Adsorption Of Micelles Research Articles

Direct Visualization of Cationic Surfactant Aggregates at a Cellulose−Water Interface

The structure of adsorbed aggregates of the cationic surfactant cetyltrimethylammonium bromide (C(16)TAB) at the cellulose-water interface was determined using soft-contact atomic force microscopy imaging. C(16)TAB was adsorbed to the surface from a solution with a concentration above the critical micelle concentration. Imaging of the surfactant aggregate layer showed predominantly spherical micellar structures at the cellulose-water interface with some areas of short rodlike aggregates. These structures are similar to those previously observed for C(16)TAB adsorbed to other hydrophilic surfaces such as silica; hence, a similar mechanism for the arrangement of C(16)TAB on cellulose is suggested, in agreement with previous neutron reflectivity data. The buildup of the surfactant layer proceeds via direct micelle adsorption to the uncharged cellulose surface. This occurs through polar interactions between the C(16)TAB headgroup and the hydrophilic substrate to form the observed admicelle structures.

Role of Surface Reorganization on Preferential Adsorption of Macromolecular Ensembles at the Solid/Fluid Interface

The adsorption of micelles made from precisely synthesized branched block copolymers is investigated and analyzed using a model framework that incorporates the effects of mass transport and dynamic relaxation/reorganization events occurring at the solid/fluid interface. Both processes are required to represent adequately the adsorption profile over the entire progression to pseudoequilibrium. Insight into the relative importance of the two processes, the terminus of the diffusion-dominated regime, and differences between diffusion in free solution and in confinement is also provided. The results demonstrate commonality between adsorption of micelle-forming surfactant-like copolymers and biomimetic vesicles formed by small-molecule surfactants, both of which are systems dominated by rearrangements on the surface.

Hierarchical Adsorption of Network-Forming Associative Polymers

In this paper, we discuss the hierarchical adsorption of micelles formed from network-forming, telechelic, associative polymers at an air-water interface. We propose an interfacial mechanism that involves three distinct steps: (i) adsorption of the micellar coronas at the interface, (ii) unfolding of the micelles to anchor the hydrophobic tails at the interface, and (iii) formation of a secondary adsorption layer by bridging between the primary layer and micelles in the bulk. While the first, transport-limited process is relatively fast, the latter processes are surprisingly slow; it may take up to 10(6) s for the adsorption to complete.

Adsorption of Anionic Surfactants in a Nonionic Polymer Brush: Experiments, Comparison with Mean-Field Theory, and Implications for Brush−Particle Interaction

The adsorption of the anionic surfactants sodium dodecyl sulfate (SDS) and sodium dodecyl benzene sulfonate (SDBS) in poly(ethylene oxide) (PEO) brushes was studied using a fixed-angle optical flow-cell reflectometer. We show that, just as in solution, there is a critical association concentration (CAC) for the surfactants at which adsorption in the PEO brush starts. Above the critical micelle concentration (CMC) the adsorption is found to be completely reversible. At low brush density the adsorption per PEO monomer is equal to the adsorption of these surfactants in bulk solution. However, with increasing brush density, the number of adsorbed surfactant molecules per PEO monomer decreases rapidly. This decrease is explained in terms of excluded volume interactions plus electrostatic repulsion between the negatively charged surfactant micelles. Experimentally, a plateau value in the total adsorption is observed as a function of grafting density. The experimental results were compared to the results of an analytical self-consistent field (aSCF) model, and we found quantitative agreement. Additionally, the model predicts that the plateau value found is in fact a maximum. Both experiments and model calculations show that the adsorption scales directly with the polymerization degree of the polymers in the brush. They also show that an increase in the ionic strength leads to an increase in the adsorbed amount, which is explained as being due to a decrease in the electrostatic penalty for the adsorption of the SDS micelles. The adsorption of SDS micelles changes the interactions of the PEO brush with a silica particle. This is illustrated by atomic force microscopy (AFM) measurements of the pull-off force of a silica particle from a PEO brush: at high enough PEO densities, the addition of SDS leads to a very strong reduction in the force necessary to detach the colloidal silica particle from the PEO brush. We attribute this effect to the large amount of negative charge incorporated in the PEO brush due to SDS adsorption.

Reversible pH-Triggered Encapsulation and Release of Pyrene by Adsorbed Block Copolymer Micelles

The well-established ability of copolymer micelles to encapsulate and release hydrophobic molecules has been investigated following their adsorption onto silica particles. Here, a pH-responsive copolymer, poly(2-(dimethylamino)ethyl methacrylate)- b-poly(2-(diethylamino)ethyl methacrylate) (PDMA(106)- b-PDEA(25)), has been used to study the formation and dissociation of adsorbed micelles through pH variation. This copolymer behaves as free unimers in aqueous solutions below pH 8 and forms micelles 29 nm in hydrodynamic diameter above this pH. Encapsulation and release of a model hydrophobic compound (pyrene) by in situ adjustment of the solution pH has been compared for both free and adsorbed micelles using fluorescence spectrophotometry, epifluorescence microscopy, and zeta potential measurements. At basic pH values, pyrene is solubilized within the cores of micelles adsorbed on silica particles: addition of acid leads to micelle dissociation and release of the pyrene into the bulk aqueous solution. Micelle adsorption does not appear to hinder the extent of pyrene uptake/release. Moreover, this pH-responsive behavior is both reversible and reproducible over multiple pH cycles.

