Water reorientation dynamics in colloidal water-oil emulsions.

We study the molecular-scale properties of colloidal water-oil emulsions consisting of 120-290 nm oil droplets embedded in water. This type of emulsion can be prepared with low concentrations of surfactants and is usually kinetically stable. Even though colloidal water-oil emulsions are used ubiquitously, their molecular properties are still poorly understood. Here we study the orientational dynamics of water molecules in these emulsions using polarization resolved pump-probe infrared spectroscopy, for varying surfactant concentrations, droplet sizes, and temperatures. We find that the majority of the water molecules reorients with the same time constant as in bulk water, while a small fraction of the water molecules reorients on a much longer time scale. These slowly reorienting water molecules are interacting with the surface of the oil droplets. The fraction of slowly orienting water molecules is proportional to the oil volume fraction, and shows a negligible dependence on the average droplet size. This finding indicates that the total surface area of the oil droplets is quite independent of the average droplet size, which indicates that the larger oil droplets are quite corrugated, showing large protrusions into the water phase.

Origin of the extremely high elasticity of bulk emulsions, stabilized by Yucca Schidigera saponins.

We found experimentally that the elasticity of sunflower oil-in-water emulsions (SFO-in-W) stabilized by Yucca Schidigera Roezl saponin extract, is by >50 times higher as compared to the elasticity of common emulsions. We revealed that strong specific interactions between the phytosterols from the non-purified oil and the saponins from the Yucca extract lead to the formation of nanostructured adsorption layers which are responsible for the very high elasticity of the oil-water interface and of the respective bulk emulsions. Remarkably, this extra high emulsion elasticity inhibits the emulsion syneresis even at 65 vol% of the oil drops - these emulsions remain homogeneous and stable even after 30 days of shelf-storage. These results demonstrate that the combination of saponin and phytosterols is a powerful new approach to structure oil-in-water emulsions with potential applications for formulating healthier functional food.

Role of interfacial elasticity for the rheological properties of saponin-stabilized emulsions.

HYPOTHESIS: Saponins are natural surfactants which can provide highly viscoelastic interfaces. This property can be used to quantify precisely the effect of interfacial dilatational elasticity on the various rheological properties of bulk emulsions. EXPERIMENTS: We measured the interfacial dilatational elasticity of adsorption layers from four saponins (Quillaja, Escin, Berry, Tea) adsorbed on hexadecane-water and sunflower oil-water interfaces. In parallel, the rheological properties under steady and oscillatory shear deformations were measured for bulk emulsions, stabilized by the same saponins (oil volume fraction between 75 and 85%). FINDINGS: Quillaja saponin and Berry saponin formed solid adsorption layers (shells) on the SFO-water interface. As a consequence, the respective emulsions contained non-spherical drops. For the other systems, the interfacial elasticities varied between 2 mN/m and 500 mN/m. We found that this interfacial elasticity has very significant impact on the emulsion shear elasticity, moderate effect on the dynamic yield stress, and no effect on the viscous stress of the respective steadily sheared emulsions. The last conclusion is not trivial, because the dilatational surface viscoelasticity is known to have strong impact on the viscous stress of steadily sheared foams. Mechanistic explanations of all observed effects are described.

Molecular Origin of the Elastic State of Aqueous Hyaluronic Acid.

The macroscopic mechanical properties of biological hydrogels are broadly studied and successfully mimicked in synthetic materials, but little is known about the molecular interactions that mediate these properties. Here, we use two-dimensional infrared spectroscopy to study the pH-induced gelation of hyaluronic acid, a ubiquitous biopolymer, which undergoes a transition from a viscous to an elastic state in a narrow pH range around 2.5. We find that the gelation originates from the enhanced formation of strong interchain connections, consisting of a double amide-COOH hydrogen bond and an N-D-COO- hydrogen bond on the adjacent sugars of the hyaluronan disaccharide unit. We confirm the enhanced interchain connectivity in the elastic state by atomic force microscopy imaging.

Growth of wormlike micelles in nonionic surfactant solutions: Quantitative theory vs. experiment.

