Mapping in situ the assembly and dynamics in aqueous supramolecular polymers

Du, Huachuan; Qiu, Ruomeng; Lou, Xianwen; Jansen, Stef A. H.; Sai, Hiroaki; Wang, Yuyang; Markvoort, Albert J.; Meijer, E. W.; Stupp, Samuel I.

doi:10.1038/s41467-025-60138-0

Mapping in situ the assembly and dynamics in aqueous supramolecular polymers

Journal Article · Sat May 24 00:00:00 EDT 2025 · Nature Communications

DOI:https://doi.org/10.1038/s41467-025-60138-0· OSTI ID:3022718

^[1]; Qiu, Ruomeng ^[2]; Lou, Xianwen ^[3]; ^[3]; ^[4]; Wang, Yuyang ^[3]; ^[3]; ^[3]; ^[2]

Northwestern University, Chicago, IL (United States); Eindhoven University of Technology (The Netherlands)
Northwestern University, Chicago, IL (United States); Northwestern University, Evanston, IL (United States)
Eindhoven University of Technology (The Netherlands)
Northwestern University, Chicago, IL (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: Northwestern University, Chicago, IL (United States)

Sponsoring Organization:: National Institutes of Health (NIH); National Institutes of Health, National Institute of General Medical Sciences (NIGMS); USDOE Office of Science (SC), Basic Energy Sciences (BES). Materials Sciences & Engineering Division (MSE); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities (SUF)

Grant/Contract Number:: AC02-06CH11357; SC0012704; SC0020884

Other Award/Contract Number:: P30GM133893
S10 OD012331

OSTI ID:: 3022718

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 16; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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