Rational Design of DNA Hydrogels Based on Molecular Dynamics of Polymers

In recent years, DNA has emerged as a fascinating building material to engineer hydrogel due to its excellent programmability, which has gained considerable attention in biomedical applications. Understanding the structure–property relationship and underlying molecular determinants of DNA hydrogel is essential to precisely tailor its macroscopic properties at molecular level. In this review, the rational design principles of DNA molecular networks based on molecular dynamics of polymers on the temporal scale, which can be engineered via the backbone rigidity and crosslinking kinetics, are highlighted. By elucidating the underlying molecular mechanisms and theories, it is aimed to provide a comprehensive overview of how the tunable DNA backbone rigidity and the crosslinking kinetics lead to desirable macroscopic properties of DNA hydrogels, including mechanical properties, diffusive permeability, swelling behaviors, and dynamic features. Furthermore, it is also discussed how the tunable macroscopic properties make DNA hydrogels promising candidates for biomedical applications, such as cell culture, tissue engineering, bio‐sensing, and drug delivery. The macroscopic characteristics of DNA hydrogels can be manipulated by controlling the molecular dynamics of the DNA network at the molecular level, specifically through adjusting the backbone rigidity and crosslinking kinetics. Therefore, DNA hydrogel networks can be designed with precisely tailored macroscopic properties, making DNA hydrogels promising candidates for biomedical applications.