Rheological design of thickened alcohol-based hand rubs.

The handleability and sensory perception of hand sanitisers by consumers affect the hygiene outcome. Spillage may result in under-dosing and poor sensory properties can lead to under-utilisation. We first propose four principles (low runoff, spreadability, smoothness and non-stickiness) for designing the rheology of thickened alcohol-based hand rubs with acceptable handleability and hand feel. We then evaluate a commercial hand gel and a variety of simplified formulations thickened with microgels (Carbopol 974P, Carbopol Ultrez 20 and Sepimax Zen), or linear polymers (Jaguar HP 120 COS), and evaluate them against these design criteria. All four additives provide acceptable spreadability by shear thinning to η ≈ 10 - 1 Pa s at γ ˙ ∼ 10 3 s - 1 . Either the finite yield stress conferred by the microgels ( σ y ≳ 10 Pa ) or the increase in low-shear viscosity provided by the linear polymer ( η ≳ 1 Pa s at γ ˙ ≲ 0.1 s - 1 ) give rise to acceptably low runoff. However, the formulation using the linear polymer shows a filament breakage time of τ b ≈ 1 s in capillary rheology, which may result in stickiness and therefore a less than optimal hand feel.

Soft matter science and the COVID-19 pandemic.

Much of the science underpinning the global response to the COVID-19 pandemic lies in the soft matter domain. Coronaviruses are composite particles with a core of nucleic acids complexed to proteins surrounded by a protein-studded lipid bilayer shell. A dominant route for transmission is via air-borne aerosols and droplets. Viral interaction with polymeric body fluids, particularly mucus, and cell membranes controls their infectivity, while their interaction with skin and artificial surfaces underpins cleaning and disinfection and the efficacy of masks and other personal protective equipment. The global response to COVID-19 has highlighted gaps in the soft matter knowledge base. We survey these gaps, especially as pertaining to the transmission of the disease, and suggest questions that can (and need to) be tackled, both in response to COVID-19 and to better prepare for future viral pandemics.

Celebrating Soft Matter's 10th Anniversary: Simplicity in complexity--towards a soft matter physics of caramel.

Caramel is a mixture of sugars, milk proteins, fat and water cooked at high temperatures to initiate Maillard reactions. We study caramels as 'active emulsion-filled protein gels', in which fat droplets are chemically-bonded to a background gel matrix of cross-linked proteins in a concentrated aqueous sugar solution. We delimit a 'caramel region' in composition space. Oscillatory rheology within this region reveals that we can superpose the mechanical spectra of our caramels onto a single pair of G'(ω), G''(ω) master curves using time-composition superposition (tCS) over 12 decades of frequency, so that these caramels are instances of an underlying 'universal material'. This insight constrains the molecular mechanisms for structure formation, and implies that measuring a couple of parameters will suffice to predict the rheology of our caramels over 12 orders of magnitude in frequency.

Effects of emulsifier charge and concentration on pancreatic lipolysis. 1. In the absence of bile salts.

An in vitro study is performed with sunflower oil-in-water emulsions to clarify the effects of type of used emulsifier, its concentration, and reaction time on the degree of oil lipolysis, α. Anionic, nonionic, and cationic surfactants are studied as emulsifiers. For all systems, three regions are observed when surfactant concentration is scaled with the critical micelle concentration, C(S)/cmc: (1) At C(S) < cmc, α ≈ 0.5 after 30 min and increases up to 0.9 after 4 h. (2) At C(S) ≈ 3 × cmc, α ≈ 0.15 after 30 min and increases steeply up to 0.9 after 2 h for the cationic and nonionic surfactants, whereas it remains around 0.2 for the anionic surfactants. (3) At C(S) above certain threshold value, α = 0 for all studied surfactants, for reaction time up to 8 h. Additional experiments show that the lipase hydrolyzes molecularly soluble substrate (tributirin) at C(S) >> cmc, which is a proof that these surfactants do not denature or block the enzyme active center. Thus, we conclude that the mechanism of enzyme inhibition by these surfactants is the formation of a dense adsorption layer on an oil drop surface, which displaces the lipase from direct contact with the triglycerides.

