Abstract
Polymer-polymer aqueous two-phase systems (ATPSs) are attractive for microgel synthesis, but given the complexity of phase separation, predicting microgel material properties from ATPS formulations is not trivial. The objective of this study was to determine how the phase diagram of a poly(ethylene glycol) (PEG) and dextran ATPS is related to the material properties of PEG microgel products. PEG-dextran ATPSs were prepared from four-arm 20 kDa PEG-norbornene and 40 kDa dextran in phosphate buffered saline (PBS), and the phase diagram was constructed. PEG microgels were synthesized from five ATPS formulations using an oligopeptide cross-linker and thiol-norbornene photochemistry. Thermogravimetric analysis (TGA) revealed that the polymer concentration of microgel pellets linearly correlates with the average concentration of PEG in the ATPS rather than the separated phase compositions, as determined from the phase diagram. Atomic force microscopy (AFM) and bulk rheology studies demonstrated that the mechanical properties of microgels rely on both the average concentration of PEG in the ATPS and the ATPS volume ratio as determined from the phase diagram. These findings suggest that PEG-dextran ATPSs undergo homogenization upon mixing, which principally determines the material properties of the microgels upon gelation.