Effects of Aqueous Isotopic Substitution on the Adsorption Dynamics and Dilational Rheology of ß-Lactoglobulin Layers at the Water/Air Interface.

The effect of the degree of isotopic substitution of the aqueous medium on the adsorption kinetics and the surface dilational rheological behavior at the water/air interface of the globular protein ß-lactoglobulin was investigated. Aqueous solutions with fixed concentrations of 1 µM protein and 10 mM hydrogenous buffer with controlled pH 7 were prepared in H2O, D2O, and an isotopic mixture of 8.1% v/v D2O in H2O (called air contrast matched water, ACMW). Using a bubble shape analysis tensiometer, we obtained various experimental dependencies of the dilational viscoelasticity modulus E as a function of the dynamic surface pressure and of the frequency and amplitude of bubble surface area oscillations, either in the course of adsorption or after having reached a steady state. In general, the results revealed virtually no effect from substituting H2O by ACMW but distinct albeit relatively weak effects for intermediate adsorption times for D2O as the aqueous phase. In the final stage of adsorption, established after around 10 h, the equilibrium adsorption and the dilational rheological behavior of all protein layers under investigation are only very weakly affected by the presence of D2O. The obtained results help to design experimental protocols for protein adsorption studies, for example, by neutron reflectivity.

Evaluation of Interfacial Structure of Self-Assembled Nanoparticle Layers: Use of Standard Deviation between Calculated and Experimental Drop Profiles as a Novel Method.

The self-assembly of nanoparticles (NPs) at interfaces is currently a topic of increasing interest due to numerous applications in food technology, pharmaceuticals, cosmetology, and oil recovery. It is possible to create tunable interfacial structures with desired characteristics using tailored nanoparticles that can be precisely controlled with respect to shape, size, and surface chemistry. To address these functionalities, it is essential to develop techniques to study the properties of the underlying structure. In this work, we propose an experimental approach utilizing the standard deviation of drop profiles calculated by the Laplace equation from experimental drop profiles (STD), as an alternative to the Langmuir trough or precise microscopic methods, to detect the initiation of closely packed conditions and the collapse of the adsorbed layers of CTAB-nanosilica complexes. The experiments consist of dynamic surface/interfacial tension measurements using drop profile analysis tensiometry (PAT) and large-amplitude drop surface area compression/expansion cycles. The results demonstrate significant changes in STD values at the onset of the closely packed state of nanoparticle-surfactant complexes and the monolayer collapse. The STD trend was explained in detail and shown to be a powerful tool for analyzing the adsorption and interfacial structuring of nanoparticles. Different collapse mechanisms were reported for NP monolayers at the liquid/liquid and air/liquid interfaces. We show that the interfacial tension (IFT) is solely dependent on the extent of interfacial coverage by nanoparticles, while the surfactants regulate only the hydrophobicity of the self-assembled complexes. Also, the irreversible adsorption of nanoparticles and the increasing number of adsorbed complexes after the collapse were observed by performing consecutive drop surface compression/expansion cycles. In addition to a qualitative characterization of adsorption layers, the potential of a quantitative calculation of the parameter STD such as the number of adsorbed nanoparticles at the interface and the distance between them at different states of the interfacial layer was discussed.

Effect of surfactants on the interfacial viscoelasticity and stability of silk fibroin at different oil-water interfaces.

BACKGROUND: The biocompatible amphiphilic silk fibroin, extracted from domesticated silkworms, can adsorb at the oil-water interface and form elastic interfacial layers. In this study, three surfactants (cationic cetyltrimethylammonium bromide, the nonionic polyoxyethylene sorbitan monolaurate, and the anionic sodium dodecyl sulfate) were selected to investigate, through interfacial shear rheology, the influences of surfactants on the interfacial viscoelasticity and stability of silk fibroin at the interfaces between water and two different oils. RESULTS: The presence of surfactant prolongs the equilibration time and enhances the interfacial elastic modulus and toughness of the interfacial silk fibroin layers, especially at the nonpolar dodecane-water interface. However, when the surfactant exceeds a critical concentration, the shear modulus and stability of interfacial silk fibroin layers begin to decrease due to the competitive adsorption of surfactant molecules and the weakening of the protein network. Owing to electrostatic interactions, the ionic surfactants cetyltrimethylammonium bromide and sodium dodecyl sulfate can form more hydrophobic complexes with silk fibroin, which results in higher shear moduli than for silk fibroin and silk fibroin-polyoxyethylene sorbitan monolaurate mixture. CONCLUSION: Both the surfactant type and oil polarity play important roles in the adsorption, shear viscoelasticity, and stability of silk fibroin at the oil-water interface. Enhanced interactions between a silk fibroin-surfactant mixture and the oil phase delay the equilibration of the adsorption layers but strengthen the stability of interfacial layers. © 2023 Society of Chemical Industry.

