Deciphering the Roles of Stereoregularity in the Helical Assembly of PMMA Inclusion Complexes
Year: 2026
Type: article
Abstract: Living systems rely on the precise primary structures of biomolecules to generate complex architectures such as proteins and DNA. