Spatially Defined Chemical Functionalization of Ordered Block Copolymer Materials

Here, we report a synthesis strategy that breaks this constraint by employing self-assembled ABC triblock terpolymer base materials with a gyroid nanoarchitecture and one cross-linked end block as robust 3D templates for the spatially defined in-gel functionalization of the tethered non-cross-linked blocks.

We demonstrate this generalizable concept with selective amine attachment in the C end block for selective metal ion coordination, uptake, and nanostructure-directed metal nanoparticle synthesis. Additionally, phase-confined sulfonation is achieved selectively on both the middle B and end C blocks, respectively, producing, to the best of our knowledge, the first monolithic gyroidal hydrogels exhibiting tunable swelling up to 600 vol % and nanoconfined hydration while maintaining structural integrity.