Colloidal Particle Adsorption at Water-Water Interfaces with Ultralow Interfacial Tension.

Using fluorescence confocal microscopy we study the adsorption of single latex microparticles at a water-water interface between demixing aqueous solutions of polymers, generally known as a water-in-water emulsion. Similar microparticles at the interface between molecular liquids have exhibited an extremely slow relaxation preventing the observation of expected equilibrium states. This phenomenon has been attributed to "long-lived" metastable states caused by significant energy barriers ΔF∼γA_{d}≫k_{B}T induced by high interfacial tension (γ∼10^{-2} N/m) and nanoscale surface defects with characteristic areas A_{d}≃10-30 nm^{2}. For the studied water-water interface with ultralow surface tension (γ∼10^{-4} N/m) we are able to characterize the entire adsorption process and observe equilibrium states prescribed by a single equilibrium contact angle independent of the particle size. Notably, we observe crossovers from fast initial dynamics to slower kinetic regimes analytically predicted for large surface defects (A_{d}≃500 nm^{2}). Moreover, particle trajectories reveal a position-independent damping coefficient that is unexpected given the large viscosity contrast between phases. These observations are attributed to the remarkably diffuse nature of the water-water interface and the adsorption and entanglement of polymer chains in the semidilute solutions. This work offers some first insights on the adsorption dynamics or kinetics of microparticles at water-water interfaces in biocolloidal systems.

Electrospray-assisted drying of live probiotics in acacia gum microparticles matrix.

Acacia gum solution was employed as a carrier for electrospray-assisted drying of probiotic cells. To optimize the process, effect of gum concentration, thermal sterilization as a prerequisite for microbial studies, and surfactant addition on physical properties of feed solution was investigated. Increasing gum concentration from 20 to 40 wt.% led to a viscosity increase, whilst surface tension did not change meaningfully and electrical conductivity declined after an increasing trend up to 30 wt.% of the gum. Thermal sterilization increased the viscosity without any significant effect on the conductivity and surface tension. Surfactant addition reduced the surface tension and conductivity but the viscosity increased. Highly uniform particles were formed by electrospray-assisted drying of autoclaved 35 wt.% acacia gum solution containing 1 wt.% Tween 80. Thermal sterilization and surfactant addition improved electrospray-ability of acacia gum solution. Bacterial count showed that more than 96 percent of probiotic cells passed the process viably.

Interfacial Tension of Phase-Separated Polydisperse Mixed Polymer Solutions.

Aqueous two-phase systems provide oil-free alternatives in the formulation of emulsions in food and other applications. Theoretical interpretation of measurements on such systems, however, is complicated by the high polydispersity of the polymers. Here, phase diagrams of demixing and interfacial tensions are determined for aqueous solutions of two large polymers present in a mass ratio of 1:1, dextran (70 kDa) and nongelling gelatin (100 kDa), with or without further addition of smaller dextran molecules (20 kDa). Both in experiments and in calculations from Scheutjens-Fleer self-consistent field lattice theory, we find that small polymers decrease the interfacial tension at equal tie-line length in the phase diagram. After identifying the partial contributions of all chemical components to the interfacial tension, we conclude that excess water at the interface is partially displaced by small polymer molecules. An interpretation in terms of the Gibbs adsorption equation provides an instructive way to describe effects of polydispersity on the interfacial tension of demixed polymer solutions.

Polyelectrolytes adsorbed at water-water interfaces.

Polyelectrolytes can show strong adsorption at water-water interfaces formed by phase separation of two polymers in aqueous solution. We demonstrate this for a model system consisting of neutral polymer A and weakly positively charged polymer B. When polyelectrolyte is added with similar chemical composition as polymer A, but charge of opposite sign as polymer B, interfacial accumulation is observed. We hypothesize this accumulation to be complexation at the water-water interface. This adsorption surprisingly persists even at high salt concentrations and has only a limited effect on the interfacial tension. Complexation of polyelectrolytes at water-water interfaces may provide a new path towards the stabilization of water-in-water emulsions.