Despite the considerable advances of molecular-thermodynamic theory of micelle growth, agreement between theory and experiment has been achieved only in isolated cases. A general theory that can provide self-consistent quantitative description of the growth of wormlike micelles in mixed surfactant solutions, including the experimentally observed high peaks in viscosity and aggregation number, is still missing. As a step toward the creation of such theory, here we consider the simplest system - nonionic wormlike surfactant micelles from polyoxyethylene alkyl ethers, CiEj. Our goal is to construct a molecular-thermodynamic model that is in agreement with the available experimental data. For this goal, we systematized data for the micelle mean mass aggregation number, from which the micelle growth parameter was determined at various temperatures. None of the available models can give a quantitative description of these data. We constructed a new model, which is based on theoretical expressions for the interfacial-tension, headgroup-steric and chain-conformation components of micelle free energy, along with appropriate expressions for the parameters of the model, including their temperature and curvature dependencies. Special attention was paid to the surfactant chain-conformation free energy, for which a new more general formula was derived. As a result, relatively simple theoretical expressions are obtained. All parameters that enter these expressions are known, which facilitates the theoretical modeling of micelle growth for various nonionic surfactants in excellent agreement with the experiment. The constructed model can serve as a basis that can be further upgraded to obtain quantitative description of micelle growth in more complicated systems, including binary and ternary mixtures of nonionic, ionic and zwitterionic surfactants, which determines the viscosity and stability of various formulations in personal-care and house-hold detergency.

Hardening of particle/oil/water suspensions due to capillary bridges: Experimental yield stress and theoretical interpretation.

Suspensions of colloid particles possess the remarkable property to solidify upon the addition of minimal amount of a second liquid that preferentially wets the particles. The hardening is due to the formation of capillary bridges (pendular rings), which connect the particles. Here, we review works on the mechanical properties of such suspensions and related works on the capillary-bridge force, and present new rheological data for the weakly studied concentration range 30-55 vol% particles. The mechanical strength of the solidified capillary suspensions, characterized by the yield stress Y, is measured at the elastic limit for various volume fractions of the particles and the preferentially wetting liquid. A quantitative theoretical model is developed, which relates Y with the maximum of the capillary-bridge force, projected on the shear plane. A semi-empirical expression for the mean number of capillary bridges per particle is proposed. The model agrees very well with the experimental data and gives a quantitative description of the yield stress, which increases with the rise of interfacial tension and with the volume fractions of particles and capillary bridges, but decreases with the rise of particle radius and contact angle. The quantitative description of capillary force is based on the exact theory and numerical calculation of the capillary bridge profile at various bridge volumes and contact angles. An analytical formula for Y is also derived. The comparison of the theoretical and experimental strain at the elastic limit reveals that the fluidization of the capillary suspension takes place only in a deformation zone of thickness up to several hundred particle diameters, which is adjacent to the rheometer's mobile plate. The reported experimental results refer to water-continuous suspension with hydrophobic particles and oily capillary bridges. The comparison of data for bridges from soybean oil and hexadecane surprisingly indicate that the yield strength is greater for the suspension with soybean oil despite its lower interfacial tension against water. The result can be explained with the different contact angles of the two oils in agreement with the theoretical predictions. The results could contribute for a better understanding, quantitative prediction and control of the mechanical properties of three-phase capillary suspensions solid/liquid/liquid.

Rheology of particle/water/oil three-phase dispersions: Electrostatic vs. capillary bridge forces.

HYPOTHESIS: Particle/water/oil three-phase capillary suspensions possess the remarkable property to solidify upon the addition of minimal amount of the second (dispersed) liquid. The hardening of these suspensions is due to capillary bridges, which interconnect the particles (pendular state). Electrostatic repulsion across the oily phase, where Debye screening by electrolyte is missing, could also influence the hardness of these suspensions. EXPERIMENTS: We present data for oil-continuous suspensions with aqueous capillary bridges between hydrophilic SiO2 particles at particle volume fractions 35-45%. The hardness is characterized by the yield stress Y for two different oils: mineral (hexadecane) and vegetable (soybean oil). FINDINGS AND MODELLING: The comparison of data for the "mirror" systems of water- and oil-continuous capillary suspensions shows that Y is lower for the oil-continuous ones. The theoretical model of yield stress is upgraded by including a contribution from electrostatic repulsion, which partially counterbalances the capillary-bridge attraction and renders the suspensions softer. The particle charge density determined from data fits is close to that obtained in experiments with monolayers from charged colloid particles at oil/water interfaces. The results could contribute for better understanding, quantitative prediction and control of the mechanical properties of solid/liquid/liquid capillary suspensions.

