Regine Von Klitzing - Academia.edu (original) (raw)

Papers by Regine Von Klitzing

Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2007

In this review we present selected recent developments of responsive multilayers formed by layer-... more In this review we present selected recent developments of responsive multilayers formed by layer-by-layer assembly of oppositely charged polymers, with particular emphasis on the preparation of temperature-and pH-sensitive systems. We discuss the influence of the architecture and of the nature of the polyelectrolytes used on the responsive behavior of the films. Different strategies based on polyelectrolyte shells or films incorporating stimuli-responsive polyelectrolytes are reviewed as well as the entrapment of stimuli-responsive polymer into hollow capsules.

Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2007

In this review we summarize novel aspects of the hydration and internal properties of polyelectro... more In this review we summarize novel aspects of the hydration and internal properties of polyelectrolyte multilayers formed by layer-by-layer assembly. Reflectivity techniques monitor the water content and swelling behavior, while spin relaxation monitors water mobility. Odd-even effects in dependence on the number of layers are discussed in terms of an influence of the terminating layer. Other novel methodological approaches like X-ray microscopy or NMR cryoporometry address the water content in hollow capsules, and the water pore size distribution, respectively. Multilayer material properties are relevant for different applications. As a novel concept, dielectric properties are monitored in a field effect transistor device. Ion mobility and redox processes in multilayers are revealed by the electrochemical properties. Mechanical properties of multilayers, studied by colloidal probe atomic force microscopy depend on the conformation of the polymers involved.

We investigated the potential profile between colloidal probes floating above a polyelectrolyte m... more We investigated the potential profile between colloidal probes floating above a polyelectrolyte multilayer (PEM), built up by the layer by layer technique with Total Internal Reflection Microscopy (TIRM) .

Langmuir, Apr 1, 2007

The formation of polyelectrolyte multilayers (PEMs) is investigated using a silicon-on-insulator ... more The formation of polyelectrolyte multilayers (PEMs) is investigated using a silicon-on-insulator based thin film resistor which is sensitive to variations of the surface potential. The buildup of the PEMs at the silicon oxide surface of the device can be observed in real time as defined potential shifts. The influence of polymer charge density is studied using the strong polyanion poly(styrene sulfonate), PSS, combined with the statistical copolymer poly(diallyl-dimethylammoniumchloride-stat-N-methyl-N-vinylacetamide), P(DADMAC-stat-NMVA), at various degrees of charge (DC). The multilayer formation stops after a few deposition steps for a DC below 75%. We show that the threshold of surface charge compensation corresponds to the threshold of multilayer formation. However, no reversion of the preceding surface charge was observed. Screening of polyelectrolyte charges by mobile ions within the polymer film leads to a decrease of the potential shifts with the number of layers deposited. This decrease is much slower for PEMs consisting of P(DADMAC-stat-NMVA) and PSS as compared to PEMs consisting of poly(allylamine-hydrochloride), PAH, and PSS. From this, significant differences in the dielectric constants of the polyelectrolyte films and in the concentration of mobile ions within the films can be derived.

Langmuir, Jun 12, 2014

Microgel particles of cross-linked poly(NIPAMco-acrylic acid) with different acrylic acid content... more Microgel particles of cross-linked poly(NIPAMco-acrylic acid) with different acrylic acid contents are investigated in solution and in the adsorbed state. As a substrate, silicon with a poly(allylamine hydrochloride) (PAH) coating is used. The temperature dependence of the deswelling of the microgel particles was probed with atomic force microscopy (AFM). The inner structure of the adsorbed microgel particles was detected with grazing incidence small angle neutron scattering (GISANS). Small angle neutron scattering (SANS) on corresponding microgel suspensions was performed for comparison. Whereas the correlation length of the polymer network shows a divergence in the bulk samples, in the adsorbed microgel particles it remains unchanged over the entire temperature range. In addition, GISANS indicates changes in the particles along the surface normal. This suggests that the presence of a solid surface suppresses the divergence of internal fluctuations in the adsorbed microgels close to the volume phase transition.

