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.

合成聚合物与各种生物分子的结合使生物混合材料易于使用，这些材料结合了合成世界和自然界的优势。由于合成工具的快速发展以及对生物分子结构和功能的加深了解，这些聚合物生物共轭物不仅对生物医学应用很重要，而且可以作为材料科学中的创新构造。这篇综述总结了在结构上定义的聚合物生物共轭物的选择及其在制备分级生物杂交材料中的应用。从这个角度出发，我们讨论并说明了最近的突破，这些突破描绘了该领域可能如何发展。我们首先介绍已用于构建精密聚合物生物共轭物的一般合成方法。介绍了用于特定位置缀合的各种化学方法，控制聚合物的大小，分布，拓扑和功能的不同方法，以及对生物缀合物结构的通用操作。随后，将分别讨论基于包括蛋白质/肽，核酸，碳水化合物，脂质，甚至活细胞在内的不同生物实体的聚合物生物缀合物的最新进展。特别是，我们专注于在不同长度尺度上的各种形式的定义明确的构建体，范围从精密的聚合物和生物分子模板化的纳米结构，到溶液，散装和表面上的聚合物生物缀合物的有序组装。