DNA‐Intercalating Supramolecular Hydrogels for Tunable Thermal and Viscoelastic Properties

• Published in: Angewandte Chemie International Edition Vol. 63; no. 45; pp. e202411115 - n/a
• Main Authors: Hughes, Shaina M., Aykanat, Aylin, Pierini, Nicholas G., Paiva, Wynter A., Weeks, April A., Edwards, Austin S., Durant, Owen C., Oldenhuis, Nathan J.
• Format: Journal Article
• Language: English
• Published: Germany Wiley Subscription Services, Inc 04.11.2024
• Edition: International ed. in English
• Subjects: Acridine; Binding; Biomaterials; Biomedical materials; Deoxyribonucleic acid; DNA; DNA Intercalations; DNA structure; Entropy driven gelation; Hydrogels; Hydrophobicity; Molecular structure; Phenanthridine; Polyethylene glycol; Polymers; Psoralen; Supramolecular hydrogels; Thermal response; Viscoelasticity; Entropy driven gelation; Supramolecular hydrogels; DNA Intercalations; Biomaterials
• ISSN: 1433-7851; 1521-3773; 1521-3773
• DOI: 10.1002/anie.202411115

Polymeric supramolecular hydrogels (PSHs) leverage the thermodynamic and kinetic properties of non‐covalent interactions between polymer chains to govern their structural characteristics. As these materials are formed via endothermic or exothermic equilibria, their thermal response is challenging to control without drastically changing the nature of the chemistry used to join them. In this study, we introduce a novel class of PSHs utilizing the intercalation of double‐stranded DNA (dsDNA) as the primary dynamic non‐covalent interaction. The resulting dsDNA intercalating supramolecular hydrogels (DISHs) can be tuned to exhibit both endothermically or exothermically driven binding through strategic selection of intercalators. Bifunctional polyethylene glycol (MW~2000 Da) capped with intercalators of varying hydrophobicity, charge, and size (acridine, psoralen, thiazole orange, and phenanthridine) produced DISHs with comparable moduli (500–1000 Pa), but unique thermal viscoelastic responses. Notably, acridine‐based cross‐linkers displayed invariant and even increasing relaxation times with temperature, suggesting an endothermic binding mechanism. This methodology expands the set of structure‐properties available to biomass‐derived DNA biomaterials and promises a new material system where a broad set of thermal and viscoelastic responses can be obtained due to the sheer number and variety of intercalating molecules. We introduce DNA intercalating supramolecular hydrogels (DISHs) that leverage the intercalation of double‐stranded DNA as a cross‐linking mechanism. These DISHs exhibit tunable endothermic or exothermic driven material properties via strategic choice of intercalator. Interestingly, acridine‐PEG cross‐linkers showing increasing elasticity with increasing temperature, suggesting these materials are joined by purely entropic forces.