Divalent Multilinking Bonds Control Growth and Morphology of Nanopolymers

Assembly of nanoscale objects into linear architectures resembling molecular polymers is a basic organization resulting from divalent interactions. Such linear architectures occur for particles with two binding patches on opposite sides, known as Janus particles. However, unlike molecular systems where valence bonds can be envisioned as pointlike interactions nanoscale patches are often realized through multiple molecular linkages. The relationship between the characteristics of these linkages, the resulting interpatch connectivity, and assembly morphology is not well-explored. Here, we investigate assembly behavior of model divalent nanomonomers, DNA nanocuboid with tailorable multilinking bonds. Our study reveals that the characteristics of individual molecular linkages and their collective properties have a profound effect on nanomonomer reactivity and resulting morphologies. Beyond linear nanopolymers, a common signature of divalent nanomonomers, we observe an effective valence increase as linkages lengthened, leading to the nanopolymer bundling. The experimental findings are rationalized by molecular dynamics simulations.

Automated summary

The assembly of nanoscale objects into linear structures resembling molecular polymers is influenced by divalent interactions, such as those seen in Janus particles with binding patches on opposite sides. The study of DNA nanocuboids with tailorable multilinking bonds reveals that the characteristics of individual molecular linkages and their collective properties significantly impact nanomonomer reactivity and resulting morphologies. As the linkages lengthen, an effective increase in valence is observed in divalent nanomonomers, leading to nanopolymer bundling.