Effects of emulsifier charge and concentration on pancreatic lipolysis: 2. Interplay of emulsifiers and biles.

As a direct continuation of the first part of our in vitro study (Vinarov et al., Langmuir 2012, 28, 8127), here we investigate the effects of emulsifier type and concentration on the degree of triglyceride lipolysis, in the presence of bile salts. Three types of surfactants are tested as emulsifiers: anionic, nonionic, and cationic. For all systems, we observe three regions in the dependence degree of fat lipolysis, α, versus emulsifier-to-bile ratio, f(s): α is around 0.5 in Region 1 (f(s) < 0.02); α passes through a maximum close to 1 in Region 2 (0.02 < f(s) < f(TR)); α is around zero in Region 3 (f(s) > f(TR)). The threshold ratio for complete inhibition of lipolysis, f(TR), is around 0.4 for the nonionic, 1.5 for the cationic, and 7.5 for the anionic surfactants. Measurements of interfacial tensions and optical observations revealed the following: In Region 1, the emulsifier molecules are solubilized in the bile micelles, and the adsorption layer is dominated by bile molecules. In Region 2, mixed surfactant-bile micelles are formed, with high solubilization capacity for the products of triglyceride lipolysis; rapid solubilization of these products leads to complete lipolysis. In Region 3, the emulsifier molecules prevail in the adsorption layer and completely block the lipolysis.

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.

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.

Unique properties of bubbles and foam films stabilized by HFBII hydrophobin.

The HFBII hydrophobin is an amphiphilic protein that can irreversibly adsorb at the air/water interface. The formed protein monolayers can reach a state of two-dimensional elastic solid that exhibits a high mechanical strength as compared to adsorption layers of typical amphiphilic proteins. Bubbles formed in HFBII solutions preserve the nonspherical shape they had at the moment of solidification of their surfaces. The stirring of HFBII solutions leads to the formation of many bubbles of micrometer size. Measuring the electrophoretic mobility of such bubbles, the ζ-potential was determined. Upon compression, the HFBII monolayers form periodic wrinkles of wavelength 11.5 µm, which corresponds to bending elasticity k(c) = 1.1 × 10(-19) J. The wrinkled hydrophobin monolayers are close to a tension-free state, which prevents the Ostwald ripening and provides bubble longevity in HFBII stabilized foams. Films formed between two bubbles are studied by experiments in a capillary cell. In the absence of added electrolyte, the films are electrostatically stabilized. The appearance of protein aggregates is enhanced with the increase of the HFBII and electrolyte concentrations and at pH close to the isoelectric point. When the aggregate concentration is not too high (to block the film thinning), the films reach a state with 12 nm uniform thickness, which corresponds to two surface monolayers plus HFBII tetramers sandwiched between them. In water, the HFBII molecules can stick to each other not only by their hydrophobic moieties but also by their hydrophilic parts. The latter leads to the attachment of HFBII aggregates such as dimers, tetramers, and bigger ones to the interfacial adsorption monolayers, which provides additional stabilization of the liquid films.

Role of the counterions on the adsorption of ionic surfactants.

A theory accounting for the effect of the counterions on the adsorption constant, K, is proposed. The experimental values of K were determined by using surface and interfacial tension isotherms measured by us or available in the literature. By accounting for the adsorption energy u 0 of the counterion, a generalization of Gouy equation and a modified expression for the adsorption constant, K, are derived. The adsorption energy is calculated from the London equation, which involves the polarizabilities alpha 0i and the ionization potentials Ii of the respective components and the radius Rh of the hydrated ion. By careful analysis of the available experimental data for alpha 0i, Ii and Rh, coupled with some reasonable hypothesis, we succeeded to obtain linear dependences between the calculated values of u 0 and the experimental data for lnK with slopes rather close to the theoretical ones. The obtained results for u 0 were used to calculate the disjoining pressure isotherms of foam films stabilized by DTAF, DTACl and DTABr. It turned out that the type of the counterion has significant effect on the disjoining pressure.

