Nucleobase-functionalized ABC triblock copolymers: self-assembly of supramolecular architectures

Abstract

RAFT polymerization afforded acrylic ABC triblock copolymers with self-complementary nucleobase-functionalized external blocks and a low-Tg soft central block. ABC triblock copolymers self-assembled into well-defined lamellar microphase-separated morphologies for potential applications as thermoplastic elastomers. Complementary hydrogen bonding within the hard phase facilitated self-assembly and enhanced mechanical performance.

Synthesis of urea‐containing ABA triblock copolymers: Influence of pendant hydrogen bonding on morphology and thermomechanical properties

“…The lamellar thickness was ∼50 nm. The microphase separated lamellar morphology showed limited long‐range order, owing to the lack of long‐range parallel lamellar domains . Upon increasing the hard segment (67 wt % UrMA), the triblock copolymer films showed a less defined lamellar thickness, and the potential beginning of phase reversal.…”

“…In contrast, pendant hydrogen bonding sites retain higher mobility, suggesting less ordered hydrogen bonding networks. Previous work in our laboratories demonstrated the ability of quadruple pendant hydrogen bonding moieties to promote long range, ordered microphase morphology despite increased mobility . However, for more weakly associated hydrogen bonds, the enhanced mobility of pendant sites may result in less ordered microstructures, imparting a different influence on polymer physical properties compared to main chain hydrogen bonding.…”

“…Urea sites associate through relatively weak hydrogen bonding compared to multiple hydrogen bonding containing nucleobases, serving as an ideal hydrogen bonding site to study pendant hydrogen bonding . Earlier literature widely describes urea sites within the polymer backbone, which generally demonstrates obvious shifts from ordered structures to disordered structures with increasing temperatures .…”

Bio-inspired self-assembled molecular capsules

“…Chemists used this interaction beyond natural realm to assemble molecular building blocks. 5 Many examples such as triblock copolymer, 6 biocompatible materials with embedding nucleobase to poly(e-caprolactone), 7 Being bowl shaped, CTG is a good candidate for preparation of molecular capsule. Also, it has phenolic functional groups that can easily be modified to desired functional group.…”

Surface modification and pattern formation by nucleobases and their coordination complexes

“…Nucleobases are useful building blocks, modulators or templates for nanomaterial synthesis and our ability to further ne-tune surfacepatterning could provide entry to novel applications in functional materials science. [45][46][47][48][49][50][51]74,77 Here, subsequent sections describe the surface patterns of unmodied nucleobases, their derivatives, metal-complexes and their functionalized forms. Considerable attention has been invested toward patterning and high-resolution imaging of custom surfaces.…”