Role of Nanomechanical Properties in the Tribological Performance of Phospholipid Biomimetic Surfaces

The role of phospholipid bilayers in controlling and reducing frictional forces between biological surfaces is investigated by three complementary experiments: friction forces are measured using a homemade tribometer, mechanical resistance to indentation is measured by AFM, and lipid bilayer degradation is controlled in situ during friction testing using fluorescence microscopy. DPPC lipid bilayers in the solid phase generate friction coefficients as low as 0.002 (comparable to that found for cartilage) that are stable through time. DOPC bilayers formed by the vesicle fusion method or the adsorption of mixed micelles generate higher friction coefficients. These coefficients increased through time, during which the bilayers degraded. The friction coefficient is correlated with the force needed to penetrate the bilayer with the AFM tip. With only one bilayer in the contact region, the friction increased to a similar value of about 0.08 for the DPPC and DOPC. Our study therefore shows that good mechanical stability of the bilayers is essential and suggests that the low friction coefficient is ensured by the hydration layers between adjacent lipid bilayers.

Electrostatic Charging of Nonpolar Colloids by Reverse Micelles

Colloids dispersed in a nonpolar solvent become charged when reverse micelles are added. We study the charge of individual sterically stabilized poly(methyl methacrylate) spheres dispersed in micellar solutions of the surfactants sodium bis(2-ethyl 1-hexyl) sulfosuccinate [AOT], zirconyl 2-ethyl hexanoate [Zr(Oct)2], and a copolymer of poly(12-hydroxystearic acid)-poly(methyl methacrylate) [PHSA-PMMA]. Although the sign of the particle charge is positive for Zr(Oct)2, negative for AOT, and essentially neutral for PHSA-PMMA, the different micellar systems display a number of common features. In particular, we demonstrate that over a wide range of concentrations the particle potential is a constant, independent of the number of micelles added and independent of the colloid size. A simple thermodynamic model, in which the particle charge is generated by the competitive adsorption of both positive and negative micelles, is in good agreement with the experimental data.

Internal Structure of a Thin Film of Mixed Polymeric Micelles on a Solid/Liquid Interface

The adsorption of mixed micelles of poly(4-(2-amino hydrochloride-ethylthio)-butylene)- block-poly(ethylene oxide), PAETB 49- b-PEO 212 and poly(4-(2-sodium carboxylate-ethylthio)-butylene)- block-poly(ethylene oxide), PCETB 47- b-PEO 212 on solid/liquid interfaces has been studied with light, X-ray, and neutron reflectometry. The structure of the adsorbed layer can be described with a two-layer model consisting of an inner layer formed by the coacervate of the polyelectrolyte blocks PAETB 49 and PCETB 47 ( approximately 1 nm) and an outer layer of PEO 212 blocks ( approximately 6 nm). The micelles unfold upon adsorption forming a rather homogeneous flat layer that exposes its polyethylene oxide chains into the solution, thus rendering the surface antifouling after modification with the micelles.

Hierarchical Nanoporous Structures by Self‐Assembled Hybrid Materials Based on Block Copolymers

AbstractHierarchical nanoporous structures are fabricated by adsorption of micelles of diblock copolymer‐templated Au‐nanoparticles onto a hydrophilic solid substrate. Gold nanoparticles are prepared using micelles (19 nm) of polystyrene‐block‐poly(4‐vinylpyridine) (PS‐b‐P4VP) as nanoreactors. Deposition of thin films of the micellar solution, modified with a non‐selective solvent (THF), on hydrophilic surfaces leads to the formation of hierarchical nanoporous morphologies. The thin films exhibit two different pore diameters and a total pore density of 15 × 108 holes per cm2. The structure was analyzed in terms of topography and chemical composition using AFM, TEM and XPS measurements. The PS‐b‐P4VP template was subsequently removed by oxygen plasma etching, to leave behind metallic nanopores that mimic the original thin film morphology.magnified image

