Sequence-selective dynamic covalent assembly of information-bearing oligomers

Area of Science:

• Supramolecular Chemistry
• Materials Science
• Chemical Engineering

Background:

• Dynamic covalent chemistry (DCC) is widely used for molecular self-assembly.
• Traditional DCC methods often result in kinetically-trapped, non-equilibrium mixtures.
• Achieving selective and ordered assembly remains a significant challenge.

Purpose of the Study:

• To develop a DCC strategy that mitigates kinetic trapping in self-assembly.
• To enable the formation of well-defined, in-registry molecular architectures.
• To demonstrate sequence-selective hybridization and information encoding/retrieval.

Main Methods:

• Utilized dynamic covalent interactions for self-assembly of oligomers with coreactive pendant groups.
• Implemented a reagent concentration cycling strategy (analogous to thermal cycling) to control dissociation and rearrangement.
• Achieved simultaneous, sequence-selective hybridization with complementary strands.

Main Results:

• Successfully mitigated kinetic trapping, leading to ordered molecular ladders with covalent rungs.
• Demonstrated the ability to form multiple unique oligomers that assemble selectively.
• Showcased retrieval of encoded information via hybridization with mass-labeled complementary sequences.

Conclusions:

• The developed method provides a robust pathway to thermodynamically controlled dynamic covalent self-assembly.
• This approach enables the construction of complex, biomimetic molecular architectures with high fidelity.
• The process has potential applications in molecular information storage and advanced materials design.