Ultrasound-Induced Adsorption of Acousto-Responsive Microgels at Water-Oil Interface.

Ultrasonic mixing is a well-established method to disperse and mix substances. However, the effects of ultrasound on dispersed soft particles as well as on their adsorption kinetics at interfaces remain unexplored. Ultrasound not only accelerates the movement of particles via acoustic streaming, but recent research indicates that it can also manipulate the interaction of soft particles with the surrounding liquid. In this study, it evaluates the adsorption kinetics of microgel at the water-oil interface under the influence of ultrasound. It quantifies how acoustic streaming accelerates the reduction of interfacial tension. It uses high-frequency and low-amplitude ultrasound, which has no destructive effects. Furthermore, it discusses the ultrasound-induced shrinking and thus interfacial rearrangement of the microgels, which plays a secondary but non-negligible role on interfacial tension reduction. It shows that the decrease in interfacial tension due to the acoustic streaming is stronger for microgels with higher cross-linker density. Moreover, it shows that ultrasound can induce a reversible decrease in interfacial tension due to the shrinkage of microgels at the interface. The presented results may lead to a better understanding in any field where ultrasonic waves meet soft particles, e.g., controlled destabilization in foams and emulsions or systems for drug release.

Effect of non-ionic surfactants on the adsorption of polycyclic aromatic compounds at water/oil interface: A molecular simulation study.

HYPOTHESIS: Molecular simulations can provide unique insights into the adsorption and intermolecular interactions of polycyclic aromatic compounds (PACs) and non-ionic surfactants at water/oil interface. METHODS: Molecular dynamic simulations were performed to study the adsorption of PACs at water/oil interface, and the effect of adding non-ionic surfactants. PAC architecture, solvent type, structure and concentration of non-ionic surfactants were varied to address the complex interplay between PAC-surfactant interaction, PAC solubility, and structure-dependent PAC aggregation. FINDINGS: PACs with multiple cores (PacM) partially adsorbed on the interface, in the form of small and loosely structured aggregates. Adding non-ionic surfactant Brij-93 induced desorption of PacM at both water/toluene and water/heptane interfaces. Another non-ionic surfactant, (EO)5(PO)10(EO)5, also reduced the adsorption of PacM at water/toluene interface but enhanced their adsorption at water/heptane interface. PACs with a single large core strongly adsorbed on both interfaces, forming compact aggregated structures. Adding the two types of non-ionic surfactants did not induce desorption. This work identified two opposite roles of non-ionic surfactants in the adsorption of PACs, namely competition and co-adsorption, and provided useful insights into how the roles of non-ionic surfactants might be affected by their concentration, as well as the solubility and interfacial behaviors of the PACs.

Tip-to-tip assembly of urchin-like Au nanostar at water-oil interface for surface-enhanced Raman spectroscopy detection.

Au Nanostar (NS) monolayer as a surface enhanced Raman scattering (SERS) substrate has been synthesized by self-assembly at a water-oil interface. It is confirmed from the experiment and simulation results that the Au NS monolayer includes lots of "hot spots" at or between the tips of the Au NSs, enhancing the local electromagnetic fields and giving rise to strong SERS signals sequentially. The limit of detection is determined to be down to 4.2 × 10-12 M for rhodamine 6G. Furthermore, the Au NS monolayer can detect multiple molecules, including thiabendazole, methylene blue, 4-mercaptobenzoic acid, and p-amino thiophenol, indicating that the SERS substrate composed of Au NS monolayer has potential applications in analytical chemistry, food safety, and environmental safety.

Adsorption model and phase transitions of diblock perfluoroalkylated surfactants at the water∣alkane interface.

We present a theory of the adsorption behaviour and phase transitions in monolayers of perfluoroalkylated alcohols, n-CnF2n+1CmH2mOH, at the water∣oil interface, and validate it for a range of temperatures and surfactant structures. The reason for the observed cohesive behaviour is identified as dispersion attraction between the fluorocarbon blocks. The London constant is determined from the increment of the lateral attraction parameter with the size of the fluorocarbon chain. The monolayers exhibit phase transition from liquid expanded state to van der Waals crystal. However, they are supercritical with respect to the gas-liquid transition. For the description of the liquid phase, we use the sticky disc model - fluid monolayer made of hard discs interacting with a short-ranged sticky potential. For the crystalline phase, a two-dimensional cell model is developed using the same interaction potential. This new model coincides with the empirical equation of state of Jura and Harkins, and ascribes physical meaning to its parameters. We extend the theory of Ivanov et al. for the adsorption constant Ka to diblock molecules; it predicts accurately the dependence of Ka and the adsorption heat on the surfactant structure. An invariant phase diagram of the monolayers is constructed.

Dilational interfacial rheology of tridecyl dimethyl phosphine oxide adsorption layers at the water/hexane interface.

