Dodecagonal quasicrystals of oil-swollen ionic surfactant micelles

Ashish Jayaraman, Carlos M. Baez-Cotto, Tyler J. Mann, Mahesh K. Mahanthappa

Research output: Contribution to journalArticlepeer-review

3 Scopus citations

Abstract

A delicate balance of noncovalent interactions directs the hierarchical self-assembly of molecular amphiphiles into spherical micelles that pack into three-dimensional periodic arrays, which mimic intermetallic crystals. Herein, we report the discovery that adding water to a mixture of an ionic surfactant and n-decane induces aperiodic ordering of oil-swollen spherical micelles into previously unrecognized, aqueous lyotropic dodecagonal quasicrystals (DDQCs), which exhibit local 12-fold rotational symmetry and no long-range translational order. The emergence of these DDQCs at the nexus of dynamically arrested micellar glasses and a periodic Frank–Kasper (FK) σ phase approximant sensitively depends on the mixing order of molecular constituents in the assembly process and on sample thermal history. Addition of n-decane to mixtures of surfactant and water instead leads only to periodic FK A15 and σ approximants with no evidence for aperiodic order, while extended ambient temperature annealing of the DDQC also reveals its transformation into a σ phase. Thus, these lyotropic DDQCs are long-lived metastable morphologies, which nucleate and grow from a stochastic distribution of micelle sizes formed by abrupt segregation of varied amounts of oil into surfactant micelles on hydration. These findings indicate that molecular building block complexity is not a prerequisite for the formation of aperiodic supramolecular order, while also establishing the generic nature of quasicrystalline states across metal alloys and self-assembled micellar materials.

Original languageEnglish (US)
Article numbere2101598118
JournalProceedings of the National Academy of Sciences of the United States of America
Volume118
Issue number31
DOIs
StatePublished - Aug 3 2021

Bibliographical note

Funding Information:
ACKNOWLEDGMENTS. This work was supported by US NSF Award CHE-1807330. Synchrotron SAXS experiments were conducted at Sector 12-ID-B of the Advanced Photon Source, a US Department of Energy Office of Science User Facility operated by Argonne National Laboratory under Contract DE-AC02-06CH11357.

Publisher Copyright:
© 2021 National Academy of Sciences. All rights reserved.

Keywords

  • Frank–Kasper phases
  • Liquid crystals
  • Quasicrystals
  • Self-assembly

PubMed: MeSH publication types

  • Journal Article

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