Colloids in low-frequency (<1 kHz) oscillatory electric fields near planar electrodes aggregate in neutral pH electrolytes due to electrohydrodynamic (EHD) flow but separate in alkaline pH electrolytes. Colloid ζ-potential and electrolyte ion mobilities are thought to play roles in the underlying mechanism for this phenomenon, but a unifying theory for why particles aggregate in some electrolytes and separate in others remains to be established. Here, we show that increasing local pH near the electrode with an electrochemical reaction causes a colloidal aggregation-to-separation transition in oscillatory electric fields that induce strong attractive EHD flows. An electroactive molecule, para-benzoquinone, was electrochemically reduced at the electrode to locally increase the solution pH near the colloids. Superimposing a sufficiently large steady electrochemical potential onto an oscillatory potential caused a reversible aggregation-to-separation transition. Counterintuitively, decreasing frequency, which increases attractive EHD drag forces, caused a similar aggregation-to-separation transition. Even more interesting, multiple transitions were observed while varying the oscillatory potential. Taken together, these results suggested that the oscillatory potential induced a repulsive hydrodynamic drag force. Scaling arguments for the recently discovered asymmetric rectified electric field (AREF) showed that a repulsive AREF-induced electroosmotic (EO) flow competed with attractive EHD flow. A pairwise colloidal force balance including these competing flows exhibited flow inversions qualitatively consistent with experimentally observed aggregation-to-separation transitions. Broadly, these results emphasize the importance of AREF-induced EO flows in colloid aggregation and separation in low-frequency oscillatory electric fields.

Microgels of biopolymers such as alginate are widely used to encapsulate cells and other biological payloads. Alginate is an attractive material for cell encapsulation because it is nontoxic and convenient: spherical alginate gels are easily created by contacting aqueous droplets of sodium alginate with divalent cations such as Ca2+. Alginate chains in the gel become cross-linked by Ca2+ cations into a 3-D network. When alginate gels are placed in a buffer, however, the Ca2+ cross-links are eliminated by exchange with Na+, thereby weakening and degrading the gels. With time, encapsulated cells are released into the external solution. Here, we describe a simple solution to the above problem, which involves forming alginate gels enveloped by a thin shell of a covalently cross-linked gel. The shell is formed via free-radical polymerization using conventional monomers such as acrylamide (AAm) or acrylate derivatives, including polyethylene glycol diacrylate (PEGDA). The entire process is performed in a single step at room temperature (or 37 °C) under mild, aqueous conditions. It involves combining the alginate solution with a radical initiator, which is then introduced as droplets into a reservoir containing Ca2+ and monomers. Within minutes of either simple incubation or exposure to ultraviolet (UV) light, the droplets are converted into alginate–polymer microcapsules with a core of alginate and a shell of the polymer (AAm or PEGDA). The microcapsules are mechanically more robust than conventional alginate/Ca2+ microgels, and while the latter swell and degrade when placed in buffers or in chelators like sodium citrate, the former remain stable under all conditions. We encapsulate both bacteria and mammalian cells in these microcapsules and find that the cells remain viable and functional over time. Lastly, a variation of the synthesis technique is shown to generate multilayered microcapsules with a liquid core surrounded by concentric layers of alginate and AAm gels. We anticipate that the approaches presented here will find application in a variety of areas including cell therapies, artificial cells, drug delivery, and tissue engineering.

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