Directed co-assembly of hemeproteins with amphiphilic block copolymers toward functional biomolecular materials

Directed co-assembly of block copolymers and proteins/peptides may lead to hierarchically structured functional biomolecular materials. However, this requires one to synergistically direct multiple self-assembly processes. Retaining proper cofactor binding is essential to utilize many bio-motifs for catalytic reactions and sensing. Here, by using a heme-binding helix bundle peptide-polymer conjugate and a holomyoglobin-polymer conjugate as examples, we show that the simultaneous, macroscopic assembly of heme-binding proteins and diblock copolymers can be achieved in thin films without compromising protein structures, cofactor binding and enzymatic activities. To our knowledge, this is the first example of a protein/cofactor complex formed upon being co-assembled with an amphiphilic block copolymer in thin films. Molecular assemblyvia a combination of biomolecular recognition and polymer phase separation in this fashion will lead to hybrid materials combining properties of both synthetic and biological building blocks.