concentration in methanol and water. This enabled the determination of critical aggregation concentrations, The Solubility was lower in water. In dilute solution, diffusion coefficients revealed the presence of intermediate aggregates in concentrated solution, coexisting with NMR-silent larger aggregates, presumed to be beta-sheets. In water, diffusion coefficients did not change appreciably with concentration, indicating the presence mainly of monomers, coexisting with larger aggregates in more concentrated solution. Concentration-dependent chemical shift measurements indicated a folded conformation for the monomers/intermediate aggregates in dilute methanol, with unfolding at higher concentration. In water, an antiparallel arrangement of strands was indicated by certain ROESY peak correlations. The temperature-dependent solubility of AAKLVFF in methanol was well described by a van't Hoff analysis, providing a solubilization enthalpy and entropy. This pointed to the importance of solvophobic interactions in the self-assembly process. Molecular dynamics Simulations constrained by NOE values from NMR suggested disordered reverse turn structures for the monomer, with an antiparallel twisted conformation for dimers. To model the beta-sheet structures formed at higher concentration, possible model arrangements of strands into beta-sheets with parallel and antiparallel configurations and different stacking sequences were used as the basis for MD simulations; two particular arrangements of antiparallel beta-sheets were found to be stable, one being linear and twisted and the other twisted in two directions. These structures Were used to simulate Circular dichroism spectra. The roles of aromatic stacking interactions and charge transfer effects were also examined. Simulated spectra were found to be similar to those observed experimentally.(in water or methanol) which show a maximum at 215 or 218 nm due to pi-pi* interactions, when allowance is made for a 15-18 nm red-shift that may be due to light scattering effects.

Self-consistent field theory for diblock copolymers grafted to a sphere

An efficient numerical self-consistent field theory (SCFT) algorithm is developed for treating structured polymers on spherical surfaces. The method solves the diffusion equations of SCFT with a pseudospectral approach that combines a spherical-harmonics expansion for the angular coordinates with a modified real-space Crank–Nicolson method for the radial direction. The self-consistent field equations are solved with Anderson-mixing iterations using dynamical parameters and an alignment procedure to prevent angular drift of the solution. A demonstration of the algorithm is provided for thin films of diblock copolymer grafted to the surface of a spherical core, in which the sequence of equilibrium morphologies is predicted as a function of diblock composition. The study reveals an array of interesting behaviors as the block copolymer pattern is forced to adapt to the finite surface area of the sphere.

Engineering of 3D self-directed quantum dot ordering in multilayer InGaAs/GaAs nanostructures by means of flux gas composition

Lateral ordering of InGaAs quantum dots on the GaAs (001) surface has been achieved in earlier reports, resembling an anisotropic pattern. In this work, we present a method of breaking the anisotropy of ordered quantum dots (QDs) by changing the growth environment. We show experimentally that using As(2) molecules instead of As(4) as a background flux is efficient in controlling the diffusion of distant Ga adatoms to make it possible to produce isotropic ordering of InGaAs QDs over GaAs (001). The control of the lateral ordering of QDs under As(2) flux has enabled us to improve their optical properties. Our results are consistent with reported experimental and theoretical data for structure and diffusion on the GaAs surface.

Microgranitic Enclaves as Products of Self-mixing Events: a Study of Open-system Processes in the Maua Granite, Sao Paulo, Brazil, Based on in situ Isotopic and Trace Elements in Plagioclase

