Complex coacervates formed through the association of charged polymers with oppositely charged species are often investigated for controlled release applications and can provide highly sustained (multi-day, -week or -month) release of both small-molecule and macromolecular actives. This release, however, can sometimes be too slow to deliver the active molecules in the doses needed to achieve the desired effect. Here, we explore how the slow release of small molecules from coacervate matrices can be accelerated through mechanical stimulation. Using coacervates formed through the association of poly(allylamine hydrochloride) (PAH) with pentavalent tripolyphosphate (TPP) ions and Rhodamine B dye as the model coacervate and payload, we demonstrate that slow payload release from complex coacervates can be accelerated severalfold through mechanical stimulation (akin to flavor release from a chewed piece of gum). The stimulation leading to this effect can be readily achieved through either perforation (with needles) or compression of the coacervates and, besides accelerating the release, can result in a deswelling of the coacervate phases. The mechanical activation effect evidently reflects the rupture and collapse of solvent-filled pores, which form due to osmotic swelling of the solute-charged coacervate pellets and is most pronounced in release media that favor swelling. This stimulation effect is therefore strong in deionized water (where the swelling is substantial) and only subtle and shorter-lived in phosphate buffered saline (where the PAH/TPP coacervate swelling is inhibited). Taken together, these findings suggest that mechanical activation could be useful in extending the complex coacervate matrix efficacy in highly sustained release applications where the slowly releasing coacervate-based sustained release vehicles undergo significant osmotic swelling.
Keywords: complex coacervate; controlled release; polyamine; polyelectrolyte; stimulus-responsive materials.