Toward Scalable Fabrication of Hierarchical Silica Capsules with Integrated Micro-, Meso-, and Macropores.

Hierarchical porous structures are ubiquitous in biological organisms and inorganic systems. Although such structures have been replicated, designed, and fabricated, they are often inferior to naturally occurring analogues. Apart from the complexity and multiple functionalities developed by the biological systems, the controllable and scalable production of hierarchically porous structures and building blocks remains a technological challenge. Herein, a facile and scalable approach is developed to fabricate hierarchical hollow spheres with integrated micro-, meso-, and macropores ranging from 1 nm to 100 µm (spanning five orders of magnitude). (Macro)molecules, micro-rods (which play a key role for the creation of robust capsules), and emulsion droplets have been successfully employed as multiple length scale templates, allowing the creation of hierarchical porous macrospheres. Thanks to their specific mechanical strength, these hierarchical porous spheres could be incorporated and assembled as higher level building blocks in various novel materials.

Adhesion of bubbles and drops to solid surfaces, and anisotropic surface tensions studied by capillary meniscus dynamometry.

Here, we review the principle and applications of two recently developed methods: the capillary meniscus dynamometry (CMD) for measuring the surface tension of bubbles/drops, and the capillary bridge dynamometry (CBD) for quantifying the bubble/drop adhesion to solid surfaces. Both methods are based on a new data analysis protocol, which allows one to decouple the two components of non-isotropic surface tension. For an axisymmetric non-fluid interface (e.g. bubble or drop covered by a protein adsorption layer with shear elasticity), the CMD determines the two different components of the anisotropic surface tension, σs and σφ, which are acting along the "meridians" and "parallels", and vary throughout the interface. The method uses data for the instantaneous bubble (drop) profile and capillary pressure, but the procedure for data processing is essentially different from that of the conventional drop shape analysis (DSA) method. In the case of bubble or drop pressed against a substrate, which forms a capillary bridge, the CBD method allows one to determine also the capillary-bridge force for both isotropic (fluid) and anisotropic (solidified) adsorption layers. The experiments on bubble (drop) detachment from the substrate show the existence of a maximal pulling force, Fmax, that can be resisted by an adherent fluid particle. Fmax can be used to quantify the strength of adhesion of bubbles and drops to solid surfaces. Its value is determined by a competition of attractive transversal tension and repulsive disjoining pressure forces. The greatest Fmax values have been measured for bubbles adherent to glass substrates in pea-protein solutions. The bubble/wall adhesion is lower in solutions containing the protein HFBII hydrophobin, which could be explained with the effect of sandwiched protein aggregates. The applicability of the CBD method to emulsion systems is illustrated by experiments with soybean-oil drops adherent to hydrophilic and hydrophobic substrates in egg yolk solutions. The results reveal how the interfacial rigidity, as well as the bubble/wall and drop/wall adhesion forces, can be quantified and controlled in relation to optimizing the properties of foams and emulsions.

Hydrophobic modification of chitin whisker and its potential application in structuring oil.

A facile approach was developed to modify chitin whiskers by reacting them with bromohexadecane, and the potential application of modified whiskers in structuring oil was evaluated. The results of Fourier transform infrared spectra (FT-IR), wide-angle X-ray diffraction (XRD), elemental analysis, solid (13)C NMR, and differential scanning calorimeter (DSC) confirmed that the long alkyl chains were successfully introduced to the chitin whiskers and endowed them with improved hydrophobicity and thermal transition. By hot pressing the modified whiskers, the highly hydrophobic whisker sheets were constructed, showing high contact angles close to 150°. The hydrophobic interaction between the long alkyl chains and chitin backbone induced the crystal alignment with micro-nano structure, leading to the surface roughness and high hydrophobicity of the sheets. Furthermore, the modified whiskers could form a stable dispersion in sunflower oil, displaying a remarkable thickening effect. The viscosity of the oily suspension exhibited temperature dependence and shear-thinning behavior, suggesting great potentials to fabricate oleogel without adding any saturated fat. Furthermore, the intrinsic biocompatibility of α-chitin structure benefits its application in foodstuff, cosmetics, and medical fields.

