Exploring structural effects in single-chain folding mediated by intramolecular thermal Diels-Alder chemistry

We describe a method to fold single polymer chains into nanoparticles using simple thermal Diels-Alder (DA) chemistry. Two different folding strategies are explored, one employing chain-internal folding and the other using external, multi-functional cross-linkers. In the first strategy, random terpolymers were designed with varying incorporations of methyl methacrylate (MMA), furfuryl methacrylate (FMA) and a maleimide functionalized methacrylate (MIMA) to achieve internal folding through a thermal DA reaction between pendent furan and maleimide groups. In the second method, the synthesis of random copolymers of MMA and FMA forms nanoparticles after effecting a thermal DA reaction between pendent furan groups and external bi-or tri-maleimide functionalized cross-linkers. This multifaceted approach compares different synthetic designs of linear polymers as well as multiple cross-linker species as a means to explore the effect these synthetic differences have on the resulting SCNP. The two polymer series designed in this study allow for a direct comparison between chain internal cross-linking of multiple internal pendent groups and external cross-linker mediated collapse.