Felsic microgranular enclaves with structures indicating that they interacted in a plastic state with their chemically similar host granite are abundant in the Maua Pluton, SE Brazil. Larger plagioclase xenocrysts are in textural disequilibrium with the enclave groundmass and show complex zoning patterns with partially resorbed An-rich cores (locally with patchy textures) surrounded by more sodic rims. In situ laser ablation-(multi-collector) inductively coupled plasma mass spectrometry trace element and Sr isotopic analyses performed on the plagioclase xenocrysts indicate open-system crystallization; however, no evidence of derivation from more primitive basic melts is observed. The An-rich cores have more radiogenic initial Sr isotopic ratios that decrease towards the outermost part of the rims, which are in isotopic equilibrium with the matrix plagioclase. These profiles may have been produced by either (1) diffusional re-equilibration after rim crystallization from the enclave-forming magma, as indicated by relatively short calculated residence times, or (2) episodic contamination with a decrease of the contaminant ratio proportional to the extent to which the country rocks were isolated by the crystallization front. Profiles of trace elements with high diffusion coefficients would require unrealistically long residence times, and can be modeled in terms of fractional crystallization. A combination of trace element and Sr isotope data suggests that the felsic microgranular enclaves from the Maua Pluton are the products of interaction between end-member magmas that had similar compositions, thus recording `self-mixing` events.

Influence of human dentine on the antibacterial activity of self-etching adhesive systems against cariogenic bacteria

Objectives: The incorporation of antibacterial agents into adhesive systems has been proposed to eliminate residual bacteria from dentine. This study used the agar diffusion method to evaluate the antibacterial activity of Clearfil Protect Bond (CPB), Clearfil SE Bond (CSEB), Clearfil Tri-S Bond (C3SB) and Xeno-III (XIII) self-etching adhesive systems, with or without light-activation, against cariogenic bacteria, and to assess the influence of human dentine on the antibacterial activity of these materials.Methods: An aliquot of 10 mu l per material (and individual components) were pipetted onto paper and dentine discs distributed in Petri dishes containing bacterial culture in BHI agar. Positive control was 0.2% chlorhexidine digluconate (CHX).Results: After incubation, the adhesive components of CPB and CSEB, liquid A of XIII and C3SB did not present antibacterial activity when applied to paper discs. The non-light-activated CPB primer + adhesive promoted the greatest inhibition of Streptococcus mutans (p < 0.05), whereas with light-activation, there was no significant difference between primer + adhesive and primer alone. For Lactobacillus acidophilus, CPB primer presented the greatest antibacterial activity in both light-activation conditions (p < 0.05). Regarding the dentine discs, only CHX promoted an inhibitory effect, though less intense than on paper discs (p < 0.05). CHX presented greater antibacterial activity against S. mutans than against L. acidophilus (p < 0.05).Conclusions: Light-activation significantly reduced the antibacterial activity of the self-etching adhesive systems; MDPB incorporation contributed to the effect of adhesive systems against cariogenic bacteria; the components eluted from the adhesive systems were not capable to diffuse through 400 mu m-thick dentine disc to exert their antibacterial activity against cariogenic bacteria. (C) 2008 Elsevier Ltd. All rights reserved.

Mathematical models of generalized diffusion

We discuss in this paper equations describing processes involving non-linear and higher-order diffusion. We focus on a particular case (u(t) = 2 lambda (2)(uu(x))(x) + lambda (2)u(xxxx)), which is put into analogy with the KdV equation. A balance of nonlinearity and higher-order diffusion enables the existence of self-similar solutions, describing diffusive shocks. These shocks are continuous solutions with a discontinuous higher-order derivative at the shock front. We argue that they play a role analogous to the soliton solutions in the dispersive case. We also discuss several physical instances where such equations are relevant.

Electrochemical and spectroscopic characterization of screen-printed gold-based electrodes modified with self-assembled monolayers and Tc85 protein

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Growth evolution of self-textured ZnO films deposited by magnetron sputtering at low temperatures

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Tank experiments with borehole self-potential data

Despite their importance in the evaluation of petroleum and gas reservoirs, measurements of self-potential data under borehole conditions (well-logging) have found only minor applications in aquifer and waste-site characterization. This can be attributed to lower signals from the diffusion fronts in near-surface environments because measurements are made long after the drilling of the well, when concentration fronts are already disappearing. Proportionally higher signals arise from streaming potentials that prevent using simple interpretation models that assume signals from diffusion only. Our laboratory experiments found that dual-source self-potential signals can be described by a simple linear model, and that contributions (from diffusion and streaming potentials) can be isolated by slightly perturbing the borehole conditions. Perturbations are applied either by changing the concentration of the borehole-filling solution or its column height. Parameters useful for formation evaluation can be estimated from data measured during perturbations, namely, pore water resistivity, pressure drop across the borehole wall, and electrokinetic coupling parameter. These are important parameters to assess, respectively, water quality, aquifer lateral continuity, and interfacial properties of permeable formations.

