High-performance greases typically consist of a base oil and polyurea as a thickener material. To date, few alternatives to polyureas have been investigated. Polyesters could be one such alternative; however, little is known about the gelation of such polyesters because, unlike polyureas, they cannot form hydrogen bonds between the polymer chains. Here, we present studies on the gel formation of a polyester based thickener poly(hexane dodecanoate) with 1-octanol endgroups in three different base oils, i.e., a mineral oil (Brightstock 150), a synthetic Polyalphaolefin (Spectrasyn 40) and castor oil (85 to 90 wt.% ricinoleic acid triglyceride). Small- and wide-angle X-ray scattering measurements indicate a strong interaction of the polyester with castor oil and an increase in the crystalline fraction, with an increasing polymer amount from 5 to 40 wt.%. Moreover, infrared analysis of the polyester in castor oil showed gel formation at a minimum concentration of 20 wt.%. The strong interaction of the polyester with castor oil compared to the other two base oils led to an increase in the yield point γF as a measure of the mechanical stability of the gel, which was determined to be 5.9% compared to 0.8% and 1.0% in Brightstock and Spectrasyn, respectively.

Lubricating greases based on urea thickeners are frequently used in high-performance applications since their invention in 1954. One property that has so far been neglected in the further development of these systems due to their low solubility and the resulting difficulty of analysis, is to better understand how the degree of polymerization affect such polyurea lubricating systems. In this work, we prepared three different oligo- or polyurea systemswith different degrees of polymerization (DP) and investigated the influence of DP on rheological and tribological properties. The results showed that the DP has an influence on the flow limit in rheology as well as on the extreme pressure (EP) and anti-wear (AW) properties as examined by tribology measurements. By optimizing the DP for a thickener system, comparable EP and AW properties can be achieved through the use of additives. The DP showed an increasing influence on the flow limit. This could reduce damage to rolling bearings due to lateral loading at rest. Therefore, modifying the DP of the polyurea systems shows similar effects as the addition of external additives. Overall, this would reduce the use of additives in industrial applications.

The self‐organization process of polysaccharide alginate with different cationic surfactants at the water‐air interface was investigated over a wide concentration regime. The changes of surface properties determined by surface tension measurements, surface rheology, and X‐ray reflectivity are correlated with changes of bulk properties measured by turbidity, light scattering, and zeta potential measurements. We demonstrate that the interactions between the alginate and cationic surfactants result in significant changes of bulk and interfacial properties. The results of surface shear experiments point to the existence of highly viscoelastic interfacial films. In combination with X‐ray reflectivity, we demonstrate that these rheological features are related to polymer‐surfactant associations at the interface. In the regime of high surfactant concentrations, we observed the existence of multilayer structures.

This publication is focused on the structural origin of viscoelasticity in Langmuir monolayers. To improve the understanding of the structural origin of viscoelasticity of surfactant films, we systematically studied interfacial films of different sorbitan esters with saturated (Span 60 and 65) and unsaturated (Span 80 and 85) paraffin chains by means of surface rheology, Langmuir isotherms, X-ray reflectometry (XRR), and Brewster angle microscopy (BAM). The results of two-dimensional shear rheological measurements revealed the existence of temporarily cross-linked networks. In dynamic BAM experiments, we observed a swinging motion of the monolayers as a result of a sudden externally initiated mechanical perturbation. The viscoelastic film response, which relaxed with time as the external force vanished, could be traced back to the presence of foam-like supramolecular structures that interlinked solid-condensed domains. The temperature dependence of the elastic response implied that the solid domains decomposed at temperatures close to the bulk melting point of Span 60 and Span 65. We concluded that insoluble surfactants formed solid domains at the interface, which were linked with each other by nonsolid areas, giving viscoelastic films. These newly discovered insights into coherent film formations could provide new opportunities for designing mechanically stable surfactant interfaces.