Shear rheology of mixed protein adsorption layers vs their structure studied by surface force measurements.

The hydrophobins are proteins that form the most rigid adsorption layers at liquid interfaces in comparison with all other investigated proteins. The mixing of hydrophobin HFBII with other conventional proteins is expected to reduce the surface shear elasticity and viscosity, E(sh) and η(sh), proportional to the fraction of the conventional protein. However, the experiments show that the effect of mixing can be rather different depending on the nature of the additive. If the additive is a globular protein, like ß-lactoglobulin and ovalbumin, the surface rigidity is preserved, and even enhanced. The experiments with separate foam films indicate that this is due to the formation of a bilayer structure at the air/water interface. The more hydrophobic HFBII forms the upper layer adjacent to the air phase, whereas the conventional globular protein forms the lower layer that faces the water phase. Thus, the elastic network formed by the adsorbed hydrophobin remains intact, and even reinforced by the adjacent layer of globular protein. In contrast, the addition of the disordered protein ß-casein leads to softening of the HFBII adsorption layer. Similar (an even stronger) effect is produced by the nonionic surfactant Tween 20. This can be explained with the penetration of the hydrophobic tails of ß-casein and Tween 20 between the HFBII molecules at the interface, which breaks the integrity of the hydrophobin interfacial elastic network. The analyzed experimental data for the surface shear rheology of various protein adsorption layers comply with a viscoelastic thixotropic model, which allows one to determine E(sh) and η(sh) from the measured storage and loss moduli, G' and G″. The results could contribute for quantitative characterization and deeper understanding of the factors that control the surface rigidity of protein adsorption layers with potential application for the creation of stable foams and emulsions with fine bubbles or droplets.

Capillary meniscus dynamometry­method for determining the surface tension of drops and bubbles with isotropic and anisotropic surface stress distributions.

The stresses acting in interfacial adsorption layers with surface shear elasticity are, in general, anisotropic and non-uniform. If a pendant drop or buoyant bubble is covered with such elastic layer, the components of surface tension acting along the "meridians" and "parallels", σ(s) and σ(φ), can be different and, then, the conventional drop shape analysis (DSA) is inapplicable. Here, a method for determining σ(s) and σ(φ) is developed for axisymmetric menisci. This method, called 'capillary meniscus dynamometry' (CMD), is based on processing data for the digitized drop/bubble profile and capillary pressure. The principle of the CMD procedure for data processing is essentially different from that of DSA. Applying the tangential and normal surface stress balance equations, σ(s) and σ(φ) are determined in each interfacial point without using any rheological model. The computational procedure is fast and could be used in real time, during a given process. The method is applied to determine σ(s) and σ(φ) for bubbles and drops formed on the tip of a capillary immersed in solutions of the protein HFBII hydrophobin. Upon a surface compression, meridional wrinkles appear on the bubble surface below the bubble "equator", where the azimuthal tension σ(φ) takes negative values. The CMD method allows one to determine the local tensions acting in anisotropic interfacial layers (films, membranes), like those formed from proteins, polymers, asphaltenes and phospholipids. The CMD is applicable also to fluid interfaces (e.g. surfactant solutions), for which it gives the same surface tension as the conventional methods.

The role of the hydrophobic phase in the unique rheological properties of saponin adsorption layers.