Http Dx Doi Org 10 1080 1539445x 2014 945039, Nov 18, 2014

ABSTRACT When two surfaces slide past each other, energy is mainly dissipated by stick-slip event... more ABSTRACT When two surfaces slide past each other, energy is mainly dissipated by stick-slip events. Macroscopic stick-slip is usually explained by asperities that come in and out of contact. Here we probe stick-slip at the nanoscale at interfaces and polymer coated interfaces by pulling single polymers covalently attached to an AFM cantilever tip laterally over solid substrates in liquid environment. We find two different stick mechanisms, namely desorption stick (DS) and cooperative stick (CS). While DS-slip resembles the velocity dependence of macroscopic stick-slip, CS-slip shows an increase in friction with velocity. For various reasons we anticipate that both stick mechanisms are necessary for a molecular understanding of stick-slip at the interface and interphase.

Tenside Surfactants Detergents, 2000

Advan Colloid Interface Sci, 2010

Addition of surfactants to aqueous solutions of polyelectrolytes carrying an opposite charge caus... more Addition of surfactants to aqueous solutions of polyelectrolytes carrying an opposite charge causes the spontaneous formation of complexes in the bulk phase in certain concentration ranges. Under some conditions, compact monodisperse multichain complexes are obtained in the bulk. The size of these complexes depends on the mixing procedure and it can be varied in a controlled way from nanometers up to micrometers. The complexes exhibit microstructures analoguous to those of the precipitates formed at higher concentrations. In other cases, however, the bulk complexes are large, soft and polydisperse. In most cases, the dispersions are only kinetically stable and exhibit pronounced non-equilibrium features.Association at air-water interfaces readily occurs, even at very small concentrations. When the surfactant concentration is small, the surface complexes are usually made of a surfactant monolayer to which the polymer binds and adsorbs in a flat-like configuration. However, under some conditions, thicker layers can be found, with bulk complexes sticking to the surface. The association at solid-water interfaces is more complex and depends on the specific interactions between surfactants, polymers and the surface. However, the behaviour can be understood if distinctions between hydrophilic surfaces and hydrophobic surfaces are made. Note that the behaviour at air-water interfaces is closer to that of hydrophobic than that of hydrophilic solid surfaces.The relation between bulk and surface complexation will be discussed in this review. The emphasis will be given to the results obtained by the teams of the EC-funded Marie Curie RTN “SOCON”.

Journal of Physics Condensed Matter, Jun 26, 2003

ABSTRACT

Journal of colloid and interface science, 2016

In the present contribution, we evaluate the efficiency of eco-friendly microemulsions to deconta... more In the present contribution, we evaluate the efficiency of eco-friendly microemulsions to decontaminate solid surfaces by monitoring the extraction of non-toxic simulants of sulfur mustard out of model surfaces. The extraction process of the non-toxic simulants has been monitored by means of spectroscopic and chromatographic techniques. The kinetics of the removal process was analyzed by different empirical models. Based on the analysis of the kinetics, we can assess the influence of the amounts of oil and water and the microemulsion structure on the extraction process.

Langmuir : the ACS journal of surfaces and colloids, Jan 23, 2016

Biomimetic multilayers based on Layer-by-Layer (LbL) assembly were prepared as functional films w... more Biomimetic multilayers based on Layer-by-Layer (LbL) assembly were prepared as functional films with compact structure by incorporating the mussel-inspired catechol crosslinking. Dopamine modified poly(acrylic acid) (PAADopa) was synthesized as a polyanion to offer electrostatic interaction with the pre-layer polyethyleneimine (PEI) and consecutively crosslinked by zinc to generate compact multilayers with tunable physicochemical properties. In-situ layer-by-layer growth and crosslinking were monitored by Quartz Crystal Microbalance with Dissipation (QCM-D) to reveal the kinetics of the process and the influence of Dopa chemistry. Addition of Dopa enhanced the mass adsorption and led to the formation of a more compact structure. An increase of ionic strength induced an increase in mass adsorption in the Dopa-crosslinked multilayers. This is a universal approach for coating of various surfaces such as Au, SiO2, Ti and Al2O3. Roughness observed by AFM in both wet and dry conditions wa...

