The vast majority of nanomaterials studied in light of their ability to transmit chirality to or amplify their chirality in a surrounding medium, constitute an achiral core with chirality solely installed at the surface by conjugation or encapsulation with optically active ligands. Here we present the inverse approach focusing on surface‐modified cellulose nanocrystals (CNCs) with core chirality at both the molecular and the morphological level to quantify transmission and amplification of core chirality through space using a host nematic liquid crystal (N‐LC) as reporter. We find that CNCs functionalized at the surface with achiral molecules, structurally related to the N‐LC, exhibit better N‐LC solubility, thereby serving as highly efficient chiral inducers. Moreover, functionalization with chiral molecules only marginally enhances the efficacy of helical distortion in the host N‐LC matrix, indicating the high propensity of CNCs to transfer chirality from an inherently chiral core.
- Award ID(s):
- 1904091
- NSF-PAR ID:
- 10379167
- Date Published:
- Journal Name:
- Materials Advances
- Volume:
- 3
- Issue:
- 8
- ISSN:
- 2633-5409
- Page Range / eLocation ID:
- 3346 to 3354
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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Abstract The vast majority of nanomaterials studied in light of their ability to transmit chirality to or amplify their chirality in a surrounding medium, constitute an achiral core with chirality solely installed at the surface by conjugation or encapsulation with optically active ligands. Here we present the inverse approach focusing on surface‐modified cellulose nanocrystals (CNCs) with core chirality at both the molecular and the morphological level to quantify transmission and amplification of core chirality through space using a host nematic liquid crystal (N‐LC) as reporter. We find that CNCs functionalized at the surface with achiral molecules, structurally related to the N‐LC, exhibit better N‐LC solubility, thereby serving as highly efficient chiral inducers. Moreover, functionalization with chiral molecules only marginally enhances the efficacy of helical distortion in the host N‐LC matrix, indicating the high propensity of CNCs to transfer chirality from an inherently chiral core.
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Abstract The importance of and the difference between molecular versus structural core chirality of substances that form nanomaterials, and their ability to transmit and amplify their chirality to and within a surrounding condensed medium is yet to be exactly understood. Here we demonstrate that neat as well as disodium cromoglycate (DSCG) surface‐modified cellulose nanocrystals (CNCs) with both molecular and morphological core chirality can induce homochirality in racemic nematic lyotropic chromonic liquid crystal (
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Abstract Induction, transmission, and manipulation of chirality in molecular systems are well known, widely applied concepts. However, our understanding of how chirality of nanoscale entities can be controlled, measured, and transmitted to the environment is considerably lacking behind. Future discoveries of dynamic assemblies engineered from chiral nanomaterials, with a specific focus on shape and size effects, require exact methods to assess transmission and amplification of nanoscale chirality through space. Here we present a remarkably powerful chirality amplification approach by desymmetrization of plasmonic nanoparticles to nanorods. When bound to gold nanorods, a one order of magnitude lower number of chiral molecules induces a tighter helical distortion in the surrounding liquid crystal–a remarkable amplification of chirality through space. The change in helical distortion is consistent with a quantification of the change in overall chirality of the chiral ligand decorated nanomaterials differing in shape and size as calculated from a suitable pseudoscalar chirality indicator.
- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1039/d2ma00093h
