The impact of an ultrasonic standing wave on the sorption behavior of proteins: Investigation of the role of acoustically induced non-spherical bubble oscillations.

HYPOTHESIS: Protein molecules adsorb on the air/liquid interface due to possessing a hydrophobic side. A full surface coverage is important in many processes such as in protein harvesting by foam fractionation. The adsorption of proteins in low concentration solutions is preceded by a relatively long time lag known as the induction period. This has been attributed to the formation of an adsorbed monolayer, which relies on the reorientation of the protein molecules. The reduction of the induction period can significantly facilitate the sorption process to reach full protein coverage. For this purpose acoustically induced non-spherical bubble oscillations can aid in the formation of the monolayer and enhance the sorption process. EXPERIMENT: In this study, low frequency ultrasound was used to induce non-spherical oscillations on an air bubble attached to a capillary. Profile analysis tensiometry was deployed to examine the effect of these non-spherical oscillations on the sorption dynamics of different proteins. FINDINGS: We observed that during the initial stages of adsorption, when the bubble surface is almost empty, non-spherical oscillations occur, which were found to significantly expedite the adsorption process. However, during later stages of the adsorption process, despite the continued presence of several sonication phenomena such as the primary radiation force and acoustic streaming, no change in adsorption behavior of the proteins could be noted. The occurrence, duration, and intensity of the non-spherical bubble oscillations appeared to be the sole contributing factors for the change of the sorption dynamics of proteins.

Interfacial Behavior of Particle-Laden Bubbles under Asymmetric Shear Flow.

The behavior of moving bubbles has mostly been studied in an axisymmetric flow field. To extend the knowledge to practical conditions, we investigate the interfacial and hydrodynamic properties of bubbles under asymmetric shear forces. Experiments are performed with a buoyant bubble at the tip of a capillary placed in a defined shear flow in the presence of surfactants, nanoparticles, and glass beads. The response of the interface to the surrounding asymmetric flow is measured under successive reduction of the surface area. Profile analysis tensiometry is utilized to investigate the dynamic surface tension and the surface rheology of the surfactant- and nanoparticle-laden interfaces. Microscopic particle image and tracking velocimetry are used to study the bulk flow and the interfacial mobility of the buoyant bubble. According to our results, the rotational component of the shear flow provokes an interfacial flow, which redistributes the adsorbed surfactants and particles at the interface. In the presence of NPSCs, a contiguous network of particles forms at the interface through densification of surface structures. We show that this interconnected nanoparticle network eventually stops the interfacial flow and decreases the mobility of the glass beads at the interface. The immobilization of the interface is characterized by a dimensionless number, defined as the ratio of the interfacial elasticity to bulk shear forces. This number provides an estimate of the interfacial forces required to impose interfacial immobility at a defined flow field. Our findings can serve as a basis to formulate boundary conditions for refined modeling and to predict the hydrodynamics of bubbles and droplets.

Interfacial flow of a surfactant-laden interface under asymmetric shear flow.

HYPOTHESIS: The shear stress of the axisymmetric flow field triggers a nonuniform distribution of the surfactants at the surface of a rising bubble, known as stagnant cap. The formation of the stagnant cap gives rise to Marangoni stresses that reduce the mobility of the interface, which in return reduces the rising velocity. However, the conditions in technological processes usually deviate from the linear rise of a single bubble in a quiescent unbounded liquid. Asymmetric shear can act on the bubble surface e.g. due to the vorticity in the surrounding flow, bubble-bubble interactions, or influence of the reactor wall. A different surfactant distribution at the interface is expected under asymmetric shear, which can change the hydrodynamic behavior of the interface drastically. EXPERIMENTS: Here we conduct model experiments with a bubble or a drop at the tip of a capillary placed in a defined flow field. Thereby we investigate the influence of asymmetric shear forces on the interface in the presence of surfactants. Microscopic particle tracking velocimetry is employed to measure the velocity of the surfactant-laden interface for different degrees of asymmetry in the surrounding liquid flow. FINDINGS: We show a direct experimental observation of the circulating flow at the interface under asymmetric shear, which prevents the formation of the typical stagnant cap. Additionally, we reveal that the interface remains mobile regardless of the surfactant concentration. Our results confirm that increasing the degree of asymmetry increases the shear forces and thus the interfacial velocity.

The influence of negatively charged silica nanoparticles on the surface properties of anionic surfactants: electrostatic repulsion or the effect of ionic strength?

The presence of negatively charged nanoparticles affects the surface activity of anionic surfactants in an aqueous phase. Recent studies suggest that electrostatic repulsive forces play an important role in increasing the surface activity of surfactants. However, the addition of nanoparticles also increases the ionic strength of the system, which has a significant impact on the surfactant's properties, e.g. its critical micelle concentration (CMC). To investigate how and to what extent electrostatic forces and ionic strength influence the behavior of ionic surfactants, the surface tension and elasticity of different solutions were measured using drop profile tensiometry as a function of the surfactant (SDBS), nanoparticle (silica) and salt (KNO3) concentration. It is observed that the surface activity of the surfactants is mainly influenced by the change in the system's ionic strength due to the presence of nanoparticles. Several characteristic parameters including the equivalent concentration of the surfactant, the CMC and the apparent partial molar area of the adsorbed surfactant are theoretically calculated and further employed to validate experimental observations. Both the nanoparticles and electrolyte decrease the CMC, while the equivalent concentration of the surfactant remains nearly constant. This paper presents a criterion to estimate the possible influence of such forces for nanoparticles of different sizes and mass fractions.

Influence of hydrophilic silica nanoparticles on the adsorption layer properties of non-ionic surfactants at water/heptane interface.

There is a notable paucity of studies investigating the impact of charged nanoparticles on the interfacial behavior of nonionic surfactants, assuming that the interactions are negligible in the absence of electrostatic forces. Here, we argue about our observations and the existence of a complex interfacial behavior in such systems depending on the type and chemical structure of surfactant. This study set out to investigate the effects of interactions between hydrophilic silica nanoparticles (NP) and non-ionic surfactants on water/heptane dynamic interfacial properties using drop profile analysis tensiometry (PAT). Three surfactants were studied, namely Triton X-100 (significantly soluble in water phase), C12DMPO (well soluble in both phases) and SPAN 80 (oil-soluble). The different chemical structures and partition coefficients of the surfactants enabled us to cover possible interactions and differentiate between bulk and interfacial interactions. We observed that hydrophilic silica NPs had a negligible effect on the interfacial behavior of Triton X-100, that they increased the surface activity of C12DMPO when both compounds are initially in the aqueous phase. Most interestingly is that the added NPs generated unstable interfacial NP-surfactant complexes and reduced the pseudo-equilibrium interfacial tension of oil-soluble surfactant, Span 80, even though NPs and surfactants were in different bulk phases.