CONCENTRATION FIELDS NEAR AIR-WATER INTERFACES DURING INTERFACIAL MASS TRANSPORT: OXYGEN TRANSPORT AND RANDOM SQUARE WAVE ANALYSIS

Mass transfer across a gas-liquid interface was studied theoretically and experimentally, using transfer of oxygen into water as the gas-liquid system. The experimental results support the conclusions of a theoretical description of the concentration field that uses random square waves approximations. The effect of diffusion over the concentration records was quantified. It is shown that the peak of the normalized rills concentration fluctuation profiles must be lower than 0.5, and that the position of the peak of the rms value is an adequate measure of the thickness of the diffusive layer. The position of the peak is the boundary between the regions more subject to molecular diffusion or to turbulent transport of dissolved mass.

Interaction of nitrogen dioxide (NO2) with a monolayer of oleic acid at the air–water interface – A simple proxy for atmospheric aerosol

The reactions between atmospheric oxidants and organic amphiphiles at the air water interface of an aerosol droplet may affect the size and critical supersaturation required for cloud droplet formation. We demonstrate that no reaction occurs between gaseous nitrogen dioxide (1000 ppm in air) and a monolayer of an insoluble amphiphile, oleic acid (cis-9-octadecenoic acid), at the air water interface which removes material from the air water interface. We present evidence that the NO2 isomerises the cis-9-octadecenoic (oleic) acid to trans-9-octadecenoic (elaidic) acid. The study presented here is important for future and previous studies of (1) the reaction between the nitrate radical, NO3, and thin organic films as NO2 is usually present in high concentrations in these experimental systems and (2) the effect of NO2 air pollution on the unsaturated fatty acids and lipids found at the air liquid surface of human lung lining fluid.

Estimation of Mass Transfer Velocity Based on Measured Turbulence Parameters

The aim of this study is to quantify the mass transfer velocity using turbulence parameters from simultaneous measurements of oxygen concentration fields and velocity fields. The surface divergence model was considered in more detail, using data obtained for the lower range of beta (surface divergence). It is shown that the existing models that use the divergence concept furnish good predictions for the transfer velocity also for low values of beta, in the range of this study. Additionally, traditional conceptual models, such as the film model, the penetration-renewal model, and the large eddy model, were tested using the simultaneous information of concentration and velocity fields. It is shown that the film and the surface divergence models predicted the mass transfer velocity for all the range of the equipment Reynolds number used here. The velocity measurements showed viscosity effects close to the surface, which indicates that the surface was contaminated with some surfactant. Considering the results, this contamination can be considered slight for the mass transfer predictions. (C) 2009 American Institute of Chemical Engineers AIChE J, 56: 2005-2017; 2010

pH Influence on the stability of foams with protein-polysaccharide complexes at their interfaces

Food foams such as marshmallow, Chantilly and mousses have behavior and stability directly connected with their microstructure, bubble size distribution and interfacial properties. A high interfacial tension inherent to air/liquid foams interfaces affects its stability, and thus it has a direct impact on processing, storage and product handling. In this work, the interactions of egg albumin with various types of polysaccharides were investigated by drop tensiometry, interfacial rheology and foam stability. The progressive addition of egg albumin and polysaccharide in water induced a drop of the air-water surface tension which was dependent on the pH and polysaccharide type. At pH 4, that is below the isoeletric point of egg albumen (pI = 4.5) the surface tension was decreased from 70 mN/m to 42 mN/m by the presence of the protein, and from 70 mN/m to 43 mN/m, 40 mN/m and 38 mN/m by subsequent addition of xanthan, guar gum and kappa-carrageenan, respectively. At pH 7.5 the surface tension was decreased from 70 mN/m to 43 mN/m by the simultaneous presence of the protein and kappa-carrageenan. However, a higher surface tension of 48 and 50 mN/m was found when xanthan and guar gum were added, respectively, when compared with carrageenan addition. The main role on the stabilization of protein-polysaccharide stabilized interfaces was identified on the elasticity of the interface. Foam stability experiments confirmed that egg-albumin/kappa-carrageenan at pH below the protein isoeletric point are the most efficient systems to stabilize air/water interfaces. These results clearly indicate that protein-polysaccharide coacervation at the air/water interface is an efficient process to increase foam stability. (C) 2009 Elsevier Ltd. All rights reserved.