Interface Adsorption versus Bulk Micellization of Surfactants: Insights from Molecular Simulations.

Surfactants play essential roles in many commonplace applications and industrial processes. Although significant progress has been made over the past decades with regard to model-based predictions of the behavior of surfactants, important challenges have remained. Notably, the characteristic time scales of surfactant exchange among micelles, interfaces, and the bulk solution typically exceed the time scales currently accessible with atomistic molecular dynamics (MD) simulations. Here, we circumvent this problem by introducing a framework that combines the general thermodynamic principles of self-assembly and interfacial adsorption with atomistic MD simulations. This approach provides a full thermodynamic description based on equal chemical potentials and connects the surfactant bulk concentration, the experimental control parameter, with the surfactant surface density, the suitable control parameter in MD simulations. Self-consistency is demonstrated for the nonionic surfactant C12EO6 (hexaethylene glycol monododecyl ether) at an alkane/water interface, for which the adsorption and pressure isotherms are computed. The agreement between the simulation results and experiments is semiquantitative. A detailed analysis reveals that the used atomistic model captures well the interactions between surfactants at the interface but less so their adsorption affinities to the interface and incorporation into micelles. Based on a comparison with other recent studies that pursued similar modeling challenges, we conclude that the current atomistic models systematically overestimate the surfactant affinities to aggregates, which calls for improved models in the future.

Dynamic Properties of Adsorption Layers of κ-Casein Fibrils.

The dynamic surface properties of native κ-casein solutions and aqueous dispersions of its fibrils differ significantly from the corresponding properties of the systems with globular proteins. The dependence of the dynamic surface elasticity of κ-casein solutions on surface pressure has a local maximum, indicating partial displacement of macromolecules from the proximal region of the surface layer to the distal one. This dependence becomes monotonic for fibril dispersions, similar to the results for dispersions of globular protein fibrils, but unlike the latter case, the surface elasticity close to the steady state reaches values that are approximately four times higher than the data for native protein solutions at the same concentrations.

Dynamic Surface Properties of α-Lactalbumin Fibril Dispersions.

The dynamic surface properties of aqueous dispersions of α-lactalbumin (ALA) amyloid fibrils differ noticeably from the properties of the fibril dispersions of other globular proteins. As a result, the protocol of the application of ALA fibrils to form stable foams and emulsions has to be deviate from that of other protein fibrils. Unlike the fibrils of ß-lactoglobulin and lysozyme, ALA fibrils can be easily purified from hydrolyzed peptides and native protein molecules. The application of the oscillating barrier method shows that the dynamic surface elasticity of ALA fibril dispersions exceeds the surface elasticity of native protein solutions at pH 2. ALA fibrils proved to be stable at this pH, but the stability breaks at higher pH levels when the fibrils start to release small peptides of high surface activity. As a result, the dynamic surface properties of ALA coincide with those of native protein solutions. The ionic strength strongly influences the adsorption kinetics of both fibril dispersions and native protein solutions but have almost no impact on the structure of the adsorption layers.

Surface Properties of Protein-Polyelectrolyte Solutions. Impact of Polyelectrolyte Hydrophobicity.

