Temperature- and redox-directed multiple self assembly of poly(N-isopropylacrylamide) grafted dextran nanogels

Poly(N-isopropylacrylamide) (PNIPAAm) grafted dextran nanogels with dodecyl and thiol end groups have been synthesized by RAFT process. Dodecyl-terminated polymers (DexPNI) can be readily dissolved in water and further self assemble into ordered stable nanostructures through direct noncovalent interactions at room temperature. SEM, AFM and DLS measurements confirm the formation of spherical nanogels at hundred-nanometer scales. The elevation of environment temperature will indirectly result in the formation of collapsed nanostructures due to the LCST phase transition of PNIPAAm side chains. Turbidimetry results show that the phase transition behaviors of DexPNI are greatly dependent on PNIPAAm chain length and polymer concentration: increasing PNIPAAm chain length and polymer concentration both lead to lower LCSTs and sharper phase transitions. Moreover, the dodecyl-terminated polymers can transform into thiol-terminated versions by aminolysis of trithiocarbonate groups, and further into chemical (disulfide) cross-linked versions (SS-DexPNI) by oxidation. SS-DexPNI nanogels have "doubled" chain length of PNIPAAm, and hence sharper phase transitions. In situ DLS measurements of the evolution of hydrodynamic radius attest that the self assembly of SS-DexPNI nanogels can be selectively directed by the change in either external temperature or redox potential. These nanogels thus are promising candidates for triggered intracellular delivery of encapsulated cargo. We can also expect that the polymer can be noncovalently (by dodecyl end groups) or covalently (by thiol end groups) coated on a series of nanomaterials (e.g., carbon nanotubes, graphene, gold nanomaterials) to build a variety of novel smart, and robust nanomaterials.