The dilational visco-elasticity of surfactant adsorption layers was measured at low frequencies by the drop profile analysis tensiometry using oscillating drops. As the studied non-ionic surfactant C13DMPO (tridecyl dimethyl phosphine oxide) is soluble in water and in hexane, the partitioning of the surfactant between the two solvents had to be taken into consideration. The diffusion controlled exchange of matter theory was generalized in order to take into consideration the curvature of the interface, the diffusional transport in both adjacent bulk phases as well as the transfer across the liquid interface. Using two configurations, i.e. water drop in hexane and hexane drop in water, it is shown that the frequency dependence of the visco-elasticity modulus and the phase angle can be well described when the correct partition coefficient is applied. The surface activity of the selected surfactant C13DMPO is optimum to demonstrate the impact of matter transfer across the interface on the dilational visco-elasticity of interfacial adsorption layers of non-ionic surfactants.

Competition of Thermomyces lanuginosus lipase with its hydrolysis products at the oil-water interface.

Lipase-catalyzed hydrolysis of triglycerides yields glycerol and free fatty-acids, provided that the enzyme is non-regioselective. For an Sn-1,3 regioselective enzyme, such as lipase from Thermomyces lanuginosus, the final product is no longer glycerol but Sn-2 monoglyceride instead. However, surface active molecules generated by lipolysis may have a detrimental effect on the interfacial biocatalysis since it is known that low molecular weight surfactants can displace proteins from interfaces. By using drop profile analysis tensiometry, we evaluated the interfacial properties of the lipase-generated molecules and their competitive effect on the adsorption behavior of the lipase and on the proceeding lipolysis. Our results show that even at concentration ratios of 8.64×10-4M (Sn-2 monoglyceride) to 2.5×10-7M (lipase), the final interfacial pressure values are very similar as for the system containing the lipase alone (i.e. ∼26 mN/m). This is a strong indication that monoglycerides, as the most interfacially active products generated during regioselective lipolysis, are expelled from the oil-water interface by the lipase. We attribute this effect to intermolecular lipase-lipase interactions, resulting in a low desorption probability of the lipase. For low oleic acid concentrations, the interfacial tension is solely determined by the lipase, while for higher concentrations, lipase and oleic acid both contribute to the tension values. We propose a hypothesis based on the preferential interaction of oleic acid molecules with hydrophobic sites on the lipase. The pH dependence of the adsorption rate and the interfacial activity of the lipase were also investigated.

Tensiometry and dilational rheology of mixed ß-lactoglobulin/ionic surfactant adsorption layers at water/air and water/hexane interfaces.

Oscillating drop tensiometry was applied to study adsorbed interfacial layers at water/air and water/hexane interfaces formed from mixed solutions of ß-lactoglobulin (BLG, 1 µM in 10 mM buffer, pH 7 - negative net charge) and the anionic surfactant SDS or the cationic DoTAB. The interfacial pressure Π and the dilational viscoelasticity modulus |E| of the mixed layers were measured for mixtures of varying surfactant concentrations. The double capillary technique was employed which enables exchange of the protein solution in the drop bulk by surfactant solution (sequential adsorption) or by pure buffer (washing out). The first protocol allows probing the influence of the surfactant on a pre-adsorbed protein layer thus studying the protein/surfactant interactions at the interface. The second protocol gives access to the residual values of Π and |E| measured after the washing out procedure thus bringing information about the process of protein desorption. The DoTAB/BLG complexes exhibit higher surface activity and higher resistance to desorption in comparison with those for the SDS/BLG complexes due to hydrophobization via electrostatic binding of surfactant molecules. The neutral DoTAB/BLG complexes achieve maximum elastic response of the mixed layer. Mixed BLG/surfactant layers at the water/oil interface are found to reach higher surface pressure and lower maximum dilational elasticity than those at the water/air surface. The sequential adsorption mode experiments and the desorption study reveal that binding of DoTAB to pre-adsorbed BLG globules is somehow restricted at the water/air surface in comparison with the case of complex formation in the solution bulk and subsequently adsorbed at the water/air surface. Maximum elasticity is achieved with washed out layers obtained after simultaneous adsorption, i.e. isolation of the most surface active DoTAB/BLG complex. These specific effects are much less pronounced at the W/H interface.

Adsorption of ions at the interface oil|aqueous electrolyte and at interfaces with adsorbed alcohol.

We investigate the applicability of the Schmutzer's model for three types of interfaces: aqueous electrolyte|alkane, aqueous electrolyte|long chained alcohol phase, and aqueous electrolyte|alkane with adsorbed alcohol. The model predicts a strong decrease of the electrolyte desorption at water|alcohol interface in comparison with water|alkane, in quantitative agreement with the tensiometric data. The effect is related to the penetration of the alcohol -OH group into the surface layer of the aqueous solution. The same model predicts a decrease with the electrolyte concentration of the chemical potential of the alcohol molecules adsorbed at the water|oil interface, which results in an increase of the adsorption activity of oil-soluble alcohols, again in quantitative agreement with the experiment. The analysis of the deviations of Schmutzer's model predictions from the experimental data for large polarizable anions allows making qualitative conclusions for the magnitude of the ion-specific hydrophobic and dispersion forces at water|gas and water|oil interfaces.