The strong influence of an amphiphilic polyelectrolyte, poly(N,N-diallyl-N-hexyl-N-methylammonium chloride), on the surface properties of solutions of globular proteins (lysozyme, ß-lactoglobulin, bovine serum albumin, and green fluorescent protein) depends on the protein structure and allows elucidation of the contribution of hydrophobic interactions in the protein-polyelectrolyte complex formation at the liquid-gas interface. At the beginning of adsorption, the surface properties are determined by the unbound amphiphilic component, but the influence of the protein-polyelectrolyte complexes of high surface activity increases at the approach to equilibrium. The kinetic dependencies of the dilational dynamic surface elasticity with one or two local maxima give a possibility to distinguish clearly between different steps of the adsorption process and to trace the formation of the distal region of the adsorption layer. The conclusions from the surface rheological data are corroborated by ellipsometric and tensiometric results.

Advances in CO2-switchable surfactants towards the fabrication and application of responsive colloids.

CO2-switchable surfactants have selective surface-activity, which can be activated or deactivated either by adding or removing CO2 from the solution. This feature enables us to use them in the fabrication of responsive colloids, a group of dispersed systems that can be controlled by changing the environmental conditions. In chemical processes, including extraction, reaction, or heterogeneous catalysis, colloids are required in some specific steps of the processes, in which maximum contact area between immiscible phases or reactants is desired. Afterward, the colloids must be broken for the postprocessing of products, solvents, and agents, which can be facilitated by using CO2-switchable surfactants in surfactant-stabilized colloids. These surfactants are mainly cationic and can be activated by the protonation of a nitrogen-containing group upon sparging CO2 gas. Also, CO2-switchable superamphiphiles can be formed by non-covalent bonding between components at least one of which is CO2-switchable. So far, CO2-switchable surfactants have been used in CO2-switchable spherical and wormlike micelles, vesicles, emulsions, foams, and Pickering emulsions. Here, we review the fabrication procedure, chemical structure, switching scheme, stability, environmental conditions, and design philosophy of such responsive colloids. Their fields of application are wide, including emulsion polymerization, catalysis, soil washing, drug delivery, extraction, viscosity control, and oil transportation. We also emphasize their application for the CO2-assisted enhanced oil recovery (EOR) process as a promising approach for carbon capture, utilization, and storage to combat climate change.

Dynamic interfacial properties and foam behavior of licorice root extract solutions.

Licorice (Glycyrrhiza glabra) is a useful plant of the family Fabaceae, with sweet-tasting roots. The root extract of this plant is rich in saponins, so it can be considered a source of natural surfactants. This research provides some applicable information about the dynamic surface tension and foam behavior of aqueous solutions of licorice root extract (LRE). The pendant drop shape analysis was utilized to study the surface tension and dilational surface rheology of LRE at the water/air interface. The Bikerman type experiment was used to measure foamability and foam stability of aqueous LRE solutions. The equilibrium surface tensions reveal that the LRE contains surface-active components and is capable of reducing the surface tension by 25 mN/m at the critical aggregation concentration (CAC). The surface dilational visco-elasticity measurements proved that the adsorption layers are predominantly of elastic nature. Also the foamability and foam stability show a meaningful correlation with the dynamic surface properties. This study aims to contribute to the development of appropriate utilization of the benefits provided by a biosurfactant source in foam-related commercial applications.

Isolating the interface of an emulsion using X-ray scattering and tensiometry to understand protein-modulated alkylglyceride crystallisation.

HYPOTHESIS: Dairy proteins and mono- and diglycerides (MDG) are often used in unison to tailor the properties of dairy-based emulsions. However, there are significant gaps in our understanding of how proteins affect lipid crystallisation at the oil-water interface. We have used a unique combination of interfacially-sensitive techniques to elucidate the impact of dairy proteins on interfacial MDG crystal formation. EXPERIMENTS: The formation temperature of interfacial MDG crystals was assessed through interfacial tension studies via drop shape analysis. Small and Wide-Angle X-ray Scattering measurements were performed on isolated oil-water interfaces, allowing for in-situ interrogation of MDG crystal structure and concentration at and near the interface. FINDINGS: Dairy proteins are seen to reduce the temperature at which MDG crystals form at the oil-water interface. The displacement of proteins upon interfacial crystal formation was also clearly observed in interfacial tension measurements. For the first time, lipid crystals formed at the oil-water interface have been characterised using X-ray scattering. All scattering studies showed no change to the MDG crystal structures at the oil-water interface in the presence of adsorbed proteins. The results demonstrate that informed selection of emulsifier components is critical to controlling interfacial crystallisation with concomitant impact on emulsion stability.