Self-assembled films from chitosan and poly(vinyl sulfonic acid) on Nafion® for direct methanol fuel cell

Chitosan/poly(vinyl sulfonic acid) (PVS) films have been prepared on Nafion® membranes by the layer-by-layer (LbL) method for use in direct methanol fuel cell (DMFC). Computational methods and Fourier transform infrared (FTIR) spectra suggest that an ionic pair is formed between the sulfonic group of PVS and the protonated amine group of chitosan, thereby promoting the growth of LbL films on the Nafion® membrane as well as partial blocking of methanol. Chronopotentiometry and potential linear scanning experiments have been carried out for investigation of methanol crossover through the Nafion® and chitosan/PVS/Nafion® membranes in a diaphragm diffusion cell. On the basis of electrical impedance measurements, the values of proton resistance of the Nafion® and chitosan/PVS/Nafion® membranes are close due to the small thickness of the LbL film. Thus, it is expected an improved DMFC performance once the additional resistance of the self-assembled film is negligible compared to the result associated with the decrease in the crossover effect.

Potential vorticity conserving flows and vortex-wave interaction : the role of vertical velocity and isopycnal diffusion on plankton heterogeneity

Programa de doctorado de oceanografía

Nanostructuring by templated synthesis of nanowires and controlled crystallization of calcium phosphate on self-assembled monolayers

The idea was to obtain nanowires in a chemical laboratory under convenient and simple conditions by employing templates. Thus it was possible to produce nanochains by interlinking of gold colloids synthesized by the two-phase-method of M. Brust with by making use of vanadiumoxide nanotubes as template. The length of the resulting nanowires is varying between 1100 nm and 200 nm with a diameter of about 16 nm. Due to a flexible linker the obtained nanowires are not completely rigid. These unique structural features could make them interesting objects for structuring and assembling in the nanoscale range. Another way to produce gold nanowires was realized by a two-step surface metallization procedure, using type I collagen fibres as a template. Gold colloids were used to label the collagen fibres by direct electrostatic interaction, followed by growth steps to enhance the size of the adsorbed colloidal gold crystals, resulting in a complete metallization of the template surface. The length of the resulting gold nanowires reaches several micrometers, with a diameter ~ 100 to 120 nm. To gain a deeper insight into the process of biomineralization the cooperative effect of self-assembled monolayers as substrate and a soluble counterpart on the nucleation and crystal growth of calcium phosphate was studied by diffusion techniques with a pH switch as initiator. As soluble component Perlucin and Nacrein were used. Both are proteins originally extracted from marine organisms, the first one from the Abalone shell and the second one from oyster pearls. Both are supposed to facilitate the calcium carbonate formation in vivo. Studies with Perlucin revealed that this protein shows a clear cooperative effect at a very low concentration with a hydrophobic surface promoting the calcium phosphate precipitation resulting in a sponge like structure of hydroxyapatite. The Perlucin molecule is very flexible and is unfolded by adsorbing to the hydrophobic surface and uncovers its active side. Hydrophilic surfaces did not have a deeper impact. Studies with Nacrein as additive have shown that the protein stabilizes octacalcium phosphate at room temperature on carboxylic self-assembled monolayer and at 34 °C on all other employed surfaces by interaction with the mineral. On the hydroxyl-, alkyl-, and amin-terminated self-assembled monolayers at room temperature the octacalcium phosphate get transformed to hydroxyapatite. Main analytical techniques which are used in this work are transmission electron microscopy, high resolution scanning electron microscopy, surface plasmon resonance spectroscopy, atomic force microscopy, Raman micro-spectroscopy and quartz crystal microbalance.