Dermaseptin 01 as antimicrobial peptide with rich biotechnological potential: study of peptide interaction with membranes containing Leishmania amazonensis lipid-rich extract and membrane models

This article addresses the interactions of the synthetic antimicrobial peptide dermaseptin 01 (GLWSTIKQKGKEAAIAAA-KAAGQAALGAL-NH(2), DS 01) with phospholipid (PL) monolayers comprising (i) a lipid-rich extract of Leishmania amazonensis (LRE-La), (ii) zwitterionic PL (dipalmitoylphosphatidylcholine, DPPC), and (iii) negatively charged PL (dipalmitoylphosphatidylglycerol, DPPG). The degree of interaction of DS 01 with the different biomembrane models was quantified from equilibrium and dynamic liquid-air interface parameters. At low peptide concentrations, interactions between DS 01 and zwitterionic PL, as well as with the LRE-La monolayers were very weak, whereas with negatively charged PLs the interactions were stronger. For peptide concentrations above 1 mu g/ml, a considerable expansion of negatively charged monolayers occurred. In the case of DPPC, it was possible to return to the original lipid area in the condensed phase, suggesting that the peptide was expelled from the monolayer. However, in the case of DPPG, the average area per lipid molecule in the presence of DS 01 was higher than pure PLs even at high surface pressures, suggesting that at least part of DS 01 remained incorporated in the monolayer. For the LRE-La monolayers, DS 01 also remained in the monolayer. This is the first report on the antiparasitic activity of AMPs using Langmuir monolayers of a natural lipid extract from L. amazonensis. Copyright (C) 2011 European Peptide Society and John Wiley & Sons, Ltd.

Experimental study of drop-interface coalescence in the presence of polymer stabilisers

An experimental study has been carried out to characterise the performance of polymer stabilisers, partially hydrolysed polyvinyl acetate (PVAc), used in suspension polymerisation processes. The stabilisers are ranked by their ability to stabilise the dispersion characterised by the median coalescence time of a single drop with its homophase at a planar liquid/liquid interface. Results show that the stability of the dispersion relates closely to the molecular properties of the PVAcs. Other conditions being equal, PVAcs with higher molecular weights or lower degrees of hydrolysis can better stabilise a liquid-liquid dispersion. The stability of the dispersion also depends strongly on where the PVAc resides. The presence of a PVAc in the dispersed phase significantly reduces stability. Consistent with results reported in the literature, considerable scatter has been observed on the coalescence times of identical drops under the same conditions. An explanation for the scatter is also proposed in the paper, based on the classical Reynolds model for film thinning. (C) 2002 Elsevier Science B.V. All rights reserved.

A double layer model of the gas bubble/water interface

Zeta potential is a physico-chemical parameter of particular importance to describe sorption of contaminants at the surface of gas bubbles. Nevertheless, the interpretation of electrophoretic mobilities of gas bubbles is complex. This is due to the specific behavior of the gas at interface and to the excess of electrical charge at interface, which is responsible for surface conductivity. We developed a surface complexation model based on the presence of negative surface sites because the balance of accepting and donating hydrogen bonds is broken at interface. By considering protons adsorbed on these sites followed by a diffuse layer, the electrical potential at the head-end of the diffuse layer is computed and considered to be equal to the zeta potential. The predicted zeta potential values are in very good agreement with the experimental data of H-2 bubbles for a broad range of pH and NaCl concentrations. This implies that the shear plane is located at the head-end of the diffuse layer, contradicting the assumption of the presence of a stagnant diffuse layer at the gas/water interface. Our model also successfully predicts the surface tension of air bubbles in a KCl solution. (c) 2012 Elsevier Inc. All rights reserved.

Estimativa do fluxo de amônia na interface ar-mar na Baía de Guanabara: estudo preliminar

In the begining of April 2004, concentrations of NHx (NH3 + NH4+) were measured in surface waters of the Guanabara Bay. Concentrations varied from 2 to 143 mmol L-1. Ammonia exchange at the air-sea interface was quantified using a numerical model. No measurement of NH3 concentration in air (c air) was performed. Thus, calculations of NH3 flux were based on the assumptions of c air = 1 and 5 µg m-3. Fluxes were predominantly from the water to the atmosphere and varied from -20 to almost 3500 µg N m-2 h-1.