Spread Layers of Lysozyme Microgel at Liquid Surface.

The spread layers of lysozyme (LYS) microgel particles were studied by surface dilational rheology, infrared reflection-absorption spectra, Brewster angle microscopy, atomic force microscopy, and scanning electron microscopy. It is shown that the properties of LYS microgel layers differ significantly from those of ß-lactoglobulin (BLG) microgel layers. In the latter case, the spread protein layer is mainly a monolayer, and the interactions between particles lead to the increase in the dynamic surface elasticity by up to 140 mN/m. In contrast, the dynamic elasticity of the LYS microgel layer does not exceed the values for pure protein layers. The compression isotherms also do not exhibit specific features of the layer collapse that are characteristic for the layers of BLG aggregates. LYS aggregates form trough three-dimensional clusters directly during the spreading process, and protein spherulites do not spread further along the interface. As a result, the liquid surface contains large, almost empty regions and some patches of high local concentration of the microgel particles.

DNA Penetration into a Lysozyme Layer at the Surface of Aqueous Solutions.

The interactions of DNA with lysozyme in the surface layer were studied by performing infrared reflection-absorption spectroscopy (IRRAS), ellipsometry, surface tensiometry, surface dilational rheology, and atomic force microscopy (AFM). A concentrated DNA solution was injected into an aqueous subphase underneath a spread lysozyme layer. While the optical properties of the surface layer changed fast after DNA injection, the dynamic dilational surface elasticity almost did not change, thereby indicating no continuous network formation of DNA/lysozyme complexes, unlike the case of DNA interactions with a monolayer of a cationic synthetic polyelectrolyte. A relatively fast increase in optical signals after a DNA injection under a lysozyme layer indicates that DNA penetration is controlled by diffusion. At low surface pressures, the AFM images show the formation of long strands in the surface layer. Increased surface compression does not lead to the formation of a network of DNA/lysozyme aggregates as in the case of a mixed layer of DNA and synthetic polyelectrolytes, but to the appearance of some folds and ridges in the layer. The formation of more disordered aggregates is presumably a consequence of weaker interactions of lysozyme with duplex DNA and the stabilization, at the same time, of loops of unpaired nucleotides at high local lysozyme concentrations in the surface layer.

Interfacial protein-protein displacement at fluid interfaces.

Protein blends are used to stabilise many traditional and emerging emulsion products, resulting in complex, non-equilibrated interfacial structures. The interface composition just after emulsification is dependent on the competitive adsorption between proteins. Over time, non-adsorbed proteins are capable of displacing the initially adsorbed ones. Such rearrangements are important to consider, since the integrity of the interfacial film could be compromised after partial displacement, which may result in the physical destabilisation of emulsions. In the present review, we critically describe various experimental techniques to assess the interfacial composition, properties and mechanisms of protein displacement. The type of information that can be obtained from the different techniques is described, from which we comment on their suitability for displacement studies. Comparative studies between model interfaces and emulsions allow for evaluating the impact of minor components and the different fluid dynamics during interface formation. We extensively discuss available mechanistic physical models that describe interfacial properties and the dynamics of complex mixed systems, with a focus on protein in-plane and bulk-interface interactions. The potential of Brownian dynamic simulations to describe the parameters that govern interfacial displacement is also addressed. This review thus provides ample information for characterising the interfacial properties over time in protein blend-stabilised emulsions, based on both experimental and modelling approaches.

A Multistate Adsorption Model for the Characterization of C13DMPO Adsorption Layers at the Aqueous Solution/Air Interface.

