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P M Claesson

Publications and source records attributed to P M Claesson.

6 recordsLinked to original sources

Surface rheology of PEO-PPO-PEO triblock copolymers at the air-water interface: comparison of spread and adsorbed layers.

The dilatational rheological properties of monolayers of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide)-type block copolymers at the air-water interface have been investigated by employing an oscillating ring trough method. The properties of adsorbed monolayers were compared to spread layers over a range of surface concentrations. The studied polymers were PEO26-PPO39-PEO26 (P85), PEO103-PPO40-PEO103 (F88), and PEO99-PPO65-PEO99 (F127). Thus, two of the polymers have similar PPO block size and two of them have similar PEO block size, which allows us to draw conclusions about the relationship between molecular structure and surface dilatational rheology. The dilatational properties of adsorbed monolayers were investigated as a function of time and bulk solution concentration. The time dependence was found to be rather complex, reflecting structural changes in the layer. When the dilatational modulus measured at different concentrations was replotted as a function of surface pressure, one unique master curve was obtained for each polymer. It was found that the dilatational behavior of spread (Langmuir) and adsorbed (Gibbs) monolayers of the same polymer is close to identical up to surface concentrations of approximately 0.7 mg/m2. At higher coverage, the properties are qualitatively alike with respect to dilatational modulus, although some differences are noticeable. Relaxation processes take place mainly within the interfacial layers by a redistribution of polymer segments. Several conformational transitions were shown to occur as the area per molecule decreased. PEO desorbs significantly from the interface at segmental areas below 20 A(2), while at higher surface coverage, we propose that segments of PPO are forced to leave the interface to form a mixed sublayer in the aqueous region.

Adsorption↗

Adsorption of poly(ethylene oxide)-b-poly(epsilon-caprolactone) copolymers at the silica-water interface.

The adsorption of amphiphilic poly(ethylene oxide)-b-poly(epsilon-caprolactone) and poly(ethylene oxide)-b-poly(gamma-methyl-epsilon-caprolactone) copolymers in aqueous solution on silica and glass surfaces has been investigated by flow microcalorimetry, small-angle neutron scattering (SANS), surface forces, and complementary techniques. The studied copolymers consist of a poly(ethylene oxide) (PEO) block of M(n) = 5000 and a hydrophobic polyester block of poly(epsilon-caprolactone) (PCL) or poly(gamma-methyl-epsilon-caprolactone) (PMCL) of M(n) in the 950-2200 range. Compared to homoPEO, the adsorption of the copolymers is significantly increased by the connection of PEO to an aliphatic polyester block. According to calorimetric experiments, the copolymers interact with the surface mainly through the hydrophilic block. At low surface coverage, the PEO block interacts with the surface such that both PEO and PCL chains are exposed to the aqueous solution. At high surface coverage, a dense copolymer layer is observed with the PEO blocks oriented toward the solution. The structure of the copolymer layer has been analyzed by neutron scattering using the contrast matching technique and by tapping mode atomic force microscopy. The experimental observations agree with the coadsorption of micelles and free copolymer chains at the interface.

Adsorption↗

The structures of complexes between polyethylene imine and sodium dodecyl sulfate in D2O: a scattering study.

The association between a highly branched polyelectrolyte with ionizable groups, polyethylene imine (PEI), and an anionic surfactant, sodium dodecyl sulfate (SDS), has been investigated at two pH values, using small-angle neutron and light scattering. The scattering data allow us to obtain a detailed picture of the association structures formed. Small-angle neutron scattering (SANS) measurements in solutions containing highly charged PEI at low pH and low SDS concentrations indicate the presence of disklike aggregates. The aggregates change to a more complex three-dimensional structure with increasing surfactant concentration. One pronounced feature in the scattering curves is the presence of a Bragg-like peak at high q-values observed at a surfactant concentration of 4.2 mM and above. This scattering feature is attributed to the formation of a common well-ordered PEI/SDS structure, in analogue to what has been reported for other polyelectrolyte-surfactant systems. Precipitation occurred at the charge neutralization point, and X-ray diffraction measurements on the precipitate confirmed the existence of an ordered structure within the PEI/SDS aggregates, which was identified as a lamellar internal organization. Polyethylene imine has a low charge density in alkaline solutions. At pH 10.1 and under conditions where the surfactant was contrast matched, the SANS scattering curves showed only small changes with increasing surfactant concentration. This suggests that the polymer acts as a template onto which the surfactant molecules aggregate. Data from both static light scattering and SANS recorded under conditions where SDS and to a lower degree PEI contribute to the scattering were found to be consistent with a structure of stacked elliptic bilayers. These structures increased in size and became more compact as the surfactant concentration was increased up to the charge neutralization point.

