TY - JOUR
T1 - Self-Assembly of Unusually Stable Thermotropic Network Phases by Cellobiose-Based Guerbet Glycolipids
AU - Das, Soumi
AU - Zheng, Caini
AU - Lodge, Timothy P.
AU - Siepmann, J. Ilja
AU - Mahanthappa, Mahesh K.
AU - Calabrese, Michelle A.
AU - Reineke, Theresa M.
N1 - Publisher Copyright:
© 2024 American Chemical Society.
PY - 2024/2/12
Y1 - 2024/2/12
N2 - Bicontinuous thermotropic liquid crystal (LC) materials, e.g., double gyroid (DG) phases, have garnered significant attention due to the potential utility of their 3D network structures in wide-ranging applications. However, the utility of these materials is significantly constrained by the lack of robust molecular design rules for shape-filling amphiphiles that spontaneously adopt the saddle curvatures required to access these useful supramolecular assemblies. Toward this aim, we synthesized anomerically pure Guerbet-type glycolipids bearing cellobiose head groups and branched alkyl tails and studied their thermotropic LC self-assembly. Using a combination of differential scanning calorimetry, polarized optical microscopy, and small-angle X-ray scattering, our studies demonstrate that Guerbet cellobiosides exhibit a strong propensity to self-assemble into DG morphologies over wide thermotropic phase windows. The stabilities of these assemblies sensitively depend on the branched alkyl tail structure and the anomeric configuration of the glycolipid in a previously unrecognized manner. Complementary molecular simulations furnish detailed insights into the observed self-assembly characteristics, thus unveiling molecular motifs that foster network phase self-assembly that will enable future designs and applications of network LC materials.
AB - Bicontinuous thermotropic liquid crystal (LC) materials, e.g., double gyroid (DG) phases, have garnered significant attention due to the potential utility of their 3D network structures in wide-ranging applications. However, the utility of these materials is significantly constrained by the lack of robust molecular design rules for shape-filling amphiphiles that spontaneously adopt the saddle curvatures required to access these useful supramolecular assemblies. Toward this aim, we synthesized anomerically pure Guerbet-type glycolipids bearing cellobiose head groups and branched alkyl tails and studied their thermotropic LC self-assembly. Using a combination of differential scanning calorimetry, polarized optical microscopy, and small-angle X-ray scattering, our studies demonstrate that Guerbet cellobiosides exhibit a strong propensity to self-assemble into DG morphologies over wide thermotropic phase windows. The stabilities of these assemblies sensitively depend on the branched alkyl tail structure and the anomeric configuration of the glycolipid in a previously unrecognized manner. Complementary molecular simulations furnish detailed insights into the observed self-assembly characteristics, thus unveiling molecular motifs that foster network phase self-assembly that will enable future designs and applications of network LC materials.
UR - http://www.scopus.com/inward/record.url?scp=85182013740&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85182013740&partnerID=8YFLogxK
U2 - 10.1021/acs.biomac.3c01266
DO - 10.1021/acs.biomac.3c01266
M3 - Article
C2 - 38170593
AN - SCOPUS:85182013740
SN - 1525-7797
VL - 25
SP - 1291
EP - 1302
JO - Biomacromolecules
JF - Biomacromolecules
IS - 2
ER -