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Microcapsules allow for the controlled containment, transport, and release of cargoes ranging from pharmaceuticals to fragrances. Given the interest from a variety of industries in microcapsules and other core–shell structures, a multitude of fabrication strategies exist. Here, we report on a method relying on a mixture of temperature-responsive microgel particles, poly( N -isopropylacrylamide) (pNIPAM), and a polymer which undergo fluid–fluid phase separation. At room temperature this mixture separates into colloid-rich (liquid) and colloid-poor (gas) fluids. By heating the sample above a critical temperature where the microgel particles shrink dramatically and develop a more deeply attractive interparticle potential, the droplets of the colloid-rich phase become gel-like. As the temperature is lowered back to room temperature, these droplets of gelled colloidal particles reliquefy and phase separation within the droplet occurs. This phase separation leads to colloid-poor droplets within the colloid-rich droplets surrounded by a continuous colloid-poor phase. The gas/liquid/gas all-aqueous double emulsion lasts only a few minutes before a majority of the inner droplets escape. However, the colloid-rich shell of the core–shell droplets can solidify with the addition of salt. That this method creates core–shell structures with a shell composed of stimuli-sensitive microgel colloidal particles using only aqueous components makes it attractive for encapsulating biological materials and making capsules that respond to changes in, for example, temperature, salt concentration, or pH.
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Designing negative feedback loops in enzymatic coacervate droplets
Membraneless organelles within the living cell use phase separation of biomolecules coupled with enzymatic reactions to regulate cellular processes. The diverse functions of these biomolecular condensates motivate the pursuit of simpler in vitro models that exhibit primitive forms of self-regulation based on internal feedback mechanisms. Here, we investigate one such model based on complex coacervation of the enzyme catalase with an oppositely charge polyelectrolyte DEAE-dextran to form pH-responsive catalytic droplets. Upon addition of hydrogen peroxide “fuel”, enzyme activity localized within the droplets causes a rapid increase in the pH. Under appropriate conditions, this reaction-induced pH change triggers coacervate dissolution owing to its pH-responsive phase behavior. Notably, this destabilizing effect of the enzymatic reaction on phase separation depends on droplet size owing to the diffusive delivery and removal of reaction components. Reaction-diffusion models informed by the experimental data show that larger drops support larger changes in the local pH thereby enhancing their dissolution relative to smaller droplets. Together, these results provide a basis for achieving droplet size control based on negative feedback between pH-dependent phase separation and pH-changing enzymatic reactions.
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- Award ID(s):
- 1938303
- PAR ID:
- 10502008
- Publisher / Repository:
- RSC
- Date Published:
- Journal Name:
- Chemical Science
- Volume:
- 14
- Issue:
- 18
- ISSN:
- 2041-6520
- Page Range / eLocation ID:
- 4735 to 4744
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/D2SC03838B