Multilayer Thin Films, 2000

Langmuir, Aug 3, 2010

We present a simple and versatile approach of using hydrogel microparticles to transfer both inor... more We present a simple and versatile approach of using hydrogel microparticles to transfer both inorganic hydrophilic nanoparticles (NPs) such as CdTe quantum dots and enzymes such as lipase B from Candida antarctica (CalB) to organic media and eventually encapsulate them in the gel microparticles by consecutive exchange of the water swollen in the hydrogel microparticles with water-miscible organic solvents and water-immiscible solvents. The entrapment of hydrophilic nanoparticles is due to their incompatibility with water-immiscible organic solvents soaked in the gel matrices and in the surrounding environment, so the present approach obviates the need for any chemical modification to the NP surface or to the hydrogel and furthermore does not require any size matching or chemical affinity of the NPs for the hydrogel networks. The solvent exchange process causes little change of the intrinsic properties of hydrophilic nanoparticles; CdTe quantum dots encapsulated in hydrogel microparticles, dispersed in water-immiscible organic solvents, remain strongly fluorescent, and CalB retains high catalytic activity. Of importance is that the hydrophilic nanoparticles encapsulated in the gel microparticles in organic media can be completely recovered in aqueous media via reversed solvent exchange. As a consequence, the present approach should hold immense promise for technical applications, especially in catalysis.

Langmuir, Sep 1, 2009

Self-assembled multilayers of a strong polyanion, poly(sodium 4-styrenesulfonate) (PSS), and a st... more Self-assembled multilayers of a strong polyanion, poly(sodium 4-styrenesulfonate) (PSS), and a strong polycation, poly[(diallyl-dimethyl-ammonium chloride)-stat-(N-methyl-N-vinyl acetamide)] (P(DADMAC-stat-NMVA)), are fabricated on silicon substrates. This article addresses the effect of electrostatics versus ion specificity. Therefore, multilayer formation and growth are investigated as a function of the charge density of the polycation, the type of salt in the polyelectrolyte dipping solution, and its ionic strength. This study focuses on monovalent ions (Li + , Na + , K + , Cs + , Rb + , F -, Cl -, Br -, and ClO 3 -). Ellipsometry and X-ray reflectometry data indicate that anions have a significantly larger effect on the thickness of the multilayer, but contrary to other studies on ion-specific effects, the influence of the type of cation is not negligible at higher salt concentrations. Larger ions, with smaller hydration shells, are highly polarizable and consequently interact strongly with charged polyelectrolytes, resulting in thicker and rougher multilayers. AFM studies confirm a higher roughness of the multilayer prepared from larger anions. The substrate can mask ion-specific effects over a distance of about 10 nm. Ion-specific effects become important above an ionic strength of 0.1 M in the case of anions and above an ionic strength of 0.25 M for cations. At lower ionic strengths, electrostatic interactions between and within the polyelectrolyte chains are dominating. Reducing the degree of polymer charge down to 75% does not shift this threshold of ionic strength. It is shown that a combination of ionic strength, polymer charge, and type of ion is a suitable tool for tuning the mobility and stability of polyelectrolyte multilayers.

J Phys Condens Matter, 2003

The present review is a topical survey of the disjoining pressure in thin liquid foam and emulsio... more The present review is a topical survey of the disjoining pressure in thin liquid foam and emulsion films from both the experimental and the theoretical points of view. Section 2 deals with the latest research work on experimental techniques with which the disjoining pressure Pi in foam, emulsion, and pseudo-emulsion films can be measured. Although a lot of techniques are available, the question of the origin of the charges at the water/air and the water/oil interfaces of films, which are stabilized by non-ionic surfactants, has not yet been answered. We address this question in section 3, reviewing the latest relevant literature. The relevance of structural forces for the disjoining pressure is outlined in section 4, which focuses on films which are stabilized by surfactant/polyelectrolyte mixtures.

