Heinz Rehage

Non-linear flow properties of viscoelastic surfactant solutions

This paper gives a quantitative description of the viscoelastic properties of aqueous solutions of entangled rod-shaped micelles. The experimental data are compared with the theoretical predictions of a special constitutive equation which is based on the concept of deformation-dependent tensorial mobility. In the regime of small deformations, shear stresses or shear rates, the dynamic features of the viscoelastic solutions are characterized by the equations of a simple Maxwell material. These phenomena are linked to the average lifetime of the micellar aggregates and the rheological properties are controlled by kinetic processes. At these conditions one observes simple scaling laws and linear relations between all theological quantities. At elevated values of shear stresses or deformations, however, this simple model fails and non-linear properties as normal stresses, stress overshoots or shear-thinning properties occur. All these phenomena can be described by a constitutive equation which was first proposed by H. Giesekus. The experimental results are in fairly good agreement with the theoretical predictions, and this model holds for a certain, well defined value of the mobility factor α. This parameter describes the anisotropic character of the particle motion. In transient and steady-state flow experiments we always observed α = 0.5. Especially at these conditions, the empirically observed Cox-Merz rule, the Yamamoto relation and both Gleißle mirror relations are automatically derived from the Giesekus model. The phenomena discussed in this paper are of general importance, and can be equally observed in different materials, such as polymers or proteins. The viscoelastic surfactant solutions can, therefore, be used as simple model systems for studies of fundamental principles of flow.

Effect of acidic, basic and fluoride-catalyzed sol-gel transitions on the preparation of sub-nanostructured silica

Abstract Amorphous porous silica can be prepared under acid, base and neutral polycondensation conditions from tetraethoxysilane by the sol-gel process. After drying and calcination of the resulting gels the glasses prepared under acidic or fluoride-catalyzed conditions are microporous with a narrow pore size distribution and high surface area, while the glass prepared under basic conditions shows a broad distribution of mesopores and a low surface area. Rheological studies of the sol-gel process under acidic conditions show a simultaneous increase of viscosity and elasticity with time, indicative of a linear polymerisation mechanism. The same is observed under the fluoride-catalyzed conditions. In the base-catalyzed sol-gel there is no elasticity component with increasing viscosity typical for particle growth and a lack of a three-dimensional network. High-resolution transmission electron microscopy (HR-TEM) studies show the acid and fluoride metal oxide to consist of amorphous continuous glass-like material even at atomic resolution, while the basic metal oxide consists of agglomerations of particles, suggesting that the observed mesoporosity of the material can be attributed to inter-particle voids. We have shown, that the final microstructure of the materials is mainly a result of the initial polycondensation conditions.

Silver-doped calcium phosphate nanoparticles: Synthesis, characterization, and toxic effects toward mammalian and prokaryotic cells

Spherical silver-doped calcium phosphate nanoparticles were synthesized in a co-precipitation route from calcium nitrate/silver nitrate and ammonium phosphate in a continuous process and colloidally stabilized by carboxymethyl cellulose. Nanoparticles with 0.39 wt% silver content and a diameter of about 50-60 nm were obtained. The toxic effects toward mammalian and prokaryotic cells were determined by viability tests and determination of the minimal inhibitory and minimal bactericidal concentrations (MIC and MBC). Three mammalian cells lines, i.e. human mesenchymal stem cells (hMSC) and blood peripheral mononuclear cells (PBMC, monocytes and T-lymphocytes), and two prokaryotic strains, i.e. Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) were used. Silver-doped calcium phosphate nanoparticles and silver acetate showed similar effect toward mammalian and prokaryotic cells with toxic silver concentrations in the range of 1-3 μg mL(-1).

Alkylcyanoacrylate nanocapsules prepared from mini-emulsions: A comparison with the conventional approach

Polyalkylcyanoacrylate nanocapsules are being prepared using two different types of o/w-emulsions: a conventional emulsion generated by intensive stirring with a home-made device and a mini-emulsion produced by the action of ultrasonic dispersion, using the alkylcyanoacrylate monomer as a hydrophobic agent. The emulsions and the resulting nanocapsule dispersions are compared using various methods of physical characterization. The formation of solid capsules is indicated by solid state NMR spectra and atomic force microscopy. Differences between the results of both synthetic approaches are found in terms of particle size distribution, zeta potential and tendency towards particle agglomeration. Capsules prepared by ultrasound via the mini-emulsion pathway tend to be smaller and more monodisperse. Their zeta potential is negative with larger absolute values as compared to capsules obtained from conventional emulsions, leading to stronger repulsive interactions and a higher stability against capsule agglomeration.

