Autonomous and Programmable Reorganization of DNA-Based Polymers Using Redox Chemistry

We demonstrate here a strategy that allows the programmable and autonomous reorganization of self-assembled DNA polymers using redox chemistry. We have rationally designed different DNA monomers (tiles) that can co-assemble into tubular structures. The tiles can be orthogonally activated/deactivated with disulfide-linked DNA fuel strands that are degraded over time upon reduction because of the presence of a reducing agent in the system. The concentration of the disulfide fuels determines the activation kinetics of each DNA tile, which controls the degree of order/disorder in the formed co-polymer. The disulfide-reduction pathway can be employed together with enzymatic fuel-degradation pathways providing an additional level of control in the re-organization of DNA structures. Taking advantage of the different pH-sensitivities of disulfide-thiol and enzymatic reactions, we show that we can control the order in DNA-based co-polymers as a function of pH.

Automated summary

We introduce a strategy for programmable and autonomous reorganization of self-assembled DNA polymers using redox chemistry. Different DNA monomers are designed to co-assemble into tubular structures, which can be orthogonally activated/deactivated with disulfide-linked DNA fuel strands that are degraded over time upon reduction. The concentration of the disulfide fuels controls the activation kinetics of each DNA tile, thus regulating the degree of order/disorder in the formed co-polymer. By combining the disulfide-reduction pathway with enzymatic fuel-degradation pathways, the re-organization of DNA structures can be further controlled. The pH sensitivity of the disulfide-thiol and enzymatic reactions allows for pH-dependent control over the order in DNA-based co-polymers.