TY - JOUR
T1 - Ultrasmall 3D network morphologies from biobased sugar–terpenoid hybrid block co-oligomers in the bulk and the thin film states
AU - Lee, Chaehun
AU - Ree, Brian J.
AU - Chen, Kai
AU - Komaki, Ryoya
AU - Katsuhara, Satoshi
AU - Yamamoto, Takuya
AU - Borsali, Redouane
AU - Tajima, Kenji
AU - Chen, Hsin Lung
AU - Satoh, Toshifumi
AU - Isono, Takuya
N1 - Publisher Copyright:
© 2023 The Author(s)
PY - 2024/3
Y1 - 2024/3
N2 - Nanoscale three-dimensional (3D) network morphologies, such as those represented by gyroids accessed by the self-assembly of block copolymers, are highly attractive platforms for the fabrication of nanostructured materials. However, it remains challenging to access such morphologies, especially in the sub-10 nm domain spacing region. Herein, we systematically investigated the microphase separation behaviors of biobased sugar–terpenoid hybrid block co-oligomers (BCOs) with different molecular parameters, including their volume fractions, the linker structures between the blocks, and the stereochemistries of the terpenoid blocks. The BCOs were synthesized using the azido–alkyne click reaction of propargyl-β-d-glucopyranoside with azido-functionalized farnesol, phytol, DL-α-tocopherol, and d-α-tocopherol, to ensure a well-defined molecular structure without any molecular weight distribution. Through X-ray scattering screening, we found that tocopherols, when combined with a glucose unit, yield BCOs capable of forming gyroid and hexagonally perforated lamellar (HPL) 3D network morphologies with ultrasmall domain spacings of ∼10 nm. Remarkably, HPL, which is known as a metastable phase in block copolymers, was obtained in both the bulk and film states. The nature of the linker structure and the stereochemistry of the tocopherol hydrocarbon chain were found to influence the resulting morphology and the long-range order of the nanostructures. We expect this study to contribute to the molecular design of precise block copolymers and the construction of intricate nanostructural templates with ultrasmall feature sizes.
AB - Nanoscale three-dimensional (3D) network morphologies, such as those represented by gyroids accessed by the self-assembly of block copolymers, are highly attractive platforms for the fabrication of nanostructured materials. However, it remains challenging to access such morphologies, especially in the sub-10 nm domain spacing region. Herein, we systematically investigated the microphase separation behaviors of biobased sugar–terpenoid hybrid block co-oligomers (BCOs) with different molecular parameters, including their volume fractions, the linker structures between the blocks, and the stereochemistries of the terpenoid blocks. The BCOs were synthesized using the azido–alkyne click reaction of propargyl-β-d-glucopyranoside with azido-functionalized farnesol, phytol, DL-α-tocopherol, and d-α-tocopherol, to ensure a well-defined molecular structure without any molecular weight distribution. Through X-ray scattering screening, we found that tocopherols, when combined with a glucose unit, yield BCOs capable of forming gyroid and hexagonally perforated lamellar (HPL) 3D network morphologies with ultrasmall domain spacings of ∼10 nm. Remarkably, HPL, which is known as a metastable phase in block copolymers, was obtained in both the bulk and film states. The nature of the linker structure and the stereochemistry of the tocopherol hydrocarbon chain were found to influence the resulting morphology and the long-range order of the nanostructures. We expect this study to contribute to the molecular design of precise block copolymers and the construction of intricate nanostructural templates with ultrasmall feature sizes.
KW - Block co-oligomer
KW - Microphase separation
KW - Saccharide
KW - Self-assembly
KW - Terpenoid
KW - Ultrasmall nanostructure
UR - http://www.scopus.com/inward/record.url?scp=85179081609&partnerID=8YFLogxK
U2 - 10.1016/j.giant.2023.100211
DO - 10.1016/j.giant.2023.100211
M3 - Article
AN - SCOPUS:85179081609
SN - 2666-5425
VL - 17
JO - Giant
JF - Giant
M1 - 100211
ER -