Decreased Interfacial Tension of Demixed Aqueous Polymer Solutions due to Charge.

Electric charge at the water-water interface of demixed solutions of neutral polymer and polyelectrolyte decreases the already ultralow interfacial tension. This is demonstrated in experiments on aqueous mixtures of dextran (neutral) and nongelling fish gelatin (charged). Upon phase separation, electric charge and a potential difference develop spontaneously at the interface, decreasing the interfacial tension purely electrostatically in a way that can be accounted for quantitatively by Poisson-Boltzmann theory. Interfacial tension is a key property when it comes to manipulating the water-water interface, for instance to create novel water-in-water emulsions.

Protein-polysaccharide interactions to alter texture.

The sensory perception of texture is an important contributor of our general appreciation of foods. Food texture is mainly described in terms of mouthfeel and afterfeel attributes. The role of oral processing in the perception of texture and the role of microstructure therein have been reviewed regularly over recent years (Chen & Engelen 2012, Foegeding et al. 2011, Stieger & van de Velde 2013) and are not, therefore, addressed in this review. The scope of this review relates to the molecules that underlay the texture of foods. Protein, carbohydrate, and fat are the major structuring components in foods. In this review we focus on the physical interactions between proteins and polysaccharides that form the basis for the microstructure and texture of these foods. In general, food products are classified in four categories by their sensory and rheological properties: liquids, semisolids, soft solids, and hard solids (van Vliet et al. 2009). These four categories provide a useful classification framework, although they are not precisely defined by specific rheological properties. The current review focuses on semisolid and soft-solid foods.

Water-in-Water Emulsions Stabilized by Nanoplates.

Ultrathin plate-like colloidal particles are effective candidates for Pickering stabilization of water-in-water emulsions, a stabilization that is complicated by the thickness and ultralow tension of the water-water interface. Plate-like particles have the advantage of blocking much of the interface while simultaneously having a low mass. Additionally, the amount of blocked interface is practically independent of the equilibrium contact angle θ at which the water-water interface contacts the nanoplates. As a result, the adsorption of nanoplates is stronger than for spheres with the same maximal cross section, except if θ = 90°.

Analysis of light scattered by turbid media in cylindrical geometry.

The angle dependence of the transmitted light through a cylindrical turbid sample (latex suspension, developing milk gel, draining/coarsening milk, and protein foams) in a standard light scattering setup was analyzed in terms of the transport mean free path length or scattering length l* (a measure for the turbidity) and the absorption length labs. By variation of the concentration of an absorbing dye, the independence of l* and labs was demonstrated. The resulting value of the specific extinction coefficient of the dye was found to be in fair agreement with direct spectroscopic determination and practically identical in milk and latex suspensions. The validity of this technique for obtaining l* was demonstrated by monitoring the acid-induced gelation of milk. The possibility to simultaneously determine l* and labs was used to follow the time development of a draining and coarsening protein foam which contained an absorbing dye. It was shown that labs can be used as a measure for the volume fraction of air in the foam. This method of monitoring the transmission of multiple light scattering provides an easy way to determine l* and, specifically for foams, quantitative data dominated by the bulk of the foam.

Donnan potentials in aqueous phase-separated polymer mixtures.

A promising approach to texturize water is by the addition of mutually incompatible polymers, leading to phase separation. Here, we demonstrate that the phase stability of aqueous polymer solutions is affected not only by chemical differences between the polymers but also by their electric charge. Direct electrochemical measurements are performed of the electric potential difference between two coexisting phases in aqueous solutions of the charged protein fish gelatin (nongelling) and the uncharged polysaccharide dextran. Charge counteracts demixing because of the entropic cost of confining the counterions to one phase, resulting in a strong shift of the critical point upon an increase of the charge on one of the polymers. Upon phase separation, the charged polymer is spatially confined, and due to the Donnan effect, an interfacial electric potential is developed. A direct proportionality is found between this Donnan potential and the difference in gelatin concentration in the two phases, for which we propose a theoretical explanation. The electrostatics may provide a new handle in the development of stable water-in-water emulsions.

