Cross‐linking in Peptide‐ and Peptoid‐Based Hierarchical Nanomaterials: A Physical Organic Chemistry Perspective

Peptide‐ and peptoid‐based biomimetic hierarchical materials have received significant attention as their structure and functionality can be precisely programmed by molecular design and self‐assembly. Although numerous reviews have highlighted their synthesis, self‐assembly behavior, and applications, the fundamental roles of noncovalent and covalent cross‐linking in governing their hierarchical organization, stability, and functionality have not been systematically examined from a physical organic chemistry perspective. This mini review discusses how molecular recognition, reaction kinetics, reaction mechanisms, and thermodynamics govern hierarchical self‐assembly and postassembly cross‐linking of peptide‐ and peptoid‐based hierarchical materials.