Protonation-Driven Aqueous Lyotropic Self-Assembly of Synthetic Six-Tail Lipidoids

James Jennings, Matthew C.D. Carter, Chang Yun Son, Qiang Cui, David M. Lynn, Mahesh K. Mahanthappa

Research output: Contribution to journalArticle

Abstract

We report the aqueous lyotropic mesophase behaviors of protonated amine-based "lipidoids,"a class of synthetic lipid-like molecules that mirrors essential structural features of the multitail bacterial amphiphile lipid A. Small-angle X-ray scattering (SAXS) studies demonstrate that the protonation of the tetra(amine) headgroups of six-tail lipidoids in aqueous HCl, HNO3, H2SO4, and H3PO4 solutions variably drives their self-assembly into lamellar (Lα) and inverse micellar (III) lyotropic liquid crystals (LLCs), depending on acid identity and concentration, amphiphile tail length, and temperature. Lipidoid assemblies formed in H2SO4(aq) exhibit rare inverse body-centered cubic (BCC) and inverse face-centered cubic (FCC) micellar morphologies, the latter of which unexpectedly coexists with zero mean curvature Lα phases. Complementary atomistic molecular dynamics (MD) simulations furnish detailed insights into this unusual self-assembly behavior. The unique aqueous lyotropic mesophase behaviors of ammonium lipidoids originate in their dichotomous ability to adopt both inverse conical and chain-extended molecular conformations depending on the number of counterions and their identity, which lead to coexisting supramolecular assemblies with remarkably different mean interfacial curvatures.

Original languageEnglish (US)
Pages (from-to)8240-8252
Number of pages13
JournalLangmuir
Volume36
Issue number28
DOIs
StatePublished - Jul 21 2020

PubMed: MeSH publication types

  • Journal Article
  • Research Support, Non-U.S. Gov't
  • Research Support, U.S. Gov't, Non-P.H.S.

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