Phys. Chem. Chem. Phys., 2016

The binding effects of osmolytes on the conformational behavior of grafted polymers are studied i... more The binding effects of osmolytes on the conformational behavior of grafted polymers are studied in this work. In particular, we focus on the interactions between urea and poly(N-isopropylacrylamide) (PNIPAM) brushes by monitoring the ellipsometric brush thickness for varying urea concentrations over a broad temperature range. The interpretation of the obtained data is supported by atomistic molecular dynamics simulations, which provide detailed insights into the experimentally observed concentration-dependent effects on PNIPAM-urea interaction. In particular, in the low concentration regime (cu ≤ 0.5 mol L(-1)) a preferential exclusion of urea from PNIPAM chains is observed, while in the high concentration regime (2 ≤ cu ≤ 7 mol L(-1)) a preferential binding of the osmolyte to the polymer surface is found. In both regimes, the volume phase transition temperature (Ttr) decreases with increasing urea concentration. This phenomenon derives from two different effects depending on urea concentration: (i) for cu ≤ 0.5 mol L(-1), the decrease of Ttr is explained by a decrease of the chemical potential of bulk water in the surrounding aqueous phase; (ii) for cu ≥ 2 mol L(-1), the lower Ttr is explained by the favorable replacement of water molecules by urea, which can be regarded as a cross-linker between adjacent PNIPAM chains. Significant effects of the concentration-dependent urea binding on the brush conformation are noticed: at cu = 0.5 mol L(-1), although urea is loosely embedded between the hydrated polymer chains, it enhances the brush swelling by excluded volume effects. Beyond 0.5 mol L(-1), the stronger interaction between PNIPAM and urea reduces the chain hydration, which in combination with cross-linking of monomer units induces the shrinkage of the polymer brush.

Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2007

In this review we present selected recent developments of responsive multilayers formed by layer-... more In this review we present selected recent developments of responsive multilayers formed by layer-by-layer assembly of oppositely charged polymers, with particular emphasis on the preparation of temperature-and pH-sensitive systems. We discuss the influence of the architecture and of the nature of the polyelectrolytes used on the responsive behavior of the films. Different strategies based on polyelectrolyte shells or films incorporating stimuli-responsive polyelectrolytes are reviewed as well as the entrapment of stimuli-responsive polymer into hollow capsules.

Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2007

In this review we summarize novel aspects of the hydration and internal properties of polyelectro... more In this review we summarize novel aspects of the hydration and internal properties of polyelectrolyte multilayers formed by layer-by-layer assembly. Reflectivity techniques monitor the water content and swelling behavior, while spin relaxation monitors water mobility. Odd-even effects in dependence on the number of layers are discussed in terms of an influence of the terminating layer. Other novel methodological approaches like X-ray microscopy or NMR cryoporometry address the water content in hollow capsules, and the water pore size distribution, respectively. Multilayer material properties are relevant for different applications. As a novel concept, dielectric properties are monitored in a field effect transistor device. Ion mobility and redox processes in multilayers are revealed by the electrochemical properties. Mechanical properties of multilayers, studied by colloidal probe atomic force microscopy depend on the conformation of the polymers involved.

We investigated the potential profile between colloidal probes floating above a polyelectrolyte m... more We investigated the potential profile between colloidal probes floating above a polyelectrolyte multilayer (PEM), built up by the layer by layer technique with Total Internal Reflection Microscopy (TIRM) .