Experimental data for tridecyl dimethyl phosphine oxide (C13DMPO) adsorption layers at the water/air interface, including equilibrium surface tension and surface dilational viscoelasticity, are measured by bubble and drop profile analysis tensiometry at different solution concentrations and surface area oscillation frequencies. The results are used to assess the applicability of a multistate model with more than two possible adsorption states. For the experiments with single drops, the depletion of surfactant molecules due to adsorption at the drop surface is taken into account. For the assessment, the same set of model parameters is used for the description of all obtained experimental dependencies. The agreement between the proposed model and the experimental data shows that for the nonionic surfactant C13DMPO, the description of the adsorption layer behavior by three adsorption states is superior to that with only two adsorption states.

Pickering foams and parameters influencing their characteristics.

Pickering foams are available in many applications and have been continually gaining interest in the last two decades. Pickering foams are multifaceted, and their characteristics are highly dependent on many factors, such as particle size, charge, hydrophobicity and concentration as well as the charge and concentration of surfactants and salts available in the system. A literature review of these individual studies at first might seem confusing and somewhat contradictory, particularly in multi-component systems with particles and surfactants with different charges in the presence of salts. This paper provides a comprehensive overview of particle-stabilized foams, also known as Pickering foams and froths. Underlying mechanisms of foam stabilization by particles with different morphology, surface chemistry, size and type are reviewed and clarified. This paper also outlines the role of salts and different factors such as pH, temperature and gas type on Pickering foams. Further, we highlight recent developments in Pickering foams in different applications such as food, mining, oil and gas, and wastewater treatment industries, where Pickering foams are abundant. We conclude this overview by presenting important research avenues based on the gaps identified here. The focus of this review is limited to Pickering foams of surfactants with added salts and does not include studies on polymers, proteins, or other macromolecules.

Experimental techniques to study protein-surfactant interactions: New insights into competitive adsorptions via drop subphase and interface exchange.

Protein surfactant (PS) interactions is an essential topic for many fundamental and technological applications such as life science, nanobiotechnology processes, food industry, biodiesel production and drug delivery systems. Several experimental techniques and data analysis approaches have been developed to characterize PS interactions in bulk and at interfaces. However, to evaluate the mechanisms and the level of interactions quantitatively, e.g., PS ratio in complexes, their stability in bulk, and reversibility of their interfacial adsorption, new experimental techniques and protocols are still needed, especially with relevance for in-situ biological conditions. The available standard techniques can provide us with the basic understanding of interactions mainly under static conditions and far from physiological criteria. However, detailed measurements at complex interfaces can be formidable due to the sophisticated tools required to carefully probe nanometric phenomena at interfaces without disturbing the adsorbed layer. Tensiometry-based techniques such as drop profile analysis tensiometry (PAT) have been among the most powerful methods for characterizing protein's and surfactant's adsorption layers at interfaces via measuring equilibrium and dynamic interfacial tension and dilational rheology analysis. PAT provides us with insightful data such as kinetics and isotherms of adsorption and related surface activity parameters. However, the data analysis and interpretation can be challenging for mixed protein-surfactant solutions via standard PAT experimental protocols. The combination of a coaxial double capillary (micro flow exchange system) with drop profile analysis tensiometry (CDC-PAT) is a promising tool to provide valuable results under different competitive adsorption/desorption conditions via novel experimental protocols. CDC-PAT provides unique experimental protocols to exchange the droplet subphase in a continuous dynamic mode during the in-situ analysis of the corresponding interfacial adsorbed layer. The contribution of diffusion/convection mechanisms on the kinetics of the adsorption/desorption processes can also be investigated using CDC-PAT. Here, firstly, we review the commonly available techniques for characterizing protein-surfactant interactions in the bulk phase and at interfaces. Secondly, we give an overview for applications of the coaxial double capillary PAT setup for investigations of mixed protein-surfactant adsorbed layers and address recently developed protocols and analysis procedures. Exploring the competitive sequential adsorption of proteins and surfactants and the reversibility of pre-adsorbed layers via the subphase exchange are the particular experiments we can perform using CDC-PAT. Also the sequential and simultaneous competitive adsorption/desorption processes of some ionic and nonionic surfactants (SDS, CTAB, DTAB, and Triton) and proteins (bovine serum albumin (BSA), lysozyme, and lipase) using CDC-PAT are discussed. Last but not least, the fabrication of micro-nanocomposite layers and membranes are additional applications of CDC-PAT discussed in this work.

