Evolution of Nucleic-Acid-Based Constitutional Dynamic Networks Revealing Adaptive and Emergent Functions

The evolution of networks is a fundamental unresolved issue in developing the area of systems chemistry. We introduce a versatile rewiring mechanism that leads to the emergence of nucleic-acid-based constitutional dynamic networks (CDNs). A two-component constituent AA′ functionalized with a Mg²⁺-ion-dependent DNAzyme activator unit forms a complex with an intact hairpin H_BB′ composed of B and B′ sequences. Cleavage of H_BB′ leads to the two-component constituent BB′, and its rewiring with AA′ yields CDN X composed of the equilibrated constituents AA′, AB′, BA′, and BB′. In analogy, subjecting AA′ to an intact hairpin H_CC′ leads to the formation of CDN Y consisting of AA′, AC′, CA′, and CC′. Subjecting AA′ to the mixture of H_BB′ and H_CC′ evolves the [3×3] CDN Z, composed of nine constituents, thus demonstrating hierarchical adaptive properties. Furthermore, the DNAzyme units associated with the constituents are applied to tailor emerging catalytic functions from the different CDNs.