Shape-memory and self-healing functions of DNA-based carboxymethyl cellulose hydrogels driven by chemical or light triggers

Abstract

Photoresponsive nucleic acid-based carboxymethyl cellulose (CMC) hydrogels are synthesized, and their application as shape-memory and self-healing functional matrices are discussed. One system involves the preparation of a carboxymethyl cellulose hydrogel crosslinked by self-complementary nucleic acid duplexes and by photoresponsive <i>trans</i>-azobenzene/β-cyclodextrin (β-CD) supramolecular complexes. Photoisomerization of the <i>trans</i>-azobenzene to the <i>cis</i>-azobenzene results in a hydrogel exhibiting lower stiffness due to the separation of the azobenzene/β-CD bridging units. The hydrogel is switched between high and low stiffness states by the cyclic and reversible light-induced isomerization of the azobenzene units between the <i>trans</i> and <i>cis</i> states. The light-controlled stiffness properties of the hydrogel are used to develop a shape-memory hydrogel, where the duplex bridging units act as permanent memory in the quasi-liquid shapeless state of the hydrogel. A second system in the study is a carboxymethyl cellulose hydrogel crosslinked by the K⁺-stabilized G-quadruplex bridging units and by <i>trans</i>-azobenzene/β-CD complexes. The resulting hydrogel includes dual-trigger functionalities, where the <i>trans</i>-azobenzene/β-CD complexes can be reversibly formed and dissociated through the <i>trans</i> and <i>cis</i> photoisomerization of the azobenzene units, and the K⁺-stabilized G-quadruplexes can be reversibly dissociated and reformed in the presence of 18-crown-6-ether/K⁺-ions. The signal-responsive crosslinked hydrogel reveals controlled stiffness properties, where the hydrogel crosslinked by the <i>trans</i>-azobenzene/β-CD and K⁺-ion-stabilized G-quadruplex reveals high stiffness and the hydrogel crosslinked only by the K⁺-ion-stabilized G-quadruplexes or only by the <i>trans</i>-azobenzene/β-CD complexes reveals low stiffness properties. The controlled stiffness properties of the hydrogel are used to develop shape-memory hydrogels, where the <i>trans</i>-azobenzene/β-CD complexes or the K⁺-ion-stabilized G-quadruplexes act as permanent memories in the shapeless and quasi-liquid states of the hydrogels. In addition, the hydrogel that includes two types of stimuli-responsive crosslinking units is used as a self-healing matrix, where each of the triggers guides the self-healing processes.