Acoustical observation of bubble oscillations induced by bubble popping.

Acoustic measurements of aqueous foams show three distinct radiation mechanisms that contribute to the sound pressure field: oscillations of a bubble surface that precede popping due to the instability of thin liquid film, impulsive radiation due to bursts of bubbles, and oscillations from neighboring bubbles excited by a burst bubble. The movies captured by a fast camera confirm that the bubbles adjacent to a breaking bubble oscillate under the influence of the pressure generated by the burst bubble. The spectra of resulting transient sounds fall in the range of 2-8 kHz and those from bubble oscillations correlate well with the bubble size.

Adsorption and structure of the adsorbed layer of ionic surfactants.

Our goal in this study was to investigate theoretically and experimentally the adsorption of ionic surfactants and the role of different factors in the mechanism of adsorption, the adsorption parameters and the structure of the adsorbed layer. We used available literature data for the interfacial tension, sigma, vs. concentration, C(s), for sodium dodecyl sulfate (SDS) in three representative systems with Air/Water (A/W), Oil/Water (O/W) and Oil/Water + 0.1 M NaCl (O/WE) interfaces. We derived 6 new adsorption isotherms and 6 new equations of state (EOS) based on the adsorption isotherms for non-ionic surfactants of Langmuir, Volmer and Helfand-Frisch-Lebowitz (HFL) with interaction term betatheta2/2 in the EOS, theta=alphaGamma being the degree of coverage, with Gamma--adsorption and alpha--minimum area per molecule. We applied Gouy equation for high surface potentials and modified it to account for partial penetration of the counterions in the adsorbed layer. The equations were written in terms of the effective concentration C=[C(s)(C(s)+C(el))](1/2), where C(s) and C(el) are, respectively concentrations of the surfactant and the electrolyte. We showed that the adsorption constant K was model independent and derived an equation for the effective thickness of the adsorbed layer, delta(s). We found also that the minimum area per molecule, alpha, is larger than the true area, alpha(0), which depends on the adsorption model and is a function of the adsorption Gamma. The interaction term betatheta2/2 in the Langmuir EOS was found to be exact for small beta<<1, but for the Volmer EOS it turned out to be only a crude approximation. Semi-quantitative considerations about the interaction between adsorbed discrete charges revealed that at A/W interface part of the adsorbed surfactant molecules are partially immersed in water, which leads to decreased repulsion and increased adsorption Gamma. At O/W the larger adsorption energy keeps the surfactant molecules on the surface, so that the electrostatic repulsion is stronger, which translates into negative beta's, larger alpha's and smaller adsorption. The addition of electrolyte partly screens the repulsion at O/W, leading to decreased alpha and increased adsorption. We determined K, alpha and beta by a three-parameter fit. The constant K was found to be model independent and smaller for A/W than for O/W, because of the smaller adsorption energy. The values of alpha were larger for O/W than for A/W and decreased for O/W upon addition of electrolyte in agreement with the theory. For the Volmer model alpha was smaller than for Langmuir's model and both were found to increase with decreasing Gamma - again in agreement with the theoretical predictions. It turned out that theta never exceeds 0.5 i.e. the adsorbed layer is never saturated. We tried to determine which adsorption model gave better results by calculating theoretically the Gibbs elasticity, but it turned out that when the results were plotted vs. an experimental variable, say C, all curves collapsed in a single one, which coincided with the respective experimental curve. This means that it is impossible to determine the adsorption model by using only interfacial tension data.

Disjoining pressure of thin films stabilized by nonionic surfactants.

