Chiral organosilica particles of size ~200 nm were synthesized from an enantio-pure multi-armed chiral D-maltose organosilane precursor in the absence of co-condensation with an achiral monomer. Two distinct experiments were performed to demonstrate the particles’ ability to induce conformational deracemization of a host liquid crystal. The first involves an electric field-induced tilt of the liquid crystal director in the deracemized smectic-A phase. The other involves domain wall curvature separating left- and right-handed liquid crystal helical pitch domains imposed by the cells’ substrates. The results demonstrate unequivocally that enantio-pure organosilica nanoparticles can be synthesized and can induce chirality in a host.
more »
« less
Chiral polymeric nanocapsules and their use for conformational deracemization of liquid crystals
We present the first preparation and properties of chiral nanocapsules. The chiral shell, a polyurea derivative, was obtained by interfacial emulsion polymerization of L-lysine with polymethylene polyphenyl isocyanate. The chirality of these nanocapsules was manifested by its ability to induce conformational deracemization of liquid crystal. This induced chirality was measured using the “Raynes experiment”, in which the cell’s boundary conditions impose a ±90o rotation of the liquid crystal director from one surface to the other. Both left and right-handed director twist domains appear on cooling from the isotropic to the nematic phase. Owing to the weak induced chirality of the liquid crystal, one sense of director rotation is energetically more favorable and its domain size expands, resulting in curvature of the domain walls. The curvature was measured as a function of capsule concentration, and serves as a metric of the induction of chirality in the surrounding liquid crystal.
more »
« less
- Award ID(s):
- 1505389
- PAR ID:
- 10067923
- Date Published:
- Journal Name:
- Journal of physical chemistry. C
- Volume:
- 122
- ISSN:
- 1932-7447
- Page Range / eLocation ID:
- 17936-17941
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Chiral periodic mesoporous organosilica (PMO) materials have been shown to deracemize a configurationally achiral, but conformationally racemic liquid crystal in which the PMO is embedded. In particular, application of an electric field E in the liquid crystal’s smectic-A phase results in a rotation of the liquid crystal director by an angle proportional to E, which is detected optically — this is the so-called “electroclinic” effect. Here we present results from electroclinic measurements as a function of frequency and temperature, which allow us to distinguish the component of optical signal that arises from liquid crystal chirality induced within the PMO’s chiral pores from that induced just outside the silica colloids. Our central result is that the overwhelming source of our electrooptic signal emanates from outside the PMO, and that the contribution from the liquid crystal embedded in the chiral pores is much smaller and below the noise level.more » « less
-
more » « less
Abstract Supramolecular chirality typically originates from either chiral molecular building blocks or external chiral stimuli. Generating chirality in achiral systems in the absence of a chiral input, however, is non-trivial and necessitates spontaneous mirror symmetry breaking. Achiral nematic lyotropic chromonic liquid crystals have been reported to break mirror symmetry under strong surface or geometric constraints. Here we describe a previously unrecognised mechanism for creating chiral structures by subjecting the material to a pressure-driven flow in a microfluidic cell. The chirality arises from a periodic double-twist configuration of the liquid crystal and manifests as a striking stripe pattern. We show that the mirror symmetry breaking is triggered at regions of flow-induced biaxial-splay configurations of the director field, which are unstable to small perturbations and evolve into lower energy structures. The simplicity of this unique pathway to mirror symmetry breaking can shed light on the requirements for forming macroscopic chiral structures.
-
Supramolecular chirality typically originates from either chiral molecular building blocks or external chiral stimuli. Generating chirality in achiral systems in the absence of a chiral input, however, is non-trivial and necessitates spontaneous mirror symmetry breaking. Achiral nematic lyotropic chromonic liquid crystals have been reported to break mirror symmetry under strong surface or geometric constraints. Here we describe a previously unrecognised mechanism for creating chiral structures by subjecting the material to a pressure-driven flow in a microfluidic cell. The chirality arises from a periodic double-twist configuration of the liquid crystal and manifests as a striking stripe pattern. We show that the mirror symmetry breaking is triggered at regions of flow-induced biaxial-splay configurations of the director field, which are unstable to small perturbations and evolve into lower energy structures. The simplicity of this unique pathway to mirror symmetry breaking can shed light on the requirements for forming macroscopic chiral structures.more » « less
-
more » « less
Abstract The giant circular photo‐galvanic effect is realized in chiral metals when illuminated by circularly polarized light. However, the structure itself is not switchable nor is the crystal chirality in the adjacent chiral domains. Here spindle‐shaped liquid crystalline elastomer microparticles that can switch from prolate to spherical to oblate reversibly upon heating above the nematic to isotropic transition temperature are synthesized. When arranged in a honeycomb lattice, the continuous shape change of the microparticles leads to lattice reconfiguration, from a right‐handed chiral state to an achiral one, then to a left‐handed chiral state, without breaking the translational symmetry. Accordingly, the sign of rotation of the polarized light passing through the lattices changes as measured by time‐domain terahertz spectroscopy. Further, it can locally alter the chirality in the adjacent domains using near‐infrared light illumination. The reconfigurable chiral microarrays will allow us to explore non‐trivial symmetry‐protected transport modes of topological lattices at the light–matter interface. Specifically, the ability to controllably create chiral states at the boundary of the achiral/chiral domains will lead to rich structures emerging from the interplay of symmetry and topology.
- Free Publicly Accessible Full Text
-
Accepted Manuscript1.0
- Journal Article:
- https://doi.org/http://dx.doi.org/10.1021/acs.jpcc.8b06005