In this article we investigated the deformation of alginate capsules in magnetic fields. The sensitivity to magnetic forces was realised by encapsulating an oil in water emulsion, where the oil droplets contained dispersed magnetic nanoparticles. We solved calcium ions in the aqueous emulsion phase, which act as crosslinking compounds for forming thin layers of alginate membranes. This encapsulating technique allows the production of flexible capsules with an emulsion as the capsule core. It is important to mention that the magnetic nanoparticles were stable and dispersed throughout the complete process, which is an important difference to most magnetic alginate-based materials. In a series of experiments, we used spinning drop techniques, capsule squeezing experiments and interfacial shear rheology in order to determine the surface Young moduli, the surface Poisson ratios and the surface shear moduli of the magnetically sensitive alginate capsules. In additional experiments, we analysed the capsule deformation in magnetic fields. In spinning drop and capsule squeezing experiments, water droplets were pressed out of the capsules at elevated values of the mechanical load. This phenomenon might be used for the mechanically triggered release of water-soluble ingredients. After drying the emulsion-filled capsules, we produced capsules, which only contained a homogeneous oil phase with stable suspended magnetic nanoparticles (organic ferrofluid). In the dried state, the thin alginate membranes of these particles were rather rigid. These dehydrated capsules could be stored at ambient conditions for several months without changing their properties. After exposure to water, the alginate membranes rehydrated and became flexible and deformable again. During this swelling process, water diffused back in the capsule. This long-term stability and rehydration offers a great spectrum of different applications as sensors, soft actuators, artificial muscles or drug delivery systems.

An X-ray reflectivity study on the adsorption behavior of human apolipoprotein A1 (apoA1) at hydrophilic and hydrophobic interfaces is presented. It is shown that the protein interacts via electrostatic and hydrophobic interactions with the interfaces, resulting in the absorption of the protein. pH dependent measurements at the solid/liquid interface between silicon dioxide and aqueous protein solution show that in a small pH range between pH 4 and 6, adsorption is increased due to electrostatic attraction. Here, the native shape of the protein seems to be conserved. In contrast, the adsorption at the liquid/gas interface is mainly driven by hydrophobic effects, presumably by extending the hydrophobic regions of the amphipathic helices, and results in a conformational change of the protein during adsorption. However, the addition of differently charged membrane-forming lipids at the liquid/gas interface illustrates the ability of apoA1 to include lipids, resulting in a depletion of the lipids from the interface.

This article reports the behavior of embryonic neural stem cells on a hydrogel that combines cationic, non-specific cell adhesion motifs with glycine-arginine-glycine-aspartic acid-serine-phenylalanine (GRGDSF)-peptides as specific cell adhesion moieties. Therefore, three hydrogels are prepared by free radical polymerization that contains either a GRGDSF-peptide residue (P1), amino ethylmethacrylate as a cationic residue (P2), or a combination of both motifs (P3). For each gel, cross linker concentrations of 8 mol% is used to have a comparable gel stiffness of 8-9 kPa. The cell experiments indicate a synergistic effect of the non-specific, cationic residues, and the specific GRGDSF-peptides on embryonic neural stem cell behavior that is especially pronounced in the cell adhesion experiments by more than doubling the number of cells after 72 h when comparing P3 with P2 and is less pronounced in the proliferation and differentiation experiments.

In this work, the structure of solid-supported lipid multilayers exposed to increased hydrostatic pressure was studied in situ by X-ray reflectometry at the solid-liquid interface between silicon and an aqueous buffer solution. The layers' vertical structure was analyzed up to a maximum pressure of 4500 bar. The multilayers showed phase transitions from the fluid into different gel phases. With increasing pressure, a gradual filling of the sublayers between the hydrophilic head groups with water was observed. This process was inverted when the pressure was decreased, yielding finally smaller water layers than those in the initial state. As is commonly known, water has an abrasive effect on lipid multilayers by the formation of vesicles. We show that increasing pressure can reverse this process so that a controlled switching between multi- and bilayers is possible.

Upon incorporation of magnetic nanoparticles (mNPs) into gels, composite materials called ferrogels are obtained. These magneto-responsive systems have a wide range of potential applications including switches and sensors as well as drug delivery systems. In this article, we focus on the properties of calcium alginate capsules, which are widely used as carrier systems in medicine and technology. We studied the incorporation of different kinds of mNPs in matrix capsules and in the core and the shell of hollow particles. We found out that not all particle-alginate or particle-CaCl2 solution combinations were suitable for a successful capsule preparation on grounds of a destabilization of the nanoparticles or the polymer. For those systems allowing the preparation of switchable beads or capsules, we systematically studied the size and microscopic structure of the capsules, their magnetic behavior and mechanical resistance.