Milk gelation studied with small angle neutron scattering techniques and Monte Carlo simulations.

The sol-gel transition of fat-free milk by acidification was studied with neutron scattering experiments and Monte Carlo simulations. Spin-echo small angle neutron scattering (SESANS) and ultrasmall angle neutron scattering (USANS) experiments were performed to measure the static structure of milk and yogurt, as well as the aggregation kinetics. Colloidal gelation was simulated from a reaction limited domain (RLCA) to the diffusion limited regime (DLCA) as cluster-cluster aggregation of adhesive, hard spheres on a three-dimensional lattice. Comparisons were drawn between experimental and numerical correlation functions. Milk was modeled as a suspension of casein micelles in water, and its structure was described with a dilute system of solid spheres with a log-normal distribution of sizes. The structure and formation of yogurt were described with a self-affine model, used for systems containing heterogeneities with a wide range of sizes. Simulation speed was increased by 1 order-of-magnitude using a new algorithm to eliminate dead time. Observations by SESANS and USANS of milk particle sizes and yogurt length scales were consistent and agreed well with literature. Kinetic USANS data yielded reliable information about the growth of typical length scale during aggregation. The simulation model predicted the measurement data qualitatively best staying close to the RLCA regime until large structures had formed. Correlation lengths were in good quantitative agreement, but longest simulated length scales were a of factor 2(1)/(2) below experimental findings. We conclude that small, mobile aggregates are formed during the first 3 h, mostly influencing the dimensionality of the system and that large, inert structures are formed from 2 up to 8 h, which determine the typical length scale.

Water uptake mechanism in crispy bread crust.

Crispness is an important quality characteristic of dry solid food products such as crispy rolls. Its retention is directly related to the kinetics of water uptake by the crust. In this study, a method for the evaluation of the water sorption kinetics in bread crust is proposed. Two different sorption experiments were used: an oscillatory sorption test and a sorption test in which the air relative humidity (RH) was increased stepwise. These two experiments had different time scales, which made it possible to get a better understanding of the mechanisms involved. Results show that the adsorption and desorption dynamics of the oscillatory sorption test could be described by a single exponential in time. The water uptake rate ( k) was one of the fitting parameters. A maximum in the water uptake rate was found for a RH value between 50 and 70%. The rate parameters of the experiment where RH was increased stepwise were around a factor 10 lower than those derived from oscillatory sorption experiments. This is an important factor when designing experiments for the determination of water uptake rates. In addition, also a parameter describing the time dependence of the rate parameters of the oscillatory sorption experiment was calculated (C), again by fitting a single exponential to the rate parameters. C was in the same range as the rate parameter of the isotherm experiment. This indicates that different (relaxation) processes are acting at the same time in the bread crust during water uptake.

Band formation on shearing in phase-separated polymer solutions.

In a phase-separated mixture of two Newtonian polymer solutions sheared in a cone-plate geometry adapted for microscopic observation at a zero-velocity plane, shear-induced coalescence of droplets of the broken-up phase, followed by band formation, was observed. Initially wormlike structures developed into doughnut-shaped bands, disconnected from the walls of the geometry. The shear rate and composition inside the bands differed from that in the outside solution. The shear-shear rate instability preceding the band formation could be qualitatively described by a van der Waals-loop-shaped shear rate dependence of droplet deformation.

Oscillatory water sorption test for determining water uptake behavior in bread crust.

In this work, water sorption kinetics of bread crust are described using an oscillatory sorption test in combination with a Langmuir type equation. Both kinetic and thermodynamic information could be obtained at the same time. An advantage of applying a Langmuir type equation for a quantitative description of the water uptake kinetics is that no prior knowledge is necessary with respect to shape and surface area of the sample. It was shown that adsorption and desorption of water to the bread crust particle surface is much faster than the experimental time used (15 min at minimum). From this, we may conclude that diffusion of water into the solid matrix is the rate-limiting step in the water sorption process. The method also allows one to calculate a Gibbs free energy. The method is suitable for use up to relative humidities of 60%.