Recent Advances in Shell Cross‐Linked Micelles

AbstractChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

Polymerized Rodlike Micelle Adsorption at the Solid−Liquid Interface

The adsorption of rodlike polymer-micelle aggregates of cetyltrimethylammonium 4-vinylbenzoate (p-C16TVB) at the silica-water interface has been characterized using a combination of quartz crystal microbalance with dissipation monitoring (QCM-D) and atomic force microscopy (AFM) studies. Adsorption isotherm data, recorded by QCM-D, indicate a two-stage mechanism: an adsorbed film of free CTA+ ions is initially produced at low concentrations until the surface is charge reversed, whereupon the weakly anionic aggregates can adsorb and the adsorbed mass is seen to increase dramatically. The adsorbed rodlike micelle aggregates are seen to form a close-packed monolayer from AFM images with a high degree of order over micrometer length scales. AFM force-distance data indicate that the adsorbed aggregates retain their cylindrical structure and little or no flattening is seen. Rinsing of the film did not result in removal of the adsorbed layer, and the persistence of these nanoscale ordered films at the solid-liquid interface suggests many possible applications.

Recent advances in shell cross-linked micelles

The field of shell cross-linked (SCL) micelles is briefly reviewed. Important advances over the last two years are emphasized, potential application areas are discussed and current technical problems with these fascinating nanoparticles are highlighted. Particular attention is paid to (i) the development of new cross-linking chemistries and (ii) the adsorption of SCL micelles at interfaces.

Adsorption of Polymeric Micelles and Vesicles on a Surface Investigated by Quartz Crystal Microbalance

Polystyrene-b-poly(N-isopropylacrylamide) (PS-b-PNIPAM) diblock copolymers either with or without thiol end groups, depending on the relative length of the two blocks, form micelles or vesicles in water. The adsorption of such micelles or vesicles on a gold surface from aqueous solution was investigated in situ at 20 degrees C by use of a quartz crystal microbalance with dissipation monitoring (QCM-D). The changes in frequency (Deltaf) and dissipation (DeltaD) revealed that the micelles and vesicles without thiol groups were intact with some deformation when they were deposited on the surface. On the other hand, the micelles and vesicles with thiol groups at the end of PNIPAM blocks would transform into trilayers due to the strong interaction between thiols and gold surface.

Behaviour of homogenized fat globules during the spray drying of whole milk

The changes in milk fat globule size and fat globule surface proteins of both low-preheated and high-preheated concentrated milks, which were homogenized at low or high pressure prior to spray drying using a disc atomization drier, were examined. The average fat globule size ( d 32) of the spray-dried milk powders was smaller than that of the corresponding concentrates, but a small proportion of very large globules (4–80 μm) was also formed during spray drying. As a consequence, total surface protein (mg protein g −1 fat) increased due to the adsorption of casein micelles at the fat globule surface during spray drying. Confocal micrographs of the powders showed some apparent spreading of the fat on the surface of the powder particles, particularly when the concentrates were homogenized at low pressure. These results indicate disruption of the milk fat globules during spray drying, which consequently causes changes in the fat globule surface protein layer.

Effect of NaCl on the Self-Aggregation of n-Octyl β-d-Thioglucopyranoside in Aqueous Medium

This report investigates the effect of sodium chloride (NaCl) on the micellization, surface activity, and the evolution in the shape and size of n-octyl beta-D-thioglucopyranoside (OTG) aggregates. By using surface tension measurements, information was obtained on both changes in the critical micelle concentration and adsorption behavior in the air-liquid interface with the electrolyte concentration. These data were used to obtain the thermodynamic properties of micellization along with the corresponding adsorption parameters in the air-liquid interface. From extended static and dynamic light scattering measurements, the micelle molecular weight, the mean aggregation number, and the second virial coefficient, the apparent diffusion coefficient and the mean hydrodynamic radius of micelles in a range of NaCl concentrations were obtained. The light scattering data have shown that when the surfactant concentration is lower to 4.5 g/L, only spherical micelles are formed. However, an increase in the surfactant concentration induces an increase in micellar size, suggesting a rodlike growth of the micelles. This deviation of micelle geometry from spherical to rodlike is supported both by the ratio between the hydrodynamic radius and the radius of gyration and by the angular dependence of light scattering. On the other hand, the studies performed in the presence of high NaCl concentration (0.2 and 0.5 M) provide strong support for the view that the micelles may overlap together to form an entangled network above certain crossover concentration.

Comparison of the Adsorption of Cationic Diblock Copolymer Micelles from Aqueous Solution onto Mica and Silica

The similarities and differences in the adsorption behavior of diblock poly(2-(dimethylamino)ethyl methacrylate)-b-poly(2-(diethylamino)ethyl methacrylate) (XqPDMA-PDEA, where X refers to a mean degree of quaternization of the PDMA of either 0, 10, 50, or 100 mol%) copolymers at the mica/ and silica/aqueous solution interfaces have been investigated. These diblock copolymers form core-shell micelles with the PDEA chains located in the cores and the more hydrophilic PDMA chains forming the cationic micelle coronas at pH 9. These micelles adsorb strongly onto both mica and silica due to electrostatic interactions. In situ atomic force microscopy (AFM) has demonstrated that the mean spacing and the dimension of the adsorbed micelles depend on both the substrate and the mean degree of quaternization of the PDMA blocks. In particular, the morphology of the adsorbed nonquaternized 0qPDMA-PDEA copolymer micelles is clearly influenced by the substrate type: these micelles form a disordered layer on silica, while much more close-packed, highly ordered layers are obtained on mica. The key reasons for this difference are suggested to be the ease of lateral rearrangement for the copolymer micelles attached to the solid substrates and the relative rates of relaxation of the coronal PDMA chains.