Fluxos de óxido nitroso na interface ar-mar na Baía de Guanabara

In Surface water concentrations of N2O were measured at 37 stations in Guanabara Bay and fluxes estimated across the air-sea interface. Concentrations averaged 8.2 ± 2.2 nmol L-1 and 90% of the stations showed supersaturation averaging 33%. N2O fluxes were estimated using a two-film model which is given by the product of the concentration difference across the film and the gas transfer coefficient (k w). Two parametrizations of k w were used which provided average fluxes of 0.3 and 3.0 µg N m-2 h-1. Flux measurements using floating chambers (not reported here) seem to agree with the upper limit of these estimates.

Propriétés supramoléculaires des cations diimidazolium disubstitués : des complexes d’inclusion en solution aux interactions à l’état cristallin et cristal liquide

Les sels d’imidazolium ont un rôle important dans certaines protéines et acides nucléiques et ont été utilisés à de nombreuses reprises dans des assemblages supramoléculaires en raison de leurs propriétés uniques. Les sels de diimidazolium dérivés sont toutefois moins connus. Ils ont pour l’instant uniquement été utilisés comme des précurseurs de carbènes N-hétérocycliques. Ils sont donc à la base de plusieurs catalyseurs utilisés pour des réactions de couplage croisés mais leurs propriétés sont toutefois méconnues dans le cadre de la chimie supramoléculaire. Cette classe de composés a nottament attiré notre attention en raison de la facilité de modification de leurs propriétés physico-chimiques par modification de leur structure chimique. L’objectif général des travaux présentés dans cette thèse est l’étude des propriétés supramoléculaires des sels de diimidazolium disubstitués en solution (aqueuse ou organique), ainsi qu’en phase solide ou cristal-liquide. L’influence de l’espaceur entre les deux noyaux imidazolium ainsi que l’influence des substituants latéraux et des contre-ions a été étudiée. Dans un premier temps, les propriétés de complexation des sels de diimidazolium à des macrocycles sont étudiées. Les sels bromure sont étudiés en solution aqueuse avec plusieurs cyclodextrines et le cucurbit[7]uril, et les sels hexafluorophosphate sont étudiés en solution organique pour leur complexation avec l’éther couronne DB24C8 et un calix[4]arène. Cette nouvelle classe de composés a montré de très bonnes propriétés de complexation à ces différents macrocycles en solution et a également permis de contrôler différents assemblages supramoléculaires à l’interface air-eau. Dans un deuxième temps, l’étude des sels de phénylènediimidazolium a permis de modifier les propriétés de complexation en solution pour obtenir la formation de complexes multiples avec le cucurbit[7]util en solution aqueuse. Cette même famille de composés a également permis la formation de cristaux liquides ioniques lorsque les substituants sont des chaînes alkyles plus longues. La résolution de plusieurs structures cristallines de différents sels de diimidazolium a finalement permis de comprendre la nature des interactions intermoléculaires à l’état cristallin. La recherche présentée dans cette thèse a donc permis une étude détaillée des propriétés supramoléculaires des sels de diimidazolium dans tous les états de la matière qui leur sont accessibles.

Nanopatterning and functionalization of phospholipid-based Langmuir-Blodgett and Langmuir-Schaefer films