Arrested segregative phase separation in capillary tubes.

Phase separation in a capillary tube with one of the phases fully wetting the capillary wall is arrested when the typical size of the phase domains reaches the value of the diameter of the tube. The arrested state consists of an alternating sequence of concave-capped and convex-capped cylindrical domains, called "plugs," "bridges," or "lenses," of wetting and nonwetting phase, respectively. A description of this arrested plug state for an aqueous mixture of two polymer solutions is the subject of this work. A phase separating system consisting of two incompatible polymers dissolved in water was studied. The phase volume ratio was close to unity. The initial state from which plugs evolve is characterized by droplets of wetting phase in a continuous nonwetting phase. Experiments show the formation of plugs by a pathway that differs from the theoretically well-described instabilities in the thickness of a fluid thread inside a confined fluid cylinder. Plugs appear to form after the wetting layer (the confined fluid cylinder) has become unstable after merging of droplet with the wetting layer. The relative density of the phases could be set by the addition of salt, enabling density matching. As a consequence, the capillary length can in principle be made infinitely large and the Bond number (which represents the force of gravity relative to the capillary force) zero, without considerably changing the interfacial tension. Using the possibility of density matching, the relations among capillary length and capillary diameter on the one hand, and the presence of plugs and their average size on the other were studied. It was found that stable plugs are present when the capillary radius does not exceed a certain value, which is probably smaller than the capillary length. However, the average plug size is independent of capillary length. At constant capillary length, average plug size was found to scale with the capillary diameter to a power 1.3, significantly higher than the expected value of 1. Plug sizes had a polydispersity between 1.1 and 1.2 for all capillary radii for which this number could be reliably determined, suggesting a universal plug size distribution. Within plug sequences, size correlations were found between plugs with one to three plugs in between. This suggests the presence of an additional length scale.

Effects of confined geometry on phase-separated dextran/gelatine mixtures exposed to shear.

The effect of shear on aqueous phase-separated dextran/fish gelatine mixtures with a total concentration of 5 and 10% was studied in a confined geometry. It was measured as a function of composition, strain rate and gap size. This was done by using both small-angle light scattering and a shear cell combined with a confocal laser scanning microscope. At a total polymer concentration of 5%, small-angle light scattering results showed that up to 100 s(-1) the deformation of the domains increases with the strain rate. At strain rates less than 100 s(-1), the response of the system to strain is dominated by strain rate-dependent deformation. At a higher strain rate there might be balance between break-up and re-coalescence. At a total concentration of 10%, small effects of the gap size were found. In confined geometry, the coalescence rate was faster than expected from viscous hydrodynamic growth. The microscope images showed that the gelatine-enriched phase forms a wetting layer on the surface of the glass wall. The degree of wetting appears to increase with increasing the strain rate up to 60 s(-1) and decreases again at higher strain rates.

The structure of kappa/iota-hybrid carrageenans II. Coil-helix transition as a function of chain composition.

This paper describes the effect of the kappa/iota-ratio on the physical properties of kappa/iota-hybrid carrageenans (synonyms: kappa-2, kappa-2, weak kappa, weak gelling kappa). To this end, a series of kappa/iota-hybrid carrageenans ranging from almost homopolymeric kappa-carrageenan (98 mol-% kappa-units) to almost homopolymeric-carrageenan (99 mol-% iota-units) have been extracted from selected species of marine red algae (Rhodophyta). The kappa/iota-ratio of these kappa/iota-hybrids was determined by NMR spectroscopy. Their rheological properties were determined by small deformation oscillatory rheology. The gel strength (storage modulus, G') of the kappa/iota-hybrids decreases with decreasing kappa-content. On the other hand, the gelation temperature of the kappa-rich kappa/iota-hybrids is independent of their composition. This allows one to control the gel strength independent of the gelation or melting temperature. The conformational order-disorder transition of the kappa/iota-hybrids was studied using optical rotation and high-sensitivity differential scanning calorimetry. High-sensitivity DSC showed that the total transition enthalpy of the kappa/iota-hybrids goes through a minimum at 60 mol-% kappa-units, whereas for the mixture of kappa- and iota-carrageenan, the total transition enthalpy is a linear function of the composition. With respect to the ordering capability, the kappa/iota-hybrid carrageenans seem to behave as random block copolymers with length sequence distributions truncated from the side of the small lengths. Intrinsic thermodynamic properties (e.g., transition temperature and enthalpy) of kappa- and iota-sequences in these copolymers are close to those of their parent homopolymers. The critical sequence length for kappa-sequences is 2-fold of that for iota-sequences.

