Fabrication of pH-degradable supramacromolecular microgels with tunable size and shape via droplet-based microfluidics

This study presents a versatile method to synthesize stimuli-responsive microgels with supramolecular cross-links exhibiting tunable size and shape via droplet-based microfluidics. The natural polyphenol tannic acid (TA) is used to cross-link poly(N-vinylcaprolactam) (PVCL) chains in aqueous droplets by the formation of hydrogen bonds and hydrophobic interactions between the phenolic groups of TA and the carbonyl group and the hydrophobic segments of lactam ring of PVCL chains. The obtained microgels exhibit diameters in the range of 130-150µm in swollen state in aqueous solution. Synthesized microgels exhibit pH-responsive behavior: at low pH microgels deswell and shrink due to the protonation of phenolic groups and enhanced hydrophobic interactions; at high pH microgels swell and disintegrate due to the deprotonation of phenolic groups and destruction of hydrogen bonds with PVCL chains. Additionally, we present supramacromolecular microgels in cylindrical shape with different aspect ratios using a new design of microfluidic chip by varying flow rates at high concentration of the prepolymerized precursor combined with rapid pH-triggered on-chip gelation. Furthermore, developed synthesis methodology allows on-chip encapsulation of colloidal objects into large supramacromolecular microgels during the cross-linking step. The complete and fast release of objects by pH-triggered degradation indicates that the pH-responsive supramacromolecular microgels can be used for controlled loading/release of various payloads, like probiotics. Moreover, cell studies of L929 fibroblast clearly show the biocompatibility of the microgels.