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Pathway Selection in Peptide Amphiphile Assembly
Abstract
The nature of supramolecular structures could be strongly affected by the pathways followed during their formation just as mechanisms and final outcomes in chemical reactions vary with the conditions selected. So far this is a largely unexplored area of supramolecular chemistry. We demonstrate here how different preparation protocols to self-assemble peptide amphiphiles in water can result in the formation of different supramolecular morphologies, either long filaments containing β-sheets or smaller aggregrates containing peptide segments in random coil conformation. We found that the assembly rate into β-sheets decreases in the presence of a destabilizing "good" solvent like hexafluoroisopropanol (HFIP) and is affected by transient conditions in solution. Also the peptide amphiphile investigated spontaneously nucleates the β-sheet-containing filaments at a critical fraction of HFIP in water below 21%. Furthermore, β-sheet assemblies have a high kinetic stability and, once formed, do not disassemble rapidly. We foresee that insights into the characteristic dynamics of a supramolecular system provide an efficient approach to select the optimum assembly pathway necessary for function.
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The formation of specific self-assembled aggregates can be guided by several parameters including salt concentration, temperature, pH, and solvent.
“Alternatively, the formation of specific self-assembled aggregates can be guided by several parameters,101 including salt concentration, temperature,102,103 pH, and solvent.104,105”
From The Pursuit of Shortwave Infrared-Emitting Nanoparticles with Bright Fluorescence through Molecular Design and Excited-State Engineering of Molecular Aggregates (2022) · cites this paper as [104]
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Liu, M., Zhang, L., & Wang, T. (2015) · Chemical Reviews · doi:10.1021/cr500671p · Cited by 2,250
Piwoński, H., Nozue, S., & Habuchi, S. (2022) · ACS Nanoscience Au · doi:10.1021/acsnanoscienceau.1c00038 · Cited by 39
Metadata
- Authors
- Korevaar, P. A., Newcomb, C. J., Meijer, E. W., & Stupp, S. I.
- Affiliations
- Eindhoven University of Technology (NL)
- Northwestern University (US)
- Corresponding author
- Meijer, E. W.
- Stupp, Samuel I.
- Venue
- Journal of the American Chemical Society
- Publisher
- American Chemical Society (ACS)
- Published
- 2014-06-09
- Volume
- 136
- Issue
- 24
- Pages
- 8540-8543
- ISSN
- 0002-7863 (ISSN-L)
- 1520-5126
- OpenAlex
- W2315191255
- Cited by
- 265
- References
- 36
- Citations by year
- 2026: 9 · 2025: 12 · 2024: 28 · 2023: 13 · 2022: 18 · 2021: 28 · 2020: 25 · 2019: 24 · 2018: 19 · 2017: 39 · 2016: 25 · 2015: 20 · 2014: 5
- FWCI
- 11.25
- Type
- journal article
- Language
- en
- Open access
- closed
- Locations
- Journal of the American Chemical Society (publishedVersion)
- PubMed (publishedVersion)
- TU/e Research Portal (submittedVersion)
- Funders
- U.S. Department of Energy (DE–FG02-00ER45810)
- European Research Council (FP7/2007-2013)
- Topics
- Physical Sciences › Materials Science › Biomaterials › Supramolecular Self-Assembly in Materials
- Physical Sciences › Chemistry › Organic Chemistry › Supramolecular Chemistry and Complexes
- Physical Sciences › Chemistry › Physical and Theoretical Chemistry › Surfactants and Colloidal Systems
- Keywords
- peptide amphiphiles, self-assembly pathways, supramolecular morphology, hexafluoroisopropanol, solvent effects, nucleation, kinetic stability, assembly kinetics
- MeSH terms
- Kinetics, Molecular Conformation, Peptides, Surface-Active Agents
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