Is the antioxidative effectiveness of a bilberry extract influenced by encapsulation

BACKGROUND Bilberries (Vaccinium myrtillus L.) have been suggested to have preventive properties against diseases associated with oxidative stress such as colon cancer or inflammatory bowel diseases. Therefore the gastrointestinal tract is regarded as a potential target for prevention. In this study the antioxidative properties of a commercially available anthocyanin-rich bilberry extract (BE) were investigated in comparison with four different BE-loaded microcapsule systems. As markers to describe the antioxidant status in this cellular system, intracellular reactive oxygen species (ROS) levels, oxidative DNA damage and total glutathione (tGSH) levels were monitored. RESULTS Incubations with the BE-loaded capsule systems showed an increase in cellular glutathione levels and reduction of ROS levels at high BE concentrations (100-500 µg mL(-1) ) and a positive effect on the formation of DNA strand breaks (5-10 µg mL(-1) BE). The biological properties of BE-loaded pectin amide core-shell capsules, whey protein matrix capsules and coated apple pectin matrix capsules were comparable to those of the non-encapsulated BE. CONCLUSION Overall, the BE and the encapsulated BE types tested have antioxidative activity under the studied assay conditions in terms of the prevention of oxidative DNA damage, the reduction of intracellular ROS and the enhancement of cellular tGSH.

Characterizing permeability and stability of microcapsules for controlled drug delivery by dynamic NMR microscopy

Microscopic capsules made from polysaccharides are used as carriers for drugs and food additives. Here, we use NMR microscopy to assess the permeability of capsule membranes and their stability under different environmental conditions. The results allow us to determine the suitability of different capsules for controlled drug delivery. As a measure of the membrane permeability, we monitor the diffusion of paramagnetic molecules into the microcapsules by dynamic NMR microimaging. We obtained the diffusion coefficients of the probe molecules in the membranes and in the capsule core by comparing the measured time dependent concentration maps with numerical solutions of the diffusion equation. The results reveal that external coatings strongly decrease the permeability of the capsules. In addition, we also visualized that the capsules are stable under gastric conditions but dissolve under simulated colonic conditions, as required for targeted drug delivery. Depending on the capsule, the timescales for these processes range from 1 to 28 h.

Hydrophobic N-Diazeniumdiolates and the Aqueous Interface of Sodium Dodecyl Sulfate (SDS) Micelles

Zwitterionic diazeniumdiolates of the form RN[N(O)NO(-)](CH(2))(2)NH(2) (+)R, where R=CH(3) (1), (CH(2))(3)CH(3) (2), (CH(2))(5)CH(3) (3), and (CH(2))(7)CH(3) (4) were synthesized by reaction of the corresponding diamines with nitric oxide. Spectrophotometrically determined pK(a)(O) values, attributed to protonation at the terminal oxygen of the diazeniumdiolate group, show shifts to higher values in dependence of the chain lengths of R. The pH dependence of the decomposition of NO donors 1-3 was studied in buffered solution between pH 5 and 8 at 22 degrees C, from which pK(a)(N) values for protonation at the amino nitrogen, leading to release of NO, were estimated. It is shown that the decomposition of these diazeniumdiolates is markedly catalyzed by anionic SDS micelles. First-order rate constants for the decay of 1-4 were determined in phosphate buffer pH 7.4 at 22 degrees C as a function of SDS concentration. Micellar binding constants, K(SM), for the association of diazeniumdiolates 1-3 with the SDS micelles were also determined, again showing a significant increase with increasing length of the alkyl side chains. The decomposition of 1-3 in micellar solution is quantitatively described by using the pseudo-phase ion-exchange (PIE) model, in which the degree of micellar catalysis is taken into account through the ratio of the second-order rate constants (k(2m)/k(2w)) for decay in the micelles and in the bulk aqueous phase. The decay kinetics of 1-3 were further studied in the presence of cosolvents and nonionic surfactants, but no effect on the rate of NO release was observed. The kinetic data are discussed in terms of association to the micelle-aqueous phase interface of the negatively charged micelles. The apparent interfacial pH value of SDS micelles was evaluated from comparison of the pH dependence of the first-order decay rate constants of 2 and 3 in neat buffer and the rate data obtained for the surfactant-mediated decay. For a bulk phase of pH 7.4, an interfacial pH of 5.7-5.8 was determined, consistent with the distribution of H(+) in the vicinity of the negatively charged micelles. The data demonstrate the utility of 2 and 3 as probes for the determination of the apparent pH value in the Stern region of anionic micelles.