Diffusivity of whey protein and gum arabic in their coacervates.

Structural properties of whey protein (WP)/gum arabic (GA) coacervates were investigated by measuring the diffusivity of WP and GA in their coacervate phase as a function of pH by means of three different complementary techniques. The combination of these measurements revealed new insights into the structure of coacervates. Nuclear magnetic resonance (NMR) measured the self-diffusion coefficient of the GA in the coacervate phase prepared at various pH values. Fluorescence recovery after photobleaching (FRAP) was measured using a confocal scanning laser microscope. The WP and GA were covalently labeled with two different dyes. The time of fluorescence recovery, related to the inverse of the diffusion coefficient, was evaluated from the measurements, and the diffusivity of the WP and GA on a long time scale could be individually estimated at each pH value. Diffusing wave spectroscopy (DWS) combined with transmission measurement was carried out in the coacervate phase, and the diffusion coefficient, corresponding to the averaged diffusion of all particles that scattered in the system, was calculated as a function of pH. Independently of the technique used, the results showed that the diffusion of the WP and GA within the coacervate phase was reduced as compared to a diluted biopolymer mixture. NMR, DWS, and FRAP measurements gave similar results, indicating that the biopolymers moved the slowest in the coacervate matrix at pH 4.0-4.2. It is assumed that the diffusion of the WP and GA is reduced because of a higher electrostatic interaction between the biopolymers. Furthermore, FRAP results showed that in the coacervate phase WP molecules diffused 10 times faster than GA molecules. This result is very relevant because it shows that WP and GA move independently in the liquid coacervate phase. Finally, DWS measurements revealed that the coacervate phase rearranged with time, as evidenced by a decrease of the diffusion coefficient and a loss of the turbidity of the sample. A more homogeneous transparent coacervate phase was obtained after a few days/weeks. Faster rearrangement was obtained at pH 3.0 and 3.5 than at higher pH values.

Coil-helix transition of iota-carrageenan as a function of chain regularity.

A series of iota-carrageenans containing different amounts of nu-carrageenan (0-23 monomer %) have been prepared from neutrally extracted carrageenan of Eucheuma denticulatum. nu-Carrageenan is the biochemical precursor of iota-carrageenan. The conformational order-disorder transition and rheological properties of these carrageenans were studied using optical rotation, rheometry, size exclusion chromatography coupled to multiangle laser light scattering, and high-sensitivity differential scanning calorimetry. The helix forming capacity of iota-carrageenan turns out to decrease monotonously with increasing amount of nu-units. In contrast, the rheological properties of iota-carrageenan are remarkably enhanced by the presence of a small amount of nu-units, yielding a maximum twofold increase in G' at 3% nu-units. It is concluded that the structure-forming capacity of iota-carrageenan, containing a small amount of nu-carrageenan, is significantly higher than that of pure iota-carrageenan. This phenomenon is explained in terms of the balance between the helical content and the number of cross-links between chains, taking into consideration the fact that nu-units introduce "kinks" in the chain conformation enabling neighboring chains to connect. Increasing amounts of nu-units increase the number of cross-links in the network, resulting in increased gel strength. On the other hand, a reduced length of the helical strands weakens the cross-links between the different chains and, consequently, the gel.