The interfacial structure of nano- and micron-sized oil and water droplets stabilized with SDS and Span80.

In this work, we provide a comparison between the stability and the interfacial structure of micrometer-sized and nanometer-sized droplets by employing a multi-instrumental approach comprised of the surface-sensitive technique of sum frequency scattering as well as dynamic light scattering and microscopy. We monitor the stability of oil-in-water and water-in-oil emulsions and the structure of surfactants at the oil/water nano-interface, when stabilized with an oil-soluble neutral surfactant (Span80), a water-soluble anionic surfactant (sodium dodecyl sulfate, SDS), or with a combination of the two. Micron-sized droplets are found to be stabilized only when a surfactant soluble in the continuous phase is present in the system, in agreement with what is traditionally observed empirically. Surprisingly, the nanodroplets behave differently. Both oil and water nanodroplets can be stabilized by the same (neutral Span80) surfactant but with different surface structures. A combination of SDS and Span80 also suffices, but for the case of water droplets, the strongly amphiphilic SDS molecules are not detected at the interface. For the case of oil droplets, both surfactants are at the interface but do not structurally affect one another. Thus, it appears that, in this study, empirical rules such as the Bancroft rule, the hydrophile-lipophile-balance scale, and the surfactant affinity difference predict the stability of the micrometer-sized droplets better than the nanometer-sized ones, probably due to a different balance of interactions on different length scales.

Bioinspired Viscoelastic Capsules: Delivery Vehicles and Beyond.

Microcapsules are often used as individually dispersed carriers of active ingredients to prolong their shelf life or to protect premature reactions with substances contained in the surrounding. This study goes beyond this application and employs microcapsules as principal building blocks of macroscopic 3D materials with well-defined granular structures. To achieve this goal and inspired by nature, capsules are fabricated from block-copolymer surfactants that are functionalized with catechols, a metal-coordinating motive. These surfactants self-assemble at the surface of emulsion drops where they are ionically cross-linked to form viscoelastic capsules that display a low permeability even toward small encapsulants. It is demonstrated that the combination of the mechanical strength, flexibility, and stickiness of the capsules enables their additive manufacturing into macroscopic granular structures. Thereby, they open up new opportunities for 3D printing of soft, self-healing materials composed of individual compartments that can be functionalized with different types of spatially separated reagents.

Cross-talk between emulsion drops: how are hydrophilic reagents transported across oil phases?

Emulsion drops are frequently used as vessels, for example, to conduct biochemical reactions in small volumes or to perform screening assays at high throughputs while consuming minimal sample volumes. These applications typically require drops that do not allow exchange of reagents such that no cross-contamination occurs. Unfortunately, in many cases, reagents are exchanged between emulsion drops even if they have a low solubility in the surrounding phase, resulting in cross-contaminations. Here, we investigate the mechanism by which hydrophilic reagents are transported across an oil phase using water-oil-water double emulsion drops as a model system. Remarkably, even large objects, including 11 000 base pair double-stranded circular DNA are transported across oil shells. Importantly, this reagent transport, that is to a large extent caused by aqueous drops that spontaneously form at the water-oil interface, is not limited to double emulsions but also occurs between single emulsion drops. We demonstrate that the uncontrolled reagent transport can be decreased by at least an order of magnitude if appropriate surfactants that lower the interfacial tension only moderately are employed or if the shell thickness of double emulsions is decreased to a few hundreds of nanometers.