We describe a new methodology to prepare loaded polyelectrolyte/surfactant films at the air/water interface by exploiting Marangoni spreading resulting from the dynamic dissociation of hydrophobic neutral aggregates dispensed from an aqueous dispersion. The system studied is mixtures of poly(sodium styrene sulfonate) with dodecyl trimethylammonium bromide. Our approach results in the interfacial confinement of more than one third of the macromolecules in the system even though they are not even surface-active without the surfactant. The interfacial stoichiometry of the films was resolved during measurements of surface pressure isotherms in situ for the first time using a new implementation of neutron reflectometry. The interfacial coverage is determined by the minimum surface area reached when the films are compressed beyond a single complete surface layer. The films exhibit linear ripples on a length scale of hundreds of micrometers during the squeezing out of material, after which they behave as perfectly insoluble membranes with consistent stoichiometric charge binding. We discuss our findings in terms of scope for the preparation of loaded membranes for encapsulation applications and in deposition-based technologies.
We demonstrate the ability to tune the formation of extended structures in films of poly(sodium styrenesulfonate)/dodecyltrimethylammonium bromide at the air/water interface through control over the charge/structure of aggregates as well as the ionic strength of the subphase. Our methodology to prepare loaded polyelectrolyte/surfactant films from self-assembled liquid crystalline aggregates exploits their fast dissociation and Marangoni spreading of material upon contact with an aqueous subphase. This process is proposed as a potential new route to prepare cheap biocompatible films for transfer applications. We show that films spread on water from swollen aggregates of low/negative charge have 1:1 charge binding and can be compressed only to a monolayer, beyond which material is lost to the bulk. For films spread on water from compact aggregates of positive charge, however, extended structures of the two components are created upon spreading or upon compression of the film beyond a monolayer. The application of ellipsometry, Brewster angle microscopy, and neutron reflectometry as well as measurements of surface pressure isotherms allow us to reason that formation of extended structures is activated by aggregates embedded in the film. The situation upon spreading on 0.1 M NaCl is different as there is a high concentration of small ions that stabilize loops of the polyelectrolyte upon film compression, yet extended structures of both components are only transient. Analogy of the controlled formation of extended structures in fluid monolayers is made to reservoir dynamics in lung surfactant. The work opens up the possibility to control such film dynamics in related systems through the rational design of particles in the future.
Reversible control of the 3D structure of polyelectrolyte/surfactant films at the air/water interface is showcased. A recently discovered mechanism is exploited to form highly efficient, stable and biocompatible films by...
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