In this article an attempt is made to derive a comprehensive theory of the disjoining pressure of thin liquid films, stabilized by low molecular nonionic surfactants. We accounted for effects playing a role in the case of surfactants with spherical hydrophilic heads: (i) The thermal fluctuations of the adsorbed surfactant molecules, due to the fact that the energy of adsorption of a -CH(2)- group is approximately equal to the average thermal energy k(B)T; (ii) The contribution of the collisions between molecules adsorbed on different surfaces; (iii) The restriction imposed on the fluctuation of the molecules by the presence of a second surface situated at a small distance h from the interface where the molecules are adsorbed; (iv) The volume of the hydrophilic heads, which expels part of the water molecules from the film region; (v) The equilibrium between the molecules adsorbed at the film surfaces and at the menisci surrounding the film. The adsorption on the film surfaces has two main effects. First, the concentration of solute inside the film region becomes larger than in the bulk solution and this will push the solvent toward the film thus creating an osmotic pressure (the disjoining pressure), which tends to increase the film thickness. Second, the higher concentration inside the film and the collisions between the polar heads lead to higher chemical potential, which pushes the surfactant toward the meniscus. We treated these effects by modifying adequately the Hildebrand-Scatchard theory for the osmotic pressure of concentrated solutions. The partition function of the surfactant, needed for this calculation, was found by deriving an expression for the configurational integral, based on virial expansion. The surface equations of state of Helfand, Frisch and Lebowitz and Volmer were critically analyzed and then generalized, by using the partition function obtained by virial expansion, to permit the derivation of partition functions of the surfactant molecules in the film. A simple thermodynamic approach was developed and applied to derive expressions for the disjoining pressure, Pi, and the chemical potential of the surfactant molecules in the film, mu. They were used to calculate numerically Pi and mu and analyze their dependence on the film thickness h and the surface coverage theta. It turned out that Pi has completely different behavior above and below h=2d, where d is the diameter of the hydrophilic head. For thick films, with h>2d, the decay of Pi is initially exponential (due mainly to the thermal fluctuations of the adsorbed molecules), followed by a long tail, proportional to h(-2), due to the contribution of the osmotic pressure of the displaced solvent molecules. At h<2d the collisions between the molecules adsorbed at different surfaces are hindered, which leads to a steady decrease of the contribution due the interaction between the molecules. The overall result of these effects is the appearance of a maximum of Pi at h=2d. It is very large (it may reach 1000 atm and even more) and depends strongly on the surfactant adsorption. To facilitate the application and the analysis of the theory, we derived several simpler asymptotic expressions. One of them is virial expansion, which is valid for small surface coverage and has the advantage of being independent of the adsorption model. The other asymptotic expression is applicable at h>2d, which is the region where the stabilization of the film occurs. We compared our theory with the simpler theory of Israelachvili and Wennerström. It turned out that while both theories lead to decay of Pi vs. h, the numerical results and the shape of the curves are usually very different. The experimental data, which could be used to verify our theory, are scarce, but we found reasonable agreement with the data of Lyle and Tiddy for bilayers of C(12)EO(4). The data of Parsegian et al. for lipid bilayers also confirmed qualitatively some of our theoretical conclusions.

Influence of electrolytes on the dynamic surface tension of ionic surfactant solutions: expanding and immobile interfaces.

Here, we derive analytical asymptotic expressions for the dynamic surface tension of ionic surfactant solutions in the general case of nonstationary interfacial expansion. Because the diffusion layer is much wider than the electric double layer, the equations contain a small parameter. The resulting perturbation problem is singular and it is solved by means of the method of matched asymptotic expansions. The derived general expression for the dynamic surface tension is simplified for the special case of immobile interface and for the maximum bubble pressure method (MBPM). The case of stationary interfacial expansion is also considered. The effective diffusivity of the ionic surfactant essentially depends on the concentrations of surfactant and nonamphiphilic salt. To test the theory, the derived equations are applied to calculate the surfactant adsorption from MBPM experimental data. The results excellently agree with the adsorption determined independently from equilibrium surface-tension isotherms. The derived theoretical expressions could find application for interpreting data obtained by MBPM and other experimental methods for investigating interfacial dynamics.