Durant les dernières décennies, la technique Langmuir-Blodgett (LB) s’est beaucoup développée dans l’approche « bottom-up » pour la création de couches ultra minces nanostructurées. Des patrons constitués de stries parallèles d’environ 100 à 200 nm de largeur ont été générés avec la technique de déposition LB de monocouches mixtes de 1,2-dilauroyl-sn-glycéro-3-phosphatidylcholine (DLPC) et de 1,2-dipalmitoyl-sn-glycéro-3-phosphatidylcholine (DPPC) sur des substrats de silicium et de mica. Afin d’amplifier la fonctionnalité de ces patrons, la 1-palmitoyl-2-(16-(S-methyldithio)hexadécanoyl)-sn-glycéro-3-phosphatidylcholine (DSDPPC) et la 1-lauroyl-2-(12-(S-methyldithio)dodédecanoyl)-sn-glycéro-3-phosphatidylcholine (DSDLPC) ont été employées pour la préparation de monocouches chimiquement hétérogènes. Ces analogues de phospholipide possèdent un groupement fonctionnel méthyldisulfide qui est attaché à la fin de l’une des chaînes alkyles. Une étude exhaustive sur la structure de la phase des monocouches Langmuir, Langmuir-Schaefer (LS) et LB de la DSDPPC et de la DSDLPC et leurs différents mélanges avec la DPPC ou la DLPC est présentée dans cette thèse. Tout d’abord, un contrôle limité de la périodicité et de la taille des motifs des stries parallèles de DPPC/DLPC a été obtenu en variant la composition lipidique, la pression de surface et la vitesse de déposition. Dans un mélange binaire de fraction molaire plus grande de lipide condensé que de lipide étendu, une vitesse de déposition plus lente et une plus basse pression de surface ont généré des stries plus continues et larges. L’addition d’un tensioactif, le cholestérol, au mélange binaire équimolaire de la DPPC/DLPC a permis la formation de stries parallèles à de plus hautes pressions de surface. La caractérisation des propriétés physiques des analogues de phospholipides a été nécessaire. La température de transition de phase de la DSDPPC de 44.5 ± 1.5 °C comparativement à 41.5 ± 0.3 °C pour la DPPC. L’isotherme de la DSDPPC est semblable à celui de la DPPC. La monocouche subit une transition de phase liquide-étendue-à-condensée (LE-C) à une pression de surface légèrement supérieure à celle de la DPPC (6 mN m-1 vs. 4 mN m-1) Tout comme la DLPC, la DSDLPC demeure dans la phase LE jusqu’à la rupture de la monocouche. Ces analogues de phospholipide existent dans un état plus étendu tout au long de la compression de la monocouche et montrent des pressions de surface de rupture plus basses que les phospholipides non-modifiés. La morphologie des domaines de monocouches Langmuir de la DPPC et de la DSDPPC à l’interface eau/air a été comparée par la microscopie à angle de Brewster (BAM). La DPPC forme une monocouche homogène à une pression de surface (π) > 10 mN/m, alors que des domaines en forme de fleurs sont formés dans la monocouche de DSDPPC jusqu’à une π ~ 30 mN m-1. La caractérisation de monocouches sur substrat solide a permis de démontrer que le patron de stries parallèles préalablement obtenu avec la DPPC/DLPC était reproduit en utilisant des mélanges de la DSDPPC/DLPC ou de la DPPC/DSDLPC donnant ainsi lieu à des patrons chimiquement hétérogènes. En général, pour obtenir le même état de phase que la DPPC, la monocouche de DSDPPC doit être comprimée à de plus hautes pressions de surface. Le groupement disulfide de ces analogues de phospholipide a été exploité, afin de (i) former des monocouches auto-assemblées sur l’or et de (ii) démontrer la métallisation sélective des terminaisons fonctionnalisées des stries. La spectrométrie de photoélectrons induits par rayons X (XPS) a confirmé que la monocouche modifiée réagit avec la vapeur d’or pour former des thiolates d’or. L’adsorption de l’Au, de l’Ag et du Cu thermiquement évaporé démontre une adsorption préférentielle de la vapeur de métal sur la phase fonctionnalisée de disulfide seulement à des recouvrements sub-monocouche.

