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Controlling the Size, Shape and Stability of Supramolecular Polymers in Water
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Selective solvent conditions influence sequence development and supramolecular assembly in step-growth
Ryan L Hamblin1, Nhu Q Nguyen1, Kateri H DuBay1
1Department of Chemistry, University of Virginia, McCormick Road, PO Box 400319, Charlottesville, VA 22903-4319, USA. dubay@virginia.edu.
Soft Matter
|December 2, 2021
Summary
Controlling synthetic copolymer sequences is key for material properties. This study shows solvent-mediated attractions between monomers can drive self-assembly and sequence control in A-B copolymerizations.
Area of Science:
- Polymer Chemistry
- Materials Science
- Supramolecular Chemistry
Background:
- Sequence control in synthetic copolymers is crucial for tuning material properties and self-organization.
- Previous simulations indicated monomer-monomer attractions influence sequence development in step-growth copolymerizations.
- Understanding sequence evolution aids in designing generalizable methods for sequence control.
Purpose of the Study:
- To investigate how solvent-mediated attractive interactions impact sequence development and supramolecular assembly in A-B copolymerization.
- To explore the role of monomer-solvent affinities in controlling copolymer sequence and aggregate morphology.
- To demonstrate a method for designing sequence-controlled amphiphilic copolymers.
Main Methods:
- Computational simulations of solution-based step-growth A-B copolymerization.
- Analysis of sequence development under varying solvent selectivity and monomer-monomer attractions.
- Characterization of emergent self-organization and supramolecular assembly.
Main Results:
- Increased effective monomer attractions, mediated by selective solvents, alter reaction kinetics and sequence development.
- Sufficiently selective solvent-mediated interactions induce self-assembly of A-B monomers into amphiphilic copolymer-like structures.
- Copolymer sequence, aggregate composition, and morphology are sensitive to monomer-solvent affinities.
Conclusions:
- Solvent-mediated interactions offer a powerful tool to control sequence development in solution-based copolymerizations.
- Emergent self-organization driven by monomer-solvent affinities leads to sequence-controlled amphiphilic structures.
- This work provides insights for designing synthetic strategies for sequence-controlled amphiphilic copolymers and their aggregates.
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