Using microcapsules for medical and technical purposes relies on capsule properties such as stability, shape, and permeability, which depend on the production process and the capsule material itself. The methods presented here, which are based on nuclear magnetic resonance microscopy, allow one to quantitatively determine these parameters for individual microcapsules with or without coatings. The experiments are noninvasive and can access such parameters as geometry, diffusion constants, or molecular correlation times in different chemical environments with a spatial resolution of ~10 μm. The influence of production parameters as well as the dynamic behavior of capsules in various test environments are characterized for potential applications in targeted drug delivery.

Hyaluronan and phospholipids play an important role in lubrication in articular joints and provide in combination with glycoproteins exceptionally low friction coefficients. We have investigated the structural organization of 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) Langmuir layers at the solution-air interface at different length scales with respect to the adsorption of hyaluronan (HA). This allows us to assemble a comprehensive picture of the adsorption and the resulting structures, and how they are affected by the molecular weight of HA and the presence of calcium ions. Brewster angle microscopy and grazing incident diffraction were used to determine the lateral structure at the micro- and macro scale. The data reveals an influence of HA on both the macro and micro structure of the DPPC Langmuir layer, and that the strength of this effect increases with decreasing molecular weight of HA and in presence of calcium ions. Furthermore, from X-ray reflectivity measurements we conclude that HA adsorbs to the hydrophilic part of DPPC, but data also suggest that two types of interfacial structures are formed at the interface. We argue that hydrophobic forces and electrostatic interactions play important rules for the association between DPPC and HA. Surface pressure area isotherms were used to determine the influence of HA on the phase behavior of DPPC while electrophoretic mobility measurements were used to gain insight into the binding of calcium ions to DPPC vesicles and hyaluronan.

A study of lysozyme adsorption below a behenic acid membrane and at the solid–liquid interface between aqueous lysozyme solution and a silicon wafer in the presence of sodium chloride is presented. The salt concentration was varied between 1 mmol L−1 and 1000 mmol L−1. X-ray reflectivity data show a clear dependence of the protein adsorption on the salt concentration. Increasing salt concentrations result in a decreased protein adsorption at the interface until a complete suppression at high concentrations is reached. This effect can be attributed to a reduced attractive electrostatic interaction between the positively charged proteins and negatively charged surfaces by charge screening. The measurements at the solid–liquid interfaces show a transition from unoriented order of lysozyme in the adsorbed film to an oriented order with the short protein axis perpendicular to the solid–liquid interface with rising salt concentration.

Three amphiphilic diblock poly(2-oxazoline) copolymers composed of the hydrophilic poly(2-methyl-2-oxazoline) and hydrophobic poly(2-alkyl-2-oxazoline) with alkyl = pentyl (P1), heptyl (P2), and nonyl side chain (P3) lengths of the hydrophobic block were synthesized by ring-opening cationic polymerization. These polymers form micelles in water above their critical micelle concentration. The temperature-dependent stability of the micellar aggregates was analyzed by DLS and turbidity measurements as Well as pyrene solubilization between 20 and 80 degrees C in water. Moreover, the chemical composition of the block copolymers was determined by H-1 NMR spectroscopy. In particular, it was possible to quantify the degree of aggregations of the individual groups of both blocks by including the chemical composition into the derived equations. It could be shown by varying the temperature that both the chemical composition and the degree of micellization depend on the number of bonds of the considered structural groups of the side chain with respect to the backbone of the hydrophobic block as well as the length of the side chain. In addition, temperature-dependent T-1 and T-2 measurements were performed to determine the dynamics of the structural groups of the hydrophilic and hydrophobic blocks. Correlation times and activation energies were determined of the individual structural groups confirming the different mobilities.

Nonionic dendritic amphiphiles that self-assemble into defined supramolecular aggregates are useful for the efficient solubilization of active agents, for example, in drug delivery. We investigated a new class of dendritic amphiphiles based on a hydrophilic polyol dendron head connected to a two-chain hydrophobic block. In analogy to phospholipids, these molecules form well-organized layers in bulk (vesicles) or at the water surface (Langmuir monolayer). The actual study focuses on the phase behavior and microscopic structure of mixed Langmuir layers of theses dendritic amphiphiles with the well-known phospholipid DPPC. The combination of surface pressure area isotherms with X-ray grazing incident diffraction and Brewster angle microscopy gives us information on the phase behavior of the mixed monolayers and the orientation of the amphiphiles inside the condensed domains with molecular resolution. We could prove that the dendritic generation and, by this, the headgroup size of the amphiphilic molecules have a significant influence on their interaction with DPPC at the air-water interface. Thus, our findings are important for the understanding of mixed lipid membranes in general as well as for the preparation of artificial membranes and vesicles with adjustable properties, e.g., their drug delivery potential.

