Counterion-Dependent Access to Low-Symmetry Lyotropic Sphere Packings of Ionic Surfactant Micelles

Jayaraman, Ashish; Mahanthappa, Mahesh K.

doi:10.1021/acs.langmuir.7b03833

Counterion-Dependent Access to Low-Symmetry Lyotropic Sphere Packings of Ionic Surfactant Micelles

Journal Article · Mon Jan 29 23:00:00 EST 2018 · Langmuir

DOI:https://doi.org/10.1021/acs.langmuir.7b03833· OSTI ID:1478083

Jayaraman, Ashish ^[1]; ^[1]

Univ. of Minnesota, Minneapolis, MN (United States)

The water-driven self-assembly of homologous dianionic surfactants into lyotropic liquid crystals (LLCs) is investigated, with a focus on understanding how surfactant headgroup and counterion identities guide supramolecular spherical mesophase selection. Using temperature-dependent small-angle X-ray scattering (SAXS), we demonstrate that 2-alkylmalonate surfactants (CnMal-M2) with n = 8 (octyl) or 10 (decyl) and M = K⁺, Cs⁺, or (CH₃)₄N⁺ form both simple and complex micelle packings. Observed spherical morphologies include body-centered cubic (BCC), hexagonally closest-packed (HCP), and tetrahedrally closest-packed Frank–Kasper (FK) A15 and σ phases (Pm3(–)n and P4₂/mnm symmetries, respectively). Previously observed in only one other minimally hydrated surfactant, the σ phase is a rare LLC morphology comprising a low-symmetry unit cell containing 30 sub-2-nm quasispherical micelles, each of which belongs to one of five symmetry-equivalent classes with discrete aggregation numbers. Temperature versus water concentration phase maps for C_nMal-M₂ LLCs reveal that σ-phase formation depends sensitively on the size and polarizability of the surfactant counterion and the length of the surfactant alkyl tail. Furthermore, these observations are rationalized in terms of a delicate interplay between global packing symmetry and local particle symmetry, and the extent to which counterion–headgroup correlations enforce the latter structures in these LLC phases.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC); National Science Foundation

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1478083

Journal Information:: Langmuir, Journal Name: Langmuir Journal Issue: 6 Vol. 34; ISSN 0743-7463

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: ENGLISH

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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Counterion-Dependent Access to Low-Symmetry Lyotropic Sphere Packings of Ionic Surfactant Micelles

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