Langmuir, Apr 1, 2007

The formation of polyelectrolyte multilayers (PEMs) is investigated using a silicon-on-insulator ... more The formation of polyelectrolyte multilayers (PEMs) is investigated using a silicon-on-insulator based thin film resistor which is sensitive to variations of the surface potential. The buildup of the PEMs at the silicon oxide surface of the device can be observed in real time as defined potential shifts. The influence of polymer charge density is studied using the strong polyanion poly(styrene sulfonate), PSS, combined with the statistical copolymer poly(diallyl-dimethylammoniumchloride-stat-N-methyl-N-vinylacetamide), P(DADMAC-stat-NMVA), at various degrees of charge (DC). The multilayer formation stops after a few deposition steps for a DC below 75%. We show that the threshold of surface charge compensation corresponds to the threshold of multilayer formation. However, no reversion of the preceding surface charge was observed. Screening of polyelectrolyte charges by mobile ions within the polymer film leads to a decrease of the potential shifts with the number of layers deposited. This decrease is much slower for PEMs consisting of P(DADMAC-stat-NMVA) and PSS as compared to PEMs consisting of poly(allylamine-hydrochloride), PAH, and PSS. From this, significant differences in the dielectric constants of the polyelectrolyte films and in the concentration of mobile ions within the films can be derived.

Langmuir, Jun 12, 2014

Microgel particles of cross-linked poly(NIPAMco-acrylic acid) with different acrylic acid content... more Microgel particles of cross-linked poly(NIPAMco-acrylic acid) with different acrylic acid contents are investigated in solution and in the adsorbed state. As a substrate, silicon with a poly(allylamine hydrochloride) (PAH) coating is used. The temperature dependence of the deswelling of the microgel particles was probed with atomic force microscopy (AFM). The inner structure of the adsorbed microgel particles was detected with grazing incidence small angle neutron scattering (GISANS). Small angle neutron scattering (SANS) on corresponding microgel suspensions was performed for comparison. Whereas the correlation length of the polymer network shows a divergence in the bulk samples, in the adsorbed microgel particles it remains unchanged over the entire temperature range. In addition, GISANS indicates changes in the particles along the surface normal. This suggests that the presence of a solid surface suppresses the divergence of internal fluctuations in the adsorbed microgels close to the volume phase transition.

Http Dx Doi Org 10 1080 1539445x 2014 945039, Nov 18, 2014

ABSTRACT When two surfaces slide past each other, energy is mainly dissipated by stick-slip event... more ABSTRACT When two surfaces slide past each other, energy is mainly dissipated by stick-slip events. Macroscopic stick-slip is usually explained by asperities that come in and out of contact. Here we probe stick-slip at the nanoscale at interfaces and polymer coated interfaces by pulling single polymers covalently attached to an AFM cantilever tip laterally over solid substrates in liquid environment. We find two different stick mechanisms, namely desorption stick (DS) and cooperative stick (CS). While DS-slip resembles the velocity dependence of macroscopic stick-slip, CS-slip shows an increase in friction with velocity. For various reasons we anticipate that both stick mechanisms are necessary for a molecular understanding of stick-slip at the interface and interphase.

Tenside Surfactants Detergents, 2000

Advan Colloid Interface Sci, 2010

Addition of surfactants to aqueous solutions of polyelectrolytes carrying an opposite charge caus... more Addition of surfactants to aqueous solutions of polyelectrolytes carrying an opposite charge causes the spontaneous formation of complexes in the bulk phase in certain concentration ranges. Under some conditions, compact monodisperse multichain complexes are obtained in the bulk. The size of these complexes depends on the mixing procedure and it can be varied in a controlled way from nanometers up to micrometers. The complexes exhibit microstructures analoguous to those of the precipitates formed at higher concentrations. In other cases, however, the bulk complexes are large, soft and polydisperse. In most cases, the dispersions are only kinetically stable and exhibit pronounced non-equilibrium features.Association at air-water interfaces readily occurs, even at very small concentrations. When the surfactant concentration is small, the surface complexes are usually made of a surfactant monolayer to which the polymer binds and adsorbs in a flat-like configuration. However, under some conditions, thicker layers can be found, with bulk complexes sticking to the surface. The association at solid-water interfaces is more complex and depends on the specific interactions between surfactants, polymers and the surface. However, the behaviour can be understood if distinctions between hydrophilic surfaces and hydrophobic surfaces are made. Note that the behaviour at air-water interfaces is closer to that of hydrophobic than that of hydrophilic solid surfaces.The relation between bulk and surface complexation will be discussed in this review. The emphasis will be given to the results obtained by the teams of the EC-funded Marie Curie RTN “SOCON”.

