Redox-Active Dynamic Self-Supporting Thixotropic 3D-Printable G-Quadruplex Hydrogels

Area of Science:

• Materials Science
• Supramolecular Chemistry
• Biomaterials

Background:

• G-quadruplex structures offer unique self-assembly properties.
• Dynamic covalent chemistry enables the creation of responsive materials.
• Ferrocene-based redox activity can be harnessed for tunable material properties.

Purpose of the Study:

• To develop novel redox-active G-quadruplex hydrogels.
• To investigate the impact of dynamic boronate ester formation on hydrogel properties.
• To explore the stimuli-responsive behavior of ferrocene-modified hydrogels.

Main Methods:

• Preparation of hydrogels via dynamic boronate ester formation between ferroceneboronic acid and guanosine.
• Characterization of hydrogel properties including thixotropy and 3D-printability.
• Investigation of redox-induced structural and property changes through oxidation/reduction of the ferrocene moiety.

Main Results:

• Successful synthesis of redox-active G-quadruplex hydrogels.
• Dynamic boronate esters conferred thixotropic behavior and 3D-printability.
• Oxidation of ferrocene to ferrocenium resulted in a weaker, green hydrogel, which subsequently reverted to a robust, hydrophobic, and water-stable ferrocene-based hydrogel.

Conclusions:

• Dynamic boronate ester linkages are effective for creating tunable and printable G-quadruplex hydrogels.
• The redox state of ferrocene provides a mechanism for controlling hydrogel stability and properties.
• These hydrogels show potential for applications requiring stimuli-responsive and robust materials.