Étude des poly(2-alkyl-2-oxazoline)s munis d'extrémités hydrophobes en solution aqueuse et à linterface eau/air

Thèse numérisée par la Division de la gestion de documents et des archives de l'Université de Montréal

Using phospholipid Langmuir and Langmuir-Blodgett films as matrix for urease immobilization

The immobilization of enzymes in organized two-dimensional matrices is a key requirement for many biotechnological applications. In this paper, we used the Langmuir-Blodgett (LB) technique to obtain controlled architectures of urease immobilized in solid supports, whose physicochemical properties were investigated in detail. Urease molecules were adsorbed at the air-water interface and incorporated into Langmuir monolayers of the phospholipid dipalmitoyl phosphatidyl glycerol (DPPG). Incorporation of urease made DPPG monolayers more flexible and caused the reduction of the equilibrium and dynamic elasticity of the film. Urease and DPPG-urease mixed monolayers could be transferred onto solid substrates, forming LB films. A close packing arrangement of urease was obtained, especially in the mixed LB films, which was inferred with nanogravimetry and electrochemistry measurements. From the blocking effect of the LB films deposited onto indium tin oxide (ITO) substrates, the electrochemical properties of the LB films pointed to a charge transport controlled by the lipid architecture. (c) 2007 Elsevier Inc. All rights reserved.

Utilização de uma coluna de flotação para remoção de compostos orgânicos da água de produção

Innovative technologies using surfactant materials have applicability in several industrial fields, including petroleum and gas areas. This study seeks to investigate the use of a surfactant derived from coconut oil (SCO saponified coconut oil) in the recovery process of organic compounds that are present in oily effluents from petroleum industry. For this end, experiments were accomplished in a column of small dimension objectifying to verify the influence of the surfactant SCO in the efficiency of oil removal. This way, they were prepared emulsions with amount it fastens of oil (50, 100, 200 and 400 ppm), being determined the great concentrations of surfactant for each one of them. Some rehearsals were still accomplished with produced water of the industry of the petroleum to compare the result with the one of the emulsions. According to the experiments, it was verified that an increase of the surfactant concentration does not implicate in a greater oil removal. The separation process use gaseous bubbles formed when a gas stream pass a liquid column, when low surfactant concentrations are used, it occurs the coalescence of the dispersed oil droplets and their transport to the top of the column, forming a new continuous phase. Such surfactants lead to a gas-liquid interface saturation, depending on the used surfactant concentration, affecting the flotation process and influencing in the removal capacity of the oily dispersed phase. A porous plate filter, with pore size varying from 40 to 250 mm, was placed at the base of the column to allow a hydrodynamic stable operation. During the experimental procedures, the operating volume of phase liquid was held constant and the rate of air flow varied in each experiment. The resulting experimental of the study hydrodynamic demonstrated what the capturing of the oil was influenced by diameter of the bubbles and air flow. With the increase flow of 300 about to 900 cm3.min-1, occurred an increase in the removal of oil phase of 44% about to 66% and the removal kinetic of oil was defined as a reaction of 1° order

Utilização de uma coluna de flotação para remoção de compostos orgânicos da água de produção

Innovative technologies using surfactant materials have applicability in several industrial fields, including petroleum and gas areas. This study seeks to investigate the use of a surfactant derived from coconut oil (SCO saponified coconut oil) in the recovery process of organic compounds that are present in oily effluents from petroleum industry. For this end, experiments were accomplished in a column of small dimension objectifying to verify the influence of the surfactant SCO in the efficiency of oil removal. This way, they were prepared emulsions with amount it fastens of oil (50, 100, 200 and 400 ppm), being determined the great concentrations of surfactant for each one of them. Some rehearsals were still accomplished with produced water of the industry of the petroleum to compare the result with the one of the emulsions. According to the experiments, it was verified that an increase of the surfactant concentration does not implicate in a greater oil removal. The separation process use gaseous bubbles formed when a gas stream pass a liquid column, when low surfactant concentrations are used, it occurs the coalescence of the dispersed oil droplets and their transport to the top of the column, forming a new continuous phase. Such surfactants lead to a gas-liquid interface saturation, depending on the used surfactant concentration, affecting the flotation process and influencing in the removal capacity of the oily dispersed phase. A porous plate filter, with pore size varying from 40 to 250 mm, was placed at the base of the column to allow a hydrodynamic stable operation. During the experimental procedures, the operating volume of phase liquid was held constant and the rate of air flow varied in each experiment. The resulting experimental of the study hydrodynamic demonstrated what the capturing of the oil was influenced by diameter of the bubbles and air flow. With the increase flow of 300 about to 900 cm3.min-1, occurred an increase in the removal of oil phase of 44% about to 66% and the removal kinetic of oil was defined as a reaction of 1° order.