Abstract
Molecular strain can be introduced to influence the outcome of chemical reactions. Once a thermodynamic product is formed, however, reversing the course of a strain-promoted reaction is challenging. Here, a reversible, strain-promoted polymerization in cyclic DNA is reported. The use of nonhybridizing, single-stranded spacers as short as a single nucleotide in length can promote DNA cyclization. Molecular strain is generated by duplexing the spacers, leading to ring opening and subsequent polymerization. Then, removal of the strain-generating duplexers triggers depolymerization and cyclic dimer recovery via enthalpy-driven cyclization and entropy-mediated ring contraction. This reversibility is retained even when a protein is conjugated to the DNA strands, and the architecture of the protein assemblies can be modulated between bivalent and polyvalent states. This work underscores the utility of using DNA not only as a programmable ligand for assembly but also as a route to access restorable bonds, thus providing a molecular basis for DNA-based materials with shape-memory, self-healing, and stimuli-responsive properties.
| Original language | English (US) |
|---|---|
| Article number | eade1650 |
| Journal | Science Advances |
| Volume | 10 |
| Issue number | 17 |
| DOIs | |
| State | Published - Apr 2024 |
Funding
Acknowledgments: We would like to thank Y. Gu for helpful discussions. this work made use of the SPid facilities of the nUAnce center and iMSeRc at northwestern University, which have received support from Soft and Hybrid nanotechnology experimental (SHyne) Resource (nSF-eccS-1542205), MRSec program (nSF dMR-1121262) at the Materials Research center, the international institute for nanotechnology (iin), the Keck Foundation, and the State of illinois. Funding: this material is based upon work supported by the following awards: national Science Foundation dMR-2104353, Air Force Office of Scientific Research FA9550-22-1-0300, and the Sherman Fairchild Foundation inc. Author contributions: conceptualization: Z.H., O.G.H., B.e.P., c.H., and c.A.M. Methodology, investigation, and visualization: Z.H. Supervision: c.A.M. Writing\u2014original draft: Z.H. Writing\u2014review and editing: Z.H., O.G.H., B.e.P., c.H., and c.A.M. Competing interests: the authors declare that they have no competing interests. Data and materials availability: All data needed to evaluate the conclusions in the paper are present in the paper and/or the Supplementary Materials.
ASJC Scopus subject areas
- General