The mechanism of lowering cholesterol absorption by calcium studied by using an in vitro digestion model.

Studies in humans show that a calcium-enriched diet leads to lower cholesterol in blood serum. This phenomenon is usually explained in the literature with a reduced cholesterol absorption in the small intestine. Our study aims to clarify the effect of calcium on the solubilisation of cholesterol and fatty acid in the dietary mixed micelles (DMM), viz. on the bioaccessibility of these lipophilic substances in the gut. We use an in vitro digestion model which mimics very closely the intestinal pH-profile and the composition of the intestinal fluids. We quantified the effects of Ca(2+) concentration on the lipid solubilization for fats and oils with different saturated/unsaturated fatty acid (FA) contents. We found that the increase of calcium significantly decreases the solubilization of cholesterol, FA and MG. Most importantly, we observe a clear positive correlation between the amounts of solubilized cholesterol, on one side, and solubilized free fatty acids and monoglycerides, on the other side. The main conclusion is that Ca(2+) ions strongly affect the bioaccessibility of both cholesterol and saturated FA. Therefore, calcium may decrease the serum cholesterol via two complementary mechanisms: (1) fatty acid precipitation by calcium ions reduces the solubilisation capacity of the DMM, thus decreasing the levels of solubilised (bioaccessible) cholesterol; (2) the observed strong decrease of the bioaccessible saturated FA, in its own turn, may suppress the cholesterol synthesis in the liver.

Interfacial rheology of adsorbed layers with surface reaction: on the origin of the dilatational surface viscosity.

A theoretical study of the phenomena, occurring in an adsorbed layer, subject to small dilatational perturbations was carried out. Two main processes, provoked by the perturbations (surface reaction and surfactant transport onto the surface) were considered. The reaction was described by means of the reaction coordinate. The derived general rheological equation for insoluble surfactants, gave as limiting cases Voight and Maxwell type equations for fast and slow reactions, respectively. Expressions for all characteristics of the process (surface elasticity, reaction elasticity, reaction relaxation time and dilatational surface viscosity) were obtained. The obtained generalized rheological equation for reactions involving soluble surfactants is a dynamic analog of Gibbs adsorption isotherms for a multi-component system with surface reaction, since similarly to Gibbs equation it relates the surface stress only to surface variables. It gives as limiting cases generalized forms for soluble surfactants of Voight and Maxwell equations. All new rheological equations were analyzed for deformations with constant rate and periodic oscillations and they were applied to three simple surface reactions (monomolecular with one product, dimerization and association). The mass transfer was analyzed initially in the absence of surface reaction. In this system the surface stress is purely elastic, but it was shown that if the adsorption perturbation is small, regardless of the type of surface perturbation and the mechanism of adsorption, the process of mass transport always obeys a Maxwell type rheological equation. For all considered processes surface viscosities were defined, but they were called "apparent", because they stem from diffusion, rather than from interaction between the surfactant molecules and they depend not only on surface parameters, but also on the geometry of the system. The often used in the literature correlations between the lifetime of emulsions and foams and the imaginary elasticity were analyzed. It was shown that this approach lacks serious scientific foundations and could lead to erroneous conclusions. Finally, the problem for the coupling of the surfactant diffusion with the chemical reaction was analyzed and it was demonstrated on a simple example how it could be tackled.

In vitro study of triglyceride lipolysis and phase distribution of the reaction products and cholesterol: effects of calcium and bicarbonate.