Deuterium Oxide↗

Disruption of viscoelastic beta-lactoglobulin surface layers at the air-water interface by nonionic polymeric surfactants.

Nonequilibrium interfacial layers formed by competitive adsorption of beta-lactoglobulin and the nonionic triblock copolymer PEO99-PPO65-PEO99 (F127) to the air-water interface were investigated in order to explain the influence of polymeric surfactants on protein film surface rheology and foam stability. Surface dilatational and shear rheological methods, surface tension measurements, dynamic thin-film measurements, diffusion measurements (from fluorescence recovery after photo bleaching), and determinations of foam stability were used as methods. The high surface viscoelasticity, both the shear and dilatational, of the protein films was significantly reduced by coadsorption of polymeric surfactant. The drainage rate of single thin films, in the presence of beta-lactoglobulin, increased with the amount of added F127, but equilibrium F127 films were found to be thicker than beta-lactoglobulin films, even at low concentration of the polymeric surfactant. It is concluded that the effect of the nonionic triblock copolymer on the interfacial rheology of beta-lactoglobulin layers is similar to that of low molecular weight surfactants. They differ however in that F127 increases the thickness of thin liquid films. In addition, the significant destabilizing effect of low molecular weight surfactants on protein foams is not found in the investigated system. This is explained as due to long-range steric forces starting to stabilize the foam films at low concentrations of F127.

Adsorption↗

Adsorption of liposomes and emulsions studied with a quartz crystal microbalance.

The adsorption from phospholipid liposome solutions (1.2%) and phospholipid stabilized oil-in-water emulsions (20% purified soybean oil) with the same phospholipid liposome concentration, has been followed by means of a quartz crystal microbalance allowing the simultaneous determination of changes in resonance frequency and energy dissipation. Both the fundamental resonance frequency and the third overtone were used for following the interfacial processes. The adsorption from the liposome solution resulted in formation of a phospholipid bilayer with an additional and incomplete outer layer of liposomes. The outer layer was removed by dilution leaving a bilayer of phospholipids on the surface. The adsorption process observed from the concentrated emulsion solution was considerably more complex. A slow spreading process that also resulted in some expulsion of material from the interface followed the rapid initial adsorption of emulsion droplets. After rinsing with water a phospholipid bilayer was retained on the surface.

Journal Article↗

Surfaces coated with protein layers: a surface force and ESCA study.

In this review article we discuss the types of non-specific forces that are of importance for the interactions between proteins and surfaces. Some of these forces are well understood theoretically, and their properties investigated in detail. The origin of other types of forces is less well understood, or even controversial, and here we will recapitulate the main experimental findings. Most of our knowledge of interfacial forces stems from the use of various surface force techniques. Two such techniques are described in this article. The typical experimental procedure is outlined and attention is drawn to the most common complications that we have met during our studies. In this article we have chosen to present data that illustrate the presence of some particular type of force, that illustrate a particular complication that occurs when evaluating the experimental findings, or that illustrate the advantage of using electron spectroscopy for chemical analysis (ESCA) in combination with surface force measurements. No system is discussed in detail, and for more detailed information we will refer the reader to the original literature. However, we present an estimate of the amount of small ions co-adsorbed with the protein calculated from a combination of the ESCA and surface force apparatus (SFA) results. This estimate is based on a simple charge balance which requires a knowledge of the adsorbed amount and the diffuse layer charge. The adsorbed amount is obtained from ESCA measurements using a quantification method that utilizes the known chemical composition of the mica surface. The diffuse layer charge is obtained from the magnitude of the double-layer force measured with a surface force technique.

Adsorption↗