LAUSR

Abstract The conjugation of synthetic polymers with various biomolecules provides an easy access to biohybrid materials which combine advantages from both the synthetic world and Nature. Due to the rapid development of synthetic tools and deepening understanding of biomolecule structure and function, these polymer bioconjugates are not only important for biomedical applications, but also can serve as innovative constructs in materials science. This review summarizes a selection of structurally defined polymer bioconjugates and their application as building blocks for preparing hierarchical biohybrid materials. From this perspective, we discuss and illustrate recent breakthroughs, which portray how the field may potentially develop. We first introduce the general synthetic approaches that have been employed for the construction of precision polymer bioconjugates. Various chemistries for site-specific conjugation, different approaches to control the size, distribution, topology, and function of polymers, as well as the versatile manipulation of bioconjugate architecture are presented. Subsequently, recent advances of polymer bioconjugates based on different biological entities including proteins/peptides, nucleic acids, carbohydrates, lipids and even live cells are discussed individually. In particular, we focus on various forms of well-defined constructs at different length scales ranging from precision polymers and nanostructures templated by biomolecules to highly ordered assemblies of polymer bioconjugates in solution, in bulk and on surfaces. Some representative applications of these biohybrids resulting from their high degree of structural precision are also highlighted.