Structure of some polymer-detergent aggregates in water

Cabane, Bernard

doi:10.1021/j100532a008

Cited by 484 publications

(449 citation statements)

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“…The behaviour of such necklaces in a dilute bulk phase has been extensively studied experimentally [20][21][22] and theoretically [24][25][26][27]. However, the interaction between densely grafted polymers and surfactants at a concentration above the CAC has not been considered.…”

Section: Introductionmentioning

confidence: 99%

Stuffed brushes: theory and experiment

Currie¹,

Gucht²,

Borisov³

et al. 1999

Pure and Applied Chemistry

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Abstract:The interaction between polymer brushes and mesoscopic particles is investigated both theoretically and experimentally. We present an analytical mean-field theory for a polymer brush (a layer of long polymer chains end-grafted to a substrate) with varying excluded volume interactions between monomer units. This system mimics the reversible adsorption of mesoscopic particles, such as surfactant micelles or proteins, on the grafted chains. The equilibrium structural properties of the brush (the brush thickness and overall degree of complexation) as well as the number of adsorbed particles per unit area, ⌫, are analysed as functions of the affinity between particle and chain, grafting density and excluded volume interactions. In our model ⌫ is found to have a maximum as a function of . Experimentally the adsorption of BSA on a hydrophobic substrate with grafted PEO chains is measured with reflectometry. In the case of short grafted chains the adsorbed amount of BSA, ⌫, decreases continuously with increasing , which agrees with previous results and model calculations in the literature. In the case of long PEO chains, however, ⌫ is found to have a maximum as a function of . Qualitatively the experimental dependence of ⌫ on is found to agree with the results of our mean-field model. PEO chains show no affinity for BSA in the bulk, whereas in a grafted conformation an effective attraction is found. Some comments are made on the nature of this affinity, which is not yet fully understood.

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Section: Introductionmentioning

confidence: 99%

Stuffed brushes: theory and experiment

Currie¹,

Gucht²,

Borisov³

et al. 1999

Pure and Applied Chemistry

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“…Many experimental approaches have been used to study polymer -surfactant interactions such as turbidimetry [21,23], light scattering [26 -30], small-angle neutron scattering [35], electrophoretic light scattering [36,37], NMR [38], dialysis [26,39,40], surface tension [41 -44], viscometry [28,41], calorimetry [45], dye-solubilization [46,47], and solvatochromic studies [48], but relatively few techniques can be utilized to identify the phase transition and to clarify the dynamics of polyelectrolyte -micelle association. Static [28,30,49] and quasielastic [25,[27][28][29]49] light scattering especially have provided important information on the size and structure of polymermicelle complexes but soluble complexes can only be detected by QELS if their lifetime (residence time) is sufficiently long and the scattering intensity of the complexes is sufficiently large compared with those of the micelles and polymers from which they form.…”

Section: Introductionmentioning

confidence: 99%

Interactions of micelles with fluorescence-labeled polyelectrolytes

Morishima

Mizusaki

Yoshida

et al. 1999

Colloids and Surfaces A: Physicochemical and Engineering Aspect

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Pyrene-labeled polyelectrolytes can be used to study the interaction between the polyelectrolyte and an oppositely charged micelle, if the micelle incorporates a fluorescence quencher. If the charge on the micelle is varied systematically, polymer-micelle complex formation can be observed at some well-defined micelle surface charge density. Applying a kinetic model to steady-state and time-dependent fluorescence quenching data, one can estimate the binding constant (K), association rate constant, and lifetime (residence time). K increases strongly with increase in micelle surface charge density (|) or decrease in ionic strength (v). These effects arise from the dependence of association rate constant and residence time on | and v. While these observations reflect the fundamental electrostatic nature of the interaction, it is also found that micelles preferentially bind to pyrene sites, so that complex formation results from the conjoint action of electrostatic and hydrophobic forces.

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“…The spectroscopy of the surfactant molecules (NMR [8][9][10], Raman [11,12] [19,24,25], a sample was synthesized which was selectively deuterated on the 3d carbon after the head group [26]. The intensity and shape of the deuterated carbon's line are drastically modified; thus that line was easily assigned; then the lines of the 4" and Sth carbons were assigned through their isotopic shifts.…”

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confidence: 99%

“…The intensity and shape of the deuterated carbon's line are drastically modified; thus that line was easily assigned; then the lines of the 4" and Sth carbons were assigned through their isotopic shifts. The other lines were assigned through their positions and relaxation times [24]. The Figure 3 shows the raw data, fi.e.…”

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confidence: 99%

Structure of the water/surfactant interface in micelles : an NMR study of SDS micelles labelled with paramagnetic ions

Cabane

1981

J. Phys. France

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Résumé. 2014 On présente une méthode nouvelle pour déterminer la structure de l'interface eau/surfactant et la configuration des molécules dans les micelles de surfactant. Cette méthode consiste à observer par RMN les interactions dipolaires entre les noyaux des molécules de surfactant et des contreions paramagnétiques adsorbés sur la surface de ces micelles. L'experience compare les vitesses de relaxation de noyaux appartenant à différents groupes chimiques dans les molécules de surfactant; dans certains cas simples ces vitesses de relaxation dépendent seulement des distances entre les noyaux et les ions. Ainsi les vitesses de relaxation mesurées peuvent être reliées aux populations des noyaux dans des couches situées à diverses profondeurs de la surface. Les résultats mènent à la discuscussion suivante pour la structure de ces couches successives : (i) couches de surface contenant les charges hydratées (sont-elles lisses ou rugueuses ?); (ii) couches de contact eau/hydrocarbone (jusqu'à quelle profondeur l'eau pénètre-t-elle dans la micelle ?); (iii) couches du coeur hydrocarboné (quel est le degré d'organisation des chaines du surfactant ?).Abstract. 2014 A method has been developed for determining the structure of the water/surfactant interface and the configuration of the surfactant molecules in micelles. In this method, NMR is used to measure the magnetic dipolar interactions between the nuclei of the surfactant molecules and paramagnetic counterions adsorbed on the surface of the micelles. The experiment compares the relaxation rates of nuclei belonging to different chemical groups in the surfactant molecules; in some simple cases these relaxation rates only depend on the distances between the nuclei and the ions. Then the measured relaxation rates can be related to the populations of the nuclei in layers located at various depths from the paramagnetic surface. According to the data, the structure of these successive layers in a spherical micelle can be discussed in the following terms : (i) outermost layers containing the hydrated charges (how smooth or regular are they ?) ; (ii) layers of water/hydrocarbon contact (how deep does water penetrate in the micelle ?) ; (iii) layers of the hydrocarbon core (how disorganized is the packing of the surfactant chains ?).J. Physique 42 (1981)

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Structure of some polymer-detergent aggregates in water

Cited by 484 publications

References 13 publications

Stuffed brushes: theory and experiment

Stuffed brushes: theory and experiment

Interactions of micelles with fluorescence-labeled polyelectrolytes

Structure of the water/surfactant interface in micelles : an NMR study of SDS micelles labelled with paramagnetic ions

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