Gel-like coacervates prepared through ionotropic gelation enable very high loading and multiple-month release of weakly amphiphilic small molecules. Conversely, strong amphiphile incorporation disrupts ionic crosslinking and strikingly alters the coacervate properties.

Swelling of polymeric hydrogels is sensitive to their cross-link densities. Here, we exploit this principle to prepare self-rupturing gels which are based on a commonly-used, nontoxic, and inexpensive polyelectrolyte, poly(acrylic acid), and are prepared through a simple and low-cost polymerization-based technique. The self-rupture of these covalently cross-linked gels is achieved by preparing them to have highly nonuniform cross-link densities. This heterogeneity in cross-linking leads to highly nonuniform swelling, which generates stresses that are high enough to induce gel rupture. The time required for this rupture to occur depends on the difference in the cross-link densities between the adjoining gel regions, gel size, order in which the variably cross-linked gel portions are synthesized, and on the ambient pH and ionic strength. Furthermore, when these self-rupturing gels are prepared to have liquid-filled (capsule-like) morphologies, they can act as timed/delayed release devices. The self-rupture of these capsules provides a burst payload release after a preprogrammed delay, which is on the timescale of days and can be easily tuned by varying the rupture time, i.e., by varying either the cross-link nonuniformity or the pH and ionic strength of the release media.

We report a simple method for preparing solid polyelectrolyte complex (PEC) beads, which provide effective barriers to diffusion and can be used for the multiple-day release of small molecules. Single-phase poly(allylamine) (PAH) and poly(styrenesulfonate) (PSS) mixtures were prepared at pH 11.6 (significantly above the effective pKa of PAH), where the PAH amine groups were deprotonated and therefore neutral. These mixtures were added dropwise into acid baths, whereupon the rapid acid diffusion into the polyelectrolyte droplets led to instant ionization of PAH amine groups and, thus, the formation of PEC beads (i.e., via phase inversion). In stark contrast to the PEC particles prepared through phase inversion in previous studies, which had (solvent-filled) capsule-like morphologies, these beads had solid internal structures. The solute permeabilities of these PEC matrices could be extensively tuned by air drying the beads, which led to the apparently-irreversible closure of pores. Thus, by tuning the drying conditions and polymer compositions used during bead preparation, a model small molecule (Fast Green FCF dye) was released over times ranging between 2 and 18 days.

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