Saponins are a diverse class of natural, plant derived surfactants, with peculiar molecular structure consisting of a hydrophobic scaffold and one or several hydrophilic oligosaccharide chains. Saponins have strong surface activity and are used as natural emulsifiers and foaming agents in food and beverage, pharmaceutical, ore processing, and other industries. Many saponins form adsorption layers at the air-water interface with extremely high surface elasticity and viscosity. The molecular origin of the observed unique interfacial visco-elasticity of saponin adsorption layers is of great interest from both scientific and application viewpoints. In the current study we demonstrate that the hydrophobic phase in contact with water has a very strong effect on the interfacial properties of saponins and that the interfacial elasticity and viscosity of the saponin adsorption layers decrease in the order: air > hexadecane ≫ tricaprylin. The molecular mechanisms behind these trends are analyzed and discussed in the context of the general structure of the surfactant adsorption layers at various nonpolar phase-water interfaces.

Growth of bubbles on a solid surface in response to a pressure reduction.

A diffusion-controlled method is presented to study the growth of bubbles on a solid surface. The bubbles are nucleated spontaneously on a hydrophobic smooth surface in response to a sudden pressure reduction and then grow with an expanding contact line. The evolution of the bubbles in the early stage is found to grow with a constant bubble radius and a decreasing contact angle, while the bubbles continue their growth with a constant contact angle and an increasing bubble radius after the contact angle reaches its equilibrium value. A total variation of about 60° of the contact angle is observed during the growth of the bubbles with the size scale of 10-100 µm in radius. The growing process is described by the diffusion theory with the validation of the growth constant.

Sonication-microfluidics for fabrication of nanoparticle-stabilized microbubbles.

An approach based upon sonication-microfluidics is presented to fabricate nanoparticle-coated microbubbles. The gas-in-liquid slug flow formed in a microchannel is subjected to ultrasound, leading to cavitation at the gas-liquid interface. Therefore, microbubbles are formed and then stabilized by the nanoparticles contained in the liquid. Compared to the conventional sonication method, this sonication-microfluidics continuous flow approach has unlimited gas nuclei for cavitation that yields continuous production of foam with shorter residence time. By controlling the flow rate ratios of the gas to the liquid, this method also achieves a higher production volume, smaller bubble size, and less waste of the nanoparticles needed to stabilize the microbubbles.

Surface pressure and elasticity of hydrophobin HFBII layers on the air-water interface: rheology versus structure detected by AFM imaging.

Here, we combine experiments with Langmuir trough and atomic force microscopy (AFM) to investigate the reasons for the special properties of layers from the protein HFBII hydrophobin spread on the air-water interface. The hydrophobin interfacial layers possess the highest surface dilatational and shear elastic moduli among all investigated proteins. The AFM images show that the spread HFBII layers are rather inhomogeneous, (i.e., they contain voids, monolayer and multilayer domains). A continuous compression of the layer leads to filling the voids and transformation of a part of the monolayer into a trilayer. The trilayer appears in the form of large surface domains, which can be formed by folding and subduction of parts from the initial monolayer. The trilayer appears also in the form of numerous submicrometer spots, which can be obtained by forcing protein molecules out of the monolayer and their self-assembly into adjacent pimples. Such structures are formed because not only the hydrophobic parts, but also the hydrophilic parts of the HFBII molecules can adhere to each other in the water medium. If a hydrophobin layer is subjected to oscillations, its elasticity considerably increases, up to 500 mN/m, which can be explained with compaction. The relaxation of the layer's tension after expansion or compression follows the same relatively simple law, which refers to two-dimensional diffusion of protein aggregates within the layer. The characteristic diffusion time after compression is longer than after expansion, which can be explained with the impedence of diffusion in the more compact interfacial layer. The results shed light on the relation between the mesoscopic structure of hydrophobin interfacial layers and their unique mechanical properties that find applications for the production of foams and emulsions of extraordinary stability; for the immobilization of functional molecules at surfaces, and as coating agents for surface modification.

Interfacial layers from the protein HFBII hydrophobin: dynamic surface tension, dilatational elasticity and relaxation times.

