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

Jayaraman, Ashish; Mahanthappa, Mahesh K.

doi:10.1021/acs.langmuir.7b03833

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

Journal Article · Tue Jan 30 00:00:00 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.

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

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

Grant/Contract Number:: AC02-06CH11357; CHE-1608115

OSTI ID:: 1478083

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

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: ENGLISH

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Cited by: 25 works

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
counterions
micelles
hydration
phase transitions
surfactants

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

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