Microfluidic fabrication of smart micro gels from macromolecular precursors

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Microuidic emulsication of a semidilute solution of crosslinkable pNIPAAm precursors in water (schematic). Subsequent gelation of the monodisperse droplets, achieved through crosslinking the polymer chains by dimerization of pendant reactive side groups, forms monodisperse microgel particles.


Microuidic templating of anisotropic microgels with two distinguishable sides (“Janus microgels”). (A) Optical micrograph of a microuidic device forming aqueous droplets from three separate semidilute pNIPAAm solutions. In the rst junction, these three solutions meet and form a laminar, co-owing stream. In the second junction, this stream is broken to form monodisperse droplets by ow focusing with parafn oil. For demonstration purposes, two of the three polymer phases are tagged with either red or green uorescent dyes while the third phase is untagged; however, note that the color in Panel A was added digitally, because the true color of these polymer solutions is visible only through uorescence. To visualize the ow pattern with greater clarity, the inset micrograph shows a similar experiment with a center phase that is doped with iron oxide nanoparticles (from Ref. [38]). Right after their formation, the droplets enter a wide basin channel, where they are gelled by UV exposure. (B) Fluorescence micrographs of the resultant microgel particles. Varying the ow rates of the two tagged outer polymer phases, the untagged center polymer phase, and the emulsifying oil phase from 105:105:30:500 mL h1 (upper row of micrographs) to 30:30:180:500 mL h1 (lower row of micrographs) yields particles with different inner morphology. All scalebars denote 100 mm.



Thermo-responsive behavior and controlled release application of pAAm-pNIPAAm core-shell microgels. (A) Fluorescence images (left column) and bright field micro-graphs (right column) of microgels consisting of a 60 mm untagged pAAm core encapsulated in a green-tagged pNIPAAm shell. At ambient temperatures (upper row), the shell is swollen, whereas it collapses at elevated temperatures (lower row). By contrast, the core dimension remains unaffected by the same changes of temperature. (B) Detailed plot of the particle-diameter, d, as a function of temperature, T. Dark blue circles represent the diameter of the entire particle, i.e., pAAm core plus pNIPAAm shell, whereas light blue squares represent only the pAAm core. The dotted lines are guides to the eye. (C) Controlled release of RITC-dextran (M 10,000 g mol-1) from the particles in Panel A. In the course of the first 10 s of this experiment, the temperature remains above 33 C, and the particles remain sealed (left three pictures). As the temperature decreases, a spontaneous release of the active incorporated in the particles is triggered by the swelling of the pNIPAAm shells. All scalebars denote 100 μm.

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1. S. Seiffert, D.A. Weitz, "Microfluidic fabrication of smart microgels from macromolecular precursors", Polymer 51 (2010) 5883-5889