The pendant-drop method (with drop-shape analysis) and Langmuir trough are applied to investigate the characteristic relaxation times and elasticity of interfacial layers from the protein HFBII hydrophobin. Such layers undergo a transition from fluid to elastic solid films. The transition is detected as an increase in the error of the fit of the pendant-drop profile by means of the Laplace equation of capillarity. The relaxation of surface tension after interfacial expansion follows an exponential-decay law, which indicates adsorption kinetics under barrier control. The experimental data for the relaxation time suggest that the adsorption rate is determined by the balance of two opposing factors: (i) the barrier to detachment of protein molecules from bulk aggregates and (ii) the attraction of the detached molecules by the adsorption layer due to the hydrophobic surface force. The hydrophobic attraction can explain why a greater surface coverage leads to a faster adsorption. The relaxation of surface tension after interfacial compression follows a different, square-root law. Such behavior can be attributed to surface diffusion of adsorbed protein molecules that are condensing at the periphery of interfacial protein aggregates. The surface dilatational elasticity, E, is determined in experiments on quick expansion or compression of the interfacial protein layers. At lower surface pressures (<11 mN/m) the experiments on expansion, compression and oscillations give close values of E that are increasing with the rise of surface pressure. At higher surface pressures, E exhibits the opposite tendency and the data are scattered. The latter behavior can be explained with a two-dimensional condensation of adsorbed protein molecules at the higher surface pressures. The results could be important for the understanding and control of dynamic processes in foams and emulsions stabilized by hydrophobins, as well as for the modification of solid surfaces by adsorption of such proteins.

Surface shear rheology of adsorption layers from the protein HFBII hydrophobin: effect of added ß-casein.

The surface shear rheology of hydrophobin HFBII adsorption layers is studied in angle-ramp/relaxation regime by means of a rotational rheometer. The behavior of the system is investigated at different shear rates and concentrations of added ß-casein. In angle-ramp regime, the experimental data comply with the Maxwell model of viscoelastic behavior. From the fits of the rheological curves with this model, the surface shear elasticity and viscosity, E(sh) and η(sh), are determined at various fixed shear rates. The dependence of η(sh) on the rate of strain obeys the Herschel-Bulkley law. The data indicate an increasing fluidization (softening) of the layers with the rise of the shear rate. The addition of ß-casein leads to more rigid adsorption layers, which exhibit a tendency of faster fluidization at increasing shear rates. In relaxation regime, the system obeys a modified Andrade's (cubic root) law, with two characteristic relaxation times. The fact that the data comply with the Maxwell model in angle-ramp regime, but follow the modified Andrade's low in relaxation regime, can be explained by the different processes occurring in the viscoelastic protein adsorption layer in these two regimes: breakage and restoration of intermolecular bonds at angle-ramp vs solidification of the layer at relaxation.

A novel hybrid system for the fabrication of a fibrous mesh with micro-inclusions.

A novel hybrid system combining microfluidic and co-axial electrospinning techniques has been used to generate different types of fibre structures with varied desirable inclusions using food grade polymers, ethyl cellulose and sodium alginate. The processing conditions in the microfluidic T-junction device, i.e. gas pressure and liquid flow rate were adjusted in order to generate near-monodisperse microbubbles which subsequently serve as a platform for particle generation. These particles exhibit micro-scale diameters and different shapes and some bubbles were incorporated into the fibrous mesh prepared by concurrent electrospinning. The fibre/particle structures obtained with different polymers via this novel method could potentially have many applications in various engineering and biological sectors.

Self-assembled bilayers from the protein HFBII hydrophobin: nature of the adhesion energy.

The hydrophobins are a class of amphiphilic proteins which spontaneously adsorb at the air/water interface and form elastic membranes of high mechanical strength as compared to other proteins. The mechanism of hydrophobin adhesion is of interest for fungal biology and for various applications in electronics, medicine, and food industry. We established that the drainage of free foam films formed from HFBII hydrophobin solutions ends with the appearance of a 6 nm thick film, which consists of two layers of protein molecules, that is, it is a self-assembled bilayer (S-bilayer), with hydrophilic domains pointing inward and hydrophobic domains pointing outward. Its formation is accompanied by a considerable energy gain, which is much greater than that typically observed with free liquid films. The experiments at different pH show that this attraction between the "hydrophilic" parts of the HFBII molecules is dominated by the short-range hydrophobic interaction rather than by the patch-charge electrostatic attraction.