Molecular Crystallization Controlled by pH Regulates Mesoscopic Membrane Morphology

Cheuk-Yui Leung †, Liam C. Palmer ‡, Bao Fu Qiao §,Sumit Kewalramani §, Rastko Sknepnek §, Christina J. Newcomb §, Megan A. Greenfield , Graziano Vernizzi §, Samuel I. Stupp ‡§¶, Michael J. Bedzyk†§, and Monica Olvera de la Cruz ‡§*

^†Physics and Astronomy, ^‡Department of Chemistry,^§Materials Science and Engineering, and Chemical and Biological Engineering, Northwestern University, Evanston, Illinois 60208, United States

 Department of Physics, Siena College, Loudonville, New York 12211, United States

^¶ Department of Medicine and Institute for BioNanotechnology in Medicine, Northwestern University, Chicago, Illinois 60611, United States

ACS Nano, Article ASAP

DOI: 10.1021/nn304321w

Publication Date (Web): November 27, 2012

Copyright © 2012 American Chemical Society

Coassembled molecular structures are known to exhibit a large variety of geometries and morphologies. A grand challenge of self-assembly design is to find techniques to control the crystal symmetries and overall morphologies of multicomponent systems. By mixing +3 and −1 ionic amphiphiles, we assemble crystalline ionic bilayers in a large variety of geometries that resemble polyhedral cellular crystalline shells and archaea wall envelopes. We combine TEM with SAXS and WAXS to characterize the coassembled structures from the mesoscopic to nanometer scale. The degree of ionization of the amphiphiles and their intermolecular electrostatic interactions are controlled by varying pH. At low and high pH values, we observe closed, faceted vesicles with two-dimensional hexagonal molecular arrangements, and at intermediate pH, we observe ribbons with rectangular-C packing. Furthermore, as pH increases, we observe interdigitation of the bilayer leaflets. Accurate atomistic molecular dynamics simulations explain the pH-dependent bilayer thickness changes and also reveal bilayers of hexagonally packed tails at low pH, where only a small fraction of anionic headgroups is charged. Coarse-grained simulations show that the mesoscale geometries at low pH are faceted vesicles where liquid-like edges separate flat crystalline domains. Our simulations indicate that the curved-to-polyhedral shape transition can be controlled by tuning the tail density in regions where sharp bends can form the polyhedral edges. In particular, the pH acts to control the overall morphology of the ionic bilayers by changing the local crystalline order of the amphiphile tails