Self-Assembled G-fold DNA/Amino Acid Amphiphiles-Based Oxidase-Mimetic Materials Exhibiting Drug-Degrading and Photoswitchable Capabilities

Recreating the intricate enzymatic sites within in artificial materials poses a significant challenge due to the complex folding characteristics of enzymes. In this study, we designed a supramolecular catalyst by assembling intramolecularly folding G-quadruplex DNA with Fmoc-amino acid aggregates and Cu2+. This supramolecular material possesses active sites and catalytic functions that rely on copper clusters, mirroring the functionality of catechol oxidase. Experimental and theoretical simulations showed that Fmoc-amino acids interact with G-quadruplex DNA through groove binding, facilitating Cu2+ coordination to both components, thereby enhancing the oxidative catalysis of Cu2+ upon assembly. Our catalyst exhibited excellent tolerance to high temperature, varying ionic strength, and extended room-temperature storage in aqueous solutions. Moreover, our supramolecular complex effectively catalyzed the degradation of doxorubicin, a drug with a high affinity for the DNA component, demonstrating its potential for removing pharmacological pollutants. Additionally, by integrating a photoisomerizable azobenzene derivative as a ligand to the G-quadruplex DNA, we can switch the activity of the enzyme-mimetic catalyst between on and off states by adjusting the irradiation wavelength. This multicomponent approach offers a promising avenue for the design and engineering of active, adaptable supramolecular catalysts.