Compartmentalized Polyampholyte Microgels by Depletion Flocculation and Coacervation of Nanogels in Emulsion Droplets

In pH-responsive drug carriers, the distribution of charges has been proven to affect delivery efficiency but is difficult to control and verify. Herein, we fabricate polyampholyte nanogel-in-microgel colloids (NiM-C) and show that the arrangement of the nanogels (NG) can easily be manipulated by adapting synthesis conditions. Positively and negatively charged pH-responsive NG are synthesized by precipitation polymerization and labelled with different fluorescent dyes. The obtained NG are integrated into microgel (MG) networks by subsequent inverse emulsion polymerization in droplet-based microfluidics. By confocal laser scanning microscopy (CLSM), we verify that depending on NG concentration, pH value and ionic strength, NiM-C with different NG arrangements are obtained, including Janus-like phase-separation of NG, statistical distribution of NG, and core-shell arrangements. Our approach is a major step towards uptake and release of oppositely charged (drug) molecules.