Can small air bubbles probe very low frother concentration faster?

The existing literature on the rise velocities of air bubbles in aqueous surfactant solutions adsorbing at the water-air interface focuses mainly on large bubbles (D > 1.2 mm). In addition, due to the way the bubbles in rising bubble experiments are formed, their size is dependent on interfacial tension (the lower the interfacial tension the smaller the bubble). In this paper, smaller air bubbles (D < 505 ± 3 µm) are used to investigate the effect of the bubble size on the detection of two flotation frothers of different adsorption kinetics via bubble rise velocity measurements. We use an alternative method for bubble generation, allowing us to compare the rise velocity of bubbles of the same size in solutions of frothers of varying bulk concentration. The approach taken (ensuring consistent bubble size) ascertains that the buoyancy force component is kept constant when comparing the different solutions. As a consequence, any variations in the bubble rise velocity can be related to changes in the hydrodynamic drag force acting on a rising bubble. The interfacial behavior of frothers, i.e. the adsorption kinetics, interfacial activity and the maximum amount of molecules adsorbed at the interface, are determined from interfacial tension measurements and adsorption isotherms. The differences in the degree of tangential immobilisation caused by two different frothers are discussed in the context of differences in the structure of the dynamic adsorption layer, which is formed during the bubble rise.

Enzymatic Hydrolysis of Triglycerides at the Water-Oil Interface Studied via Interfacial Rheology Analysis of Lipase Adsorption Layers.

The enzymatic hydrolysis of sunflower oil occurs at the water-oil interface. Therefore, the characterization of dynamic interfacial phenomena is essential for understanding the related mechanisms for process optimizations. Most of the available studies for this purpose deal with averaged interfacial properties determined via reaction kinetics and dynamic surface tension measurements. In addition to the classical approach for dynamic surface tension measurements, here, the evolution of the dilational viscoelasticity of the lipase adsorbed layer at the water-oil interface is characterized using profile analysis tensiometry. It is observed that lipase exhibits nonlinear dilational rheology depending on the concentration and age of the adsorbed layer. For reactive water-oil interfaces, the response of the interfacial tension to the sinusoidal area perturbations becomes more asymmetric with time. Surface-active products of the enzymatic hydrolysis of triglycerides render the interface less elastic during compression compared to the expansion path. The lipolysis products can facilitate desorption upon compression while inhibiting adsorption upon expansion of the interface. Lissajous plots provide an insight into how the hysteresis effect leads to different interfacial tensions along the expansion and compression routes. Also, the droplet shape increasingly deviates from a Laplacian shape, demonstrating an irreversible film formation during aging and ongoing hydrolysis reaction, which supports our findings via interfacial elasticity analysis.

Effect of selected monovalent salts on surfactant stabilized foams.

Surfactant-stabilized foams have been at the centre of scientific research for over a century due to their ubiquitous applications in different industries. Many of these applications involve inorganic salts either due to their natural presence (e.g. use of seawater in froth floatation) or their addition (e.g. in cosmetics) to manipulate foam characteristics for the best outcomes. This paper provides a clear understanding of the effect of salts on surfactant-stabilized foams through a critical literature survey of this topic. Available literature shows a double effect of salts (LiCl, NaCl and KCl) on foam characteristics in the presence of surfactants. To elucidate the underlying mechanisms of the stabilizing effect of salts on foams, the effect of salts on surfactant-free thin liquid films is first discussed, followed by a discussion on the effect of salts on surfactant-stabilized foams with the focus on anionic surfactants. We discuss two distinctive salt concentrations, salt transition concentration in surfactant-free solutions and salt critical concentration in surfactant-laden systems to explain their effects. Using the available data in literature supported by dedicated experiments, we demonstrate the destabilizing effect of salts on foams at and above their critical concentrations in the presence of anionic surfactants. This effect is attributed to retarding the adsorption of the surfactant molecules at the interface due to the formation of nano and micro-scale aggregates.