We describe a relatively simple in vitro model for triglyceride (TG) lipolysis which mimics closely the conditions in the human stomach and small intestine. The main model advantages are: (1) as in vivo, sodium bicarbonate is used for buffering; (2) the pH-profile in the small intestine is closely matched; (3) the experimental procedure does not include complex equipment. To test its performance, the proposed in vitro model is applied to quantify the effects of Ca(2+), pH, and bicarbonate on the degree of TG lipolysis and on the solubilization of the lipolysis products and cholesterol in the aqueous phase. We found that TG lipolysis passes through a shallow minimum at 3.5 mM Ca(2+) when varying the calcium concentration between 1 and 11 mM, while the presence of bicarbonate and the increase of pH led to a higher degree of lipolysis. Centrifugation and filtration were used to separate the aqueous phase and to study the solubilisation of the lipophilic components in the aqueous phase. We found that the solubilized cholesterol increases linearly with the concentration of free fatty acids (FFA) which is evidence for co-solubilization of these two components in the bile micelles. At high Ca(2+) concentrations, aggregates larger than 300 nm were observed by cryo-microscopy and light scattering, which solubilize well cholesterol and saturated FFA. In contrast, the monoglycerides were always predominantly solubilized in the small bile micelles with diameters around 4 nm.

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.

The metastable states of foam films containing electrically charged micelles or particles: experiment and quantitative interpretation.

The stepwise thinning (stratification) of liquid films containing electrically charged colloidal particles (in our case - surfactant micelles) is investigated. Most of the results are applicable also to films from nanoparticle suspensions. The aim is to achieve agreement between theory and experiment, and to better understand the physical reasons for this phenomenon. To test different theoretical approaches, we obtained experimental data for free foam films from micellar solutions of three ionic surfactants. The theoretical problem is reduced to the interpretation of the experimental concentration dependencies of the step height and of the final film thickness. The surface charges of films and micelles are calculated by means of the charge-regulation model, with a counterion-binding (Stern) constant determined from the fit of surface tension isotherms. The applicability of three models was tested: the Poisson-Boltzmann (PB) model; the jellium-approximation (JA), and the cell model (CM). The best agreement theory/experiment was obtained with the JA model without using any adjustable parameters. Two theoretical approaches are considered. First, in the energy approach the step height is identified with the effective diameter of the charged micelles, which represents an integral of the electrostatic-repulsion energy calculated by the JA model. Second, in the osmotic approach the step height is equal to the inverse cubic root of micelle number density in the bulk of solution. Both approaches are in good agreement with the experiment if the suspension of charged particles (micelles) represents a jellium, i.e. if the particle concentration is uniform despite the field of the electric double layers. The results lead to a convenient method for determining the aggregation number of ionic surfactant micelles from the experimental heights of the steps.

Method for analysis of the composition of acid soaps by electrolytic conductivity measurements.

Here, we propose a method for determining the stoichiometry of acid-soap crystallites. The method is based on dissolving the crystallites in water at an appropriate working temperature, followed by measurement of the electrolytic conductivity of the obtained solutions. The working temperature is chosen in such a way that the only precipitate in the solutions is that of carboxylic acid, whereas the carboxylate salt is dissociated, and its content in the dissolved crystals determines the solution's conductivity. In the theoretical model for data interpretation, we took into account the dependence of the molar conductance on the ionic strength. The method was applied for determining the stoichiometry of acid-soap crystals collected from solutions of potassium myristate (tetradecanoate) at 25 degrees C. The crystals were dissolved in water at working temperature of 40 degrees C, at which the conductivity was measured. The stoichiometry of all samples determined in the present study coincides with that independently obtained by another method that is based on in situ pH measurements.

Interfacial polygonal nanopatterning of stable microbubbles.

Micrometer-sized bubbles are unstable and therefore difficult to make and store for substantial lengths of time. Short-term stabilization is achieved by the addition of amphiphilic molecules, which reduce the driving force for dissolution. When these molecules crystallize on the air/liquid interface, the lifetime of individual bubbles may extend over a few months. We demonstrated low gas-fraction dispersions with mean bubble radii of less than 1 micrometer and stability lasting more than a year. An insoluble, self-assembled surfactant layer covers the surface of the microbubbles, which can result in nanometer-scale hexagonal patterning that we explain with thermodynamic and molecular models. The elastic response of the interface arrests the shrinkage of the bubbles. Our study identifies a route to fabricate highly stable dispersions of microbubbles.