Reconfigurable self-assembly through chiral control of interfacial tension.
From determining the optical properties of simple molecular crystals to establishing the preferred handedness in highly complex vertebrates, molecular chirality profoundly influences the structural, mechanical and optical properties of both synthetic and biological matter on macroscopic length scales. In soft materials such as amphiphilic lipids and liquid crystals, the competition between local chiral interactions and global constraints imposed by the geometry of the self-assembled structures leads to frustration and the assembly of unique materials. An example of particular interest is smectic liquid crystals, where the two-dimensional layered geometry cannot support twist and chirality is consequently expelled to the edges in a manner analogous to the expulsion of a magnetic field from superconductors. Here we demonstrate a consequence of this geometric frustration that leads to a new design principle for the assembly of chiral molecules. Using a model system of colloidal membranes, we show that molecular chirality can control the interfacial tension, an important property of multi-component mixtures. This suggests an analogy between chiral twist, which is expelled to the edges of two-dimensional membranes, and amphiphilic surfactants, which are expelled to oil-water interfaces. As with surfactants, chiral control of interfacial tension drives the formation of many polymorphic assemblages such as twisted ribbons with linear and circular topologies, starfish membranes, and double and triple helices. Tuning molecular chirality in situ allows dynamical control of line tension, which powers polymorphic transitions between various chiral structures. These findings outline a general strategy for the assembly of reconfigurable chiral materials that can easily be moved, stretched, attached to one another and transformed between multiple conformational states, thus allowing precise assembly and nanosculpting of highly dynamical and designable materials with complex topologies.
The Martin Fisher School of Physics, Brandeis University, 415 South Street, Waltham, Massachusetts 02454, USA.
Thomas
T
Gibaud
Edward
E
Barry
Mark J
MJ
Zakhary
Mir
M
Henglin
Andrew
A
Ward
Yasheng
Y
Yang
Cristina
C
Berciu
Rudolf
R
Oldenbourg
Michael F
MF
Hagan
Daniela
D
Nicastro
Robert B
RB
Meyer
Zvonimir
Z
Dogic
D019943:Amino Acid Substitution; D017104:Bacteriophage M13 / Q000737:chemistry* / Q000235:genetics; D001696:Biomechanical Phenomena; D003102:Colloids / Q000737:chemistry; D003198:Computer Simulation; D046529:Microscopy, Electron, Transmission; D009821:Oils / Q000737:chemistry; D013237:Stereoisomerism; D013500:Surface Tension; D013501:Surface-Active Agents / Q000737:chemistry; D014867:Water / Q000737:chemistry
D003102:Colloids; D009821:Oils; D013501:Surface-Active Agents; D014867:Water