Attractive candidates for compartmentalizing prebiotic cells are membranes comprised of single-chain fatty acids. It is generally believed that life may have originated in the depth of the protoocean, that is, under high hydrostatic pressure conditions, but the structure and physical-chemical properties of prebiotic membranes under such conditions have not yet been explored. We report the temperature- and pressure-dependent properties of membranes composed of prebiotically highly-plausible lipids and demonstrate that prebiotic membranes could not only withstand extreme temperatures, but also serve as robust models of protocells operating in extreme pressure environments. We show that pressure not only increases the stability of vesicular systems but also limits their flexibility and permeability to solutes, while still keeping the membrane in an overall fluid-like and thus functional state.

The mimicry of natural microswimmers by artificial nano- and micro-devices is extremely challenging because it is hard to achieve and control nanoscale actuation reproducibly and reversibly. In the context of recent developments, we shall review the basic phenomena of artificial swimming objects in the micrometer scale. Typically, these swimming devices were rigid, and up to now, the mechanisms of self-propulsion have only rarely been adapted to soft particles as microcapsules. The high flexibility of capsules is an important feature for more realistic descriptions of the basic swimming processes of biological cells. Additionally, micro- and nanocapsules show the advantage that they can store a defined amount of chemical or biological compounds in their core regions. This offers a high potential for the realization of diverse biological or medical applications (e.g. cargo transport and controlled drug delivery). The discussed phenomena are based on different chemical reactions or flow and diffusion principles, including bulk- and surface rheology, and they can be used to develop new ideas concerning the construction of advanced types of self-propelling microcapsules.

High resolution magic angle spinning (H-1 HR-MAS) NMR spectroscopy has been used to analyze the composition of a set of bioactive hydrogels. Therefore, a set of six hydrogels with different cross linker densities ranging from 1 to 12 mol% were prepared by free radical polymerization. The disulfide based cross linkers of the hydrogels were reduced with dithiothreitol (DTT) to generate free sulfhydryl groups giving access to soluble copolymers. Comparison of the H-1 NMR results of the soluble copolymers with those obtained from 1H HR-MAS experiments revealed that for lower cross linker densities of 1-2 mol%, HR-MAS spectroscopy of the hydrogels matches quantitatively the peptide content of the soluble copolymer. With increasing cross linker densities up to 12 mol% the signal intensity of the aromatic unit is linearly reduced to 62% compared to the results obtained by 1H NMR spectroscopy. (C) 2014 Elsevier Ltd. All rights reserved.

A group of new chiral dications with a fixed, specific configuration at the stereogenic nitrogen center was created. Stereoselective synthesis and recrystallization give the diastereomerically and enantiomerically pure dications, including a chiral amphiphile with surface-active properties.

Structural and mechanical properties of molecularly thick polysiloxane membranes were studied on different liquid subphases to investigate the impact of the subphase's pH value on the cross-linking process. The lateral structure of these films was studied in-situ by grazing incidence diffraction while torsions pendulum experiments reveal the response of the system to mechanical stress. The results show a hindered cross-linking on acidic subphases. At alkaline and neutral pH conditions the cross-linking process was not effected. The data revealed that the degree of polymerization can be tuned by regulating the subphase's pH value, which opens the opportunity to build complex polysiloxane membranes in a controlled manner. (C) 2014 Elsevier B.V. All rights reserved.

The behavior of magnetically responsive aqueous Fe(III) surfactant solutions at liquid interfaces is analyzed. Such surfactants attracted much attention, because of the ability to manipulate interfaces by magnetic fields without any use of magnetic nanoparticles. A detailed analysis of the surface properties proves that the mixing of paramagnetic electrolyte solution with anionic, cationic and nonionic surfactants yields the similar magnetic response and no effect of the surfactant charge can be observed. We conclude that the observed magnetic shiftability of interfaces is caused by a combination of the paramagnetic behavior of the bulk liquid and a reduction of the surface tension. Thus, this work gives an alternative interpretation of the properties of "magnetic surfactants" compared to the ones claimed in the literature.