Electrostatic Control of Shape Selection and Nanoscale Structure in Chiral Molecular Assemblies

Joseph M. McCourt, Sumit Kewalramani, Changrui Gao, Eric W. Roth, Steven J. Weigand, Monica Olvera De La Cruz*, Michael J. Bedzyk*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

8 Scopus citations

Abstract

How molecular chirality manifests at the nano- to macroscale has been a scientific puzzle since Louis Pasteur discovered biochirality. Chiral molecules assemble into meso-shapes such as twisted and helical ribbons, helicoidal scrolls (cochleates), or möbius strips (closed twisted ribbons). Here we analyze self-assembly for a series of amphiphiles, Cn-K, consisting of an ionizable amino acid [lysine (K)] coupled to alkyl tails with n = 12, 14, or 16 carbons. This simple system allows us to probe the effects of electrostatic and van der Waals interactions in chiral assemblies. Small/wide-angle X-ray scattering (SAXS/WAXS) reveals that at low pH, where the headgroups are ionized (+1), C16-K forms high aspect ratio, planar crystalline bilayers. Molecular dynamics (MD) simulations reveal that tilted tails of the bilayer leaflets are interdigitated. SAXS shows that, with increasing salt concentration, C16-K molecules assemble into cochleates, whereas at elevated pH (reduced degree of ionization), helices are observed for all Cn-K assemblies. The shape selection between helices and scrolls is explained by a membrane energetics model. The nano- to meso-scale structure of the chiral assemblies can be continuously controlled by solution ionic conditions. Overall, our study represents a step toward an electrostatics-based approach for shape selection and nanoscale structure control in chiral assemblies.

Original languageEnglish (US)
Pages (from-to)1169-1181
Number of pages13
JournalACS Central Science
Volume8
Issue number8
DOIs
StatePublished - Aug 24 2022

ASJC Scopus subject areas

  • General Chemistry
  • General Chemical Engineering

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