Mapping in situ the assembly and dynamics in aqueous supramolecular polymers
Supramolecular polymers, bonded through directional non-covalent interactions, closely mimic dynamic behaviors of biological nanofibers. However, the complexity of assembly pathways makes it highly challenging to unravel the nature of supramolecular dynamics in aqueous environments. Here we introduce a precise combinatorial titration methodology to probe in situ the assembly of peptide amphiphiles (PAs). This approach reveals a binary assembly mechanism governed by equilibrium between spheroidal micelles and β-sheet polymers. Weakening hydrogen bonding shifts the equilibrium towards micelles and decreases the internal structural order of filamentous polymers, promoting supramolecular dynamics. Extending this methodology to two-component copolymerization systems, we find a surprising tendency to form blocky nanostructures with reduced internal phase separation as the mismatch in peptide sequence decreases. Interestingly, while well-mixed copolymers acquire different dynamics, mismatched ones retain the characteristic supramolecular motion of their homopolymer counterparts. These critical insights into supramolecular dynamics offer strategies to tailor the dynamic functions of supramolecular nanomaterials.
Authors
- Stef A. H. Jansen (ORCID: https://orcid.org/0000-0002-1505-8462)
- Yuyang Wang (ORCID: https://orcid.org/0009-0001-9556-6001)
- Xianwen Lou (ORCID: https://orcid.org/0000-0002-5403-3647)
- Huachuan Du (ORCID: https://orcid.org/0000-0002-1684-4430)
- Hiroaki Sai (ORCID: https://orcid.org/0000-0002-4268-2148)
- Ruomeng Qiu (ORCID: https://orcid.org/0000-0001-7916-1509)
- E. W. Meijer (ORCID: https://orcid.org/0000-0003-4126-7492)
- Albert J. Markvoort (ORCID: https://orcid.org/0000-0001-6025-9557)
- Samuel Isaac Stupp (ORCID: https://orcid.org/0000-0002-5491-7442)
Institutions
- Northwestern University (US)
- UNSW Sydney (AU)
- Northwestern University (PH)
- Northwestern Medicine (US)
- Eindhoven University of Technology (NL)
Publication Details
- Journal
- Nature Communications
- Published
- 2025-05-24
- DOI
- https://doi.org/10.1038/s41467-025-60138-0
- Citations
- 6
- Primary Topic
- Supramolecular Self-Assembly in Materials
- Type
- article
- Field-Weighted Citation Impact
- 3.58
Funders
- National Science Foundation
- U.S. Department of Energy
- DuPont
- Northwestern University
- Schweizerischer Nationalfonds zur Förderung der Wissenschaftlichen Forschung
- National Institutes of Health
- Office of Science
- Materials Research Science and Engineering Center, Harvard University
- National Institute of General Medical Sciences
- Division of Materials Research
- Division of Electrical, Communications and Cyber Systems
- Basic Energy Sciences
- Biological and Environmental Research
- Medical Research and Materiel Command
- Army Research Office
- Argonne National Laboratory
- Brookhaven National Laboratory