Self-assembly of unconventional frustrated amphiphiles in solutions
Unconventional amphiphilic molecules having a rigid hydrophobic central unit and flexible or semiflexible hydrophilic chains on the rim, have proven valuable in several technological applications, for example host-guest chemistry. The further presence of alternating hydrophobic and hydrophilic tails complicates the definition of clear core and shell regions, resulting in complex segregation and frustrated self-assembly. In this study, we investigate symmetric triphenylene-based amphiphilic derivatives with alternating benzyl and alkylsulfonate groups. We characterize their self-assembly in water and different solutions using several experimental techniques — NMR, atomic force microscopy, dynamic light scattering, small-angle X-ray and neutron scattering — alongside extensive molecular dynamics simulations, both atomistic and coarse-grained with metainference. In aqueous solutions, these amphiphiles form stacked assemblies, adopting alternate up-down conformations driven by π-stacking of up to six molecules. The introduction of NaCl salt screens unfavorable electrostatic interactions thus promoting further π-stacking and leads to the formation of larger elongated aggregates.
Authors
- Ralf Schweins (ORCID: https://orcid.org/0000-0001-8078-2089)
- Cedrix J. Dongmo Foumthuim (ORCID: https://orcid.org/0000-0002-8095-0289)
- Fabrizio Menchini Fabris (ORCID: https://orcid.org/0000-0001-9209-1680)
- Henrique Musseli Cezar (ORCID: https://orcid.org/0000-0002-7553-0482)
- C. Mondelli (ORCID: https://orcid.org/0000-0002-5452-5238)
- Michele Cascella (ORCID: https://orcid.org/0000-0003-2266-5399)
- Pablo Ballester (ORCID: https://orcid.org/0000-0001-8377-6610)
- Sandro Zorzi (ORCID: https://orcid.org/0000-0001-5024-9478)
- Achille Giacometti
- Reidar Lund (ORCID: https://orcid.org/0000-0001-8017-6396)
- Alessandro Scarso (ORCID: https://orcid.org/0000-0001-6114-9181)
- Viviana Cristiglio (ORCID: https://orcid.org/0000-0003-3608-9222)
- Tommaso Lorenzetto (ORCID: https://orcid.org/0000-0002-7975-861X)
- Giacomo Berton (ORCID: https://orcid.org/0000-0003-4713-587X)
- Szymon Mikołaj Szostak (ORCID: https://orcid.org/0000-0002-3057-6225)
Institutions
- Institució Catalana de Recerca i Estudis Avançats (ES)
- University of Padua (IT)
- Ca' Foscari University of Venice (IT)
- University of Oslo (NO)
- Institut Català d'Investigació Química (ES)
- Institut Laue-Langevin (FR)
Publication Details
- Journal
- ChemRxiv
- Published
- 2025-09-09
- DOI
- https://doi.org/10.26434/chemrxiv-2025-l9qzc
- Primary Topic
- Supramolecular Self-Assembly in Materials
- Type
- article
- Field-Weighted Citation Impact
- 0.00