Does homogenization affect the human health properties of cow's milk?

During the processing of marketed milk, homogenization reduces fat droplet size and alters interface composition by adsorption of casein micelles mainly, and whey proteins. The structural consequences depend on the sequence of the homogenization and heat treatments. Regarding human health, homogenized milk seems more digestible than untreated milk. Homogenization favors milk allergy and intolerance in animals but no difference appears between homogenized and untreated milk in allergic children and lactose-intolerant or milk-hypersensitive adults. Controversies appear regarding the atherogenic or beneficial bioactivity of some casein peptides and milk fat globule membrane proteins, which might be enhanced by homogenization. In children prone to type I diabetes, early cow's milk consumption would be a risk but no link was observed in the general population and the effect of homogenization has not been studied. In the current context of obesity and allergy outbreaks, the impact of homogenization and other technological processes on the health properties of milk remains to be clarified.

Modeling Surfactant Adsorption on Hydrophobic Surfaces

Surfactant adsorption on hydrophobic surfaces is of current interest in attempts to solubilize single-wall carbon nanotubes and to render quantum dots biocompatible. A coarse grained method is presented for incorporating a hydrophobic surface into existing liquid force fields by appealing to statistical mechanics and probability theory. The dimensionality problem which arises is overcome with an approximate treatment and the entire procedure is applied to aqueous n-alkyl poly(ethylene oxide) adsorbing onto a graphite surface. The simulations are in excellent agreement with atomic force microscopy data. The mechanism of micelle adsorption onto a partially coated surface is reported for the first time and has implications for the construction of nanotemplates.

Unusual Micelle and Surface Adsorption Behavior in Mixtures of Surfactants with an Ethylene Oxide−Propylene Oxide Triblock Copolymer

Micellization and adsorption at the air-solution interface of binary mixtures of the triblock copolymer of ethylene oxide and propylene oxide, EO23PO52EO23 (EPE), and the surfactants sodium dodecyl sulfate (SDS), dodecyl trimethylammonium chloride (DTAC), and tetraethylene glycol monooctyl ether (C8EO4) have been studied by neutron reflectivity and surface tension. The synergistic attractive interaction between the polymer and the ionic surfactants has been analyzed in the framework of the pseudo phase approximation and gives rise to a stronger interaction for EPE/SDS than EPE/DTAC. In contrast, the interaction of the nonionic surfactant C8EO4 with the copolymer EPE shows an unexpected and rather different behavior, resulting in a strongly repulsive interaction, characterized by a positive interaction parameter. The neutron reflectivity measurements of the surface excess, where the predicted and measured surface excesses are directly compared, provide evidence that challenges the applicability of the pseudo phase approximation for describing the surface mixing behavior. Structural information on the mixed adsorbed layer provides evidence which in part explains the observed discrepancies between the measured surface excesses and the behavior predicted from the pseudo phase approximation. Furthermore the structural evidence can be use to rationalize the differences in behavior observed between the ionic and nonionic surfactants.

Mixed Micelle Formation and Adsorption of Anionic/Nonionic Surfactant Mixture on Barite for Drilling Fluids

Adsorption of surfactants on barite from aqueous solution is of interest for flotation and purification processes. A study of the adsorption of the anionic/nonionic surfactant mixture C10 H21N2 Φ SO3(ANO)/C9 Φ E − 12 (ETH) on barite showed that the adsorption isotherm of the nonionic C9 Φ E − 12 (ETH) was altered by the anionic, C10 H21 N2 Φ SO3(ANO). Although the adsorption of the anionic was affected by the nonionic surfactant and enhanced its isotherm. The reason for this is associated with change in the micelle composition. Variations of the surface tension of the anionic/nonionic mixed surfactant systems against mole fractionchanges were studied. Physical parameters, particularly maximum adsorption density Γ max , area occupied per molecules, activity coefficients, and free energy of micelle were also investigated. The adsorption isotherm was analyzed, these parameters confirm that the synergistic action of mixed micelle as collector for barite depends on its mole fraction. The optimum recovery of barite was obtained with 0.8 mol fraction. The results were discussed according to the obtained physical properties of the system at solution/air and barite/liquid interfaces.