Sealing liquid-filled pectinate capsules with a shellac coating

Liquid-filled pectinate capsules have a large potential for the controlled and site-specific delivery of liquid drugs. Earlier studies have shown that pure pectinate capsules can store drugs only for a few minutes. Here, we show that the retention time can be extended to several hours by coating the capsules with the natural resin shellac. A bilberry extract containing anthocyanins with promising therapeutic properties was used as model drug to characterize the permeability of the capsules by in vitro drug release measurements. Characterizing the structure of the double-layered capsule membranes by NMR microscopy, we optimized the capsule production by adjusting the pH-value in the coating process and the gelation time of the pectinate hydrogel layer. A comparison of the layer thicknesses with drug release measurements reveals that capsules with the thinnest shellac layers provide the best entrapment. Additional squeezing experiments show that the shellac layer makes the capsules also mechanically more stable.

Pendant capsule elastometry

We provide a C/C++ software for the shape analysis of deflated elastic capsules in a pendant capsule geometry, which is based on an elastic description of the capsule material as a quasi two-dimensional elastic membrane using shell theory. Pendant capsule elastometry provides a new in situ and non-contact method for interfacial rheology of elastic capsules that goes beyond determination of the Gibbs- or dilational modulus from area-dependent measurements of the surface tension using pendant drop tensiometry, which can only give a rough estimate of the elastic capsule properties as they are based on a purely liquid interface model. Given an elastic model of the capsule membrane, pendant capsule elastometry determines optimal elastic moduli by fitting numerically generated axisymmetric shapes optimally to an experimental image. For each digitized image of a deflated capsule elastic moduli can be determined, if another image of its undeformed reference shape is provided. Within this paper, we focus on nonlinear Hookean elasticity because of its low computational cost and its wide applicability, but also discuss and implement alternative constitutive laws. For Hookean elasticity, Youngs surface modulus (or, alternatively, area compression modulus) and Poissons ratio are determined; for Mooney-Rivlin elasticity, the Rivlin modulus and a dimensionless shape parameter are determined; for neo-Hookean elasticity, only the Rivlin modulus is determined, using a fixed dimensionless shape parameter. Comparing results for different models we find that nonlinear Hookean elasticity is adequate for most capsules. If series of images are available, these moduli can be evaluated as a function of the capsule volume to analyze hysteresis or aging effects depending on the deformation history or to detect viscoelastic effects for different volume change rates. An additional wrinkling wavelength measurement allows the user to determine the bending modulus, from which the layer thickness can be derived. We verify the method by analyzing several materials, compare the results to available rheological measurements, and review several applications. We make the software available under the GPL license at github.com/jhegemann/opencapsule.

Gemini-like molecular clips and tweezers: the influence of structure and guest binding on interfacial tension.

In a series of experiments, we studied the interfacial activity of aromatic aliphatic molecules with rigid gemini-like structures at the interface between toluene and water. These molecules, called clips and tweezers, have rigid central benzene or naphthalene spacer-units, each substituted with two polar groups as well as two rigid aromatic side walls. They can serve as host molecules and selectively bind a variety of electron-deficient aromatic and aliphatic guest molecules. In different experiments, we compared the interfacial tensions with the calculated hydrophilic-lipid-balance (HLB) values of these molecules. The measured interfacial tensions depend as much on the HLB values as on the geometric structure of the water insoluble molecules. The concentration dependence of the surface tension gave evidence for the formation of inverse micellar aggregates, which were formed in the oil phase above a well-defined value of the bulk concentration. The presence of aggregates in the organic liquid could also be investigated by dynamic light scattering measurements. We observed typical diameters of the inverse micellar aggregates in the order of 5.6 nm, and the critical micelle concentrations (cmcs) coincided well with the results of interfacial tension measurements. From the surface excess in the vicinity of the cmc, we calculated the space occupied by a single clip molecule on the self-assembled monolayer. The observed molecular surface area was in agreement with the effective molecular diameters of the molecules. In additional experiments, we could also show that complexes with aromatic guest molecules such as 1,2-4,5-tetracyanobenzene (TCNB) led to a reduction of the amphiphilic clip properties.