Journal of Physics Condensed Matter, Jun 26, 2003

ABSTRACT

Journal of colloid and interface science, 2016

In the present contribution, we evaluate the efficiency of eco-friendly microemulsions to deconta... more In the present contribution, we evaluate the efficiency of eco-friendly microemulsions to decontaminate solid surfaces by monitoring the extraction of non-toxic simulants of sulfur mustard out of model surfaces. The extraction process of the non-toxic simulants has been monitored by means of spectroscopic and chromatographic techniques. The kinetics of the removal process was analyzed by different empirical models. Based on the analysis of the kinetics, we can assess the influence of the amounts of oil and water and the microemulsion structure on the extraction process.

Langmuir : the ACS journal of surfaces and colloids, Jan 23, 2016

Biomimetic multilayers based on Layer-by-Layer (LbL) assembly were prepared as functional films w... more Biomimetic multilayers based on Layer-by-Layer (LbL) assembly were prepared as functional films with compact structure by incorporating the mussel-inspired catechol crosslinking. Dopamine modified poly(acrylic acid) (PAADopa) was synthesized as a polyanion to offer electrostatic interaction with the pre-layer polyethyleneimine (PEI) and consecutively crosslinked by zinc to generate compact multilayers with tunable physicochemical properties. In-situ layer-by-layer growth and crosslinking were monitored by Quartz Crystal Microbalance with Dissipation (QCM-D) to reveal the kinetics of the process and the influence of Dopa chemistry. Addition of Dopa enhanced the mass adsorption and led to the formation of a more compact structure. An increase of ionic strength induced an increase in mass adsorption in the Dopa-crosslinked multilayers. This is a universal approach for coating of various surfaces such as Au, SiO2, Ti and Al2O3. Roughness observed by AFM in both wet and dry conditions wa...

Multilayer Thin Films, 2000

Langmuir, Aug 3, 2010

We present a simple and versatile approach of using hydrogel microparticles to transfer both inor... more We present a simple and versatile approach of using hydrogel microparticles to transfer both inorganic hydrophilic nanoparticles (NPs) such as CdTe quantum dots and enzymes such as lipase B from Candida antarctica (CalB) to organic media and eventually encapsulate them in the gel microparticles by consecutive exchange of the water swollen in the hydrogel microparticles with water-miscible organic solvents and water-immiscible solvents. The entrapment of hydrophilic nanoparticles is due to their incompatibility with water-immiscible organic solvents soaked in the gel matrices and in the surrounding environment, so the present approach obviates the need for any chemical modification to the NP surface or to the hydrogel and furthermore does not require any size matching or chemical affinity of the NPs for the hydrogel networks. The solvent exchange process causes little change of the intrinsic properties of hydrophilic nanoparticles; CdTe quantum dots encapsulated in hydrogel microparticles, dispersed in water-immiscible organic solvents, remain strongly fluorescent, and CalB retains high catalytic activity. Of importance is that the hydrophilic nanoparticles encapsulated in the gel microparticles in organic media can be completely recovered in aqueous media via reversed solvent exchange. As a consequence, the present approach should hold immense promise for technical applications, especially in catalysis.

Langmuir, Sep 1, 2009

Self-assembled multilayers of a strong polyanion, poly(sodium 4-styrenesulfonate) (PSS), and a st... more Self-assembled multilayers of a strong polyanion, poly(sodium 4-styrenesulfonate) (PSS), and a strong polycation, poly[(diallyl-dimethyl-ammonium chloride)-stat-(N-methyl-N-vinyl acetamide)] (P(DADMAC-stat-NMVA)), are fabricated on silicon substrates. This article addresses the effect of electrostatics versus ion specificity. Therefore, multilayer formation and growth are investigated as a function of the charge density of the polycation, the type of salt in the polyelectrolyte dipping solution, and its ionic strength. This study focuses on monovalent ions (Li + , Na + , K + , Cs + , Rb + , F -, Cl -, Br -, and ClO 3 -). Ellipsometry and X-ray reflectometry data indicate that anions have a significantly larger effect on the thickness of the multilayer, but contrary to other studies on ion-specific effects, the influence of the type of cation is not negligible at higher salt concentrations. Larger ions, with smaller hydration shells, are highly polarizable and consequently interact strongly with charged polyelectrolytes, resulting in thicker and rougher multilayers. AFM studies confirm a higher roughness of the multilayer prepared from larger anions. The substrate can mask ion-specific effects over a distance of about 10 nm. Ion-specific effects become important above an ionic strength of 0.1 M in the case of anions and above an ionic strength of 0.25 M for cations. At lower ionic strengths, electrostatic interactions between and within the polyelectrolyte chains are dominating. Reducing the degree of polymer charge down to 75% does not shift this threshold of ionic strength. It is shown that a combination of ionic strength, polymer charge, and type of ion is a suitable tool for tuning the mobility and stability of polyelectrolyte multilayers.

J Phys Condens Matter, 2003

The present review is a topical survey of the disjoining pressure in thin liquid foam and emulsio... more The present review is a topical survey of the disjoining pressure in thin liquid foam and emulsion films from both the experimental and the theoretical points of view. Section 2 deals with the latest research work on experimental techniques with which the disjoining pressure Pi in foam, emulsion, and pseudo-emulsion films can be measured. Although a lot of techniques are available, the question of the origin of the charges at the water/air and the water/oil interfaces of films, which are stabilized by non-ionic surfactants, has not yet been answered. We address this question in section 3, reviewing the latest relevant literature. The relevance of structural forces for the disjoining pressure is outlined in section 4, which focuses on films which are stabilized by surfactant/polyelectrolyte mixtures.

Phys. Chem. Chem. Phys., 2016

The binding effects of osmolytes on the conformational behavior of grafted polymers are studied i... more The binding effects of osmolytes on the conformational behavior of grafted polymers are studied in this work. In particular, we focus on the interactions between urea and poly(N-isopropylacrylamide) (PNIPAM) brushes by monitoring the ellipsometric brush thickness for varying urea concentrations over a broad temperature range. The interpretation of the obtained data is supported by atomistic molecular dynamics simulations, which provide detailed insights into the experimentally observed concentration-dependent effects on PNIPAM-urea interaction. In particular, in the low concentration regime (cu ≤ 0.5 mol L(-1)) a preferential exclusion of urea from PNIPAM chains is observed, while in the high concentration regime (2 ≤ cu ≤ 7 mol L(-1)) a preferential binding of the osmolyte to the polymer surface is found. In both regimes, the volume phase transition temperature (Ttr) decreases with increasing urea concentration. This phenomenon derives from two different effects depending on urea concentration: (i) for cu ≤ 0.5 mol L(-1), the decrease of Ttr is explained by a decrease of the chemical potential of bulk water in the surrounding aqueous phase; (ii) for cu ≥ 2 mol L(-1), the lower Ttr is explained by the favorable replacement of water molecules by urea, which can be regarded as a cross-linker between adjacent PNIPAM chains. Significant effects of the concentration-dependent urea binding on the brush conformation are noticed: at cu = 0.5 mol L(-1), although urea is loosely embedded between the hydrated polymer chains, it enhances the brush swelling by excluded volume effects. Beyond 0.5 mol L(-1), the stronger interaction between PNIPAM and urea reduces the chain hydration, which in combination with cross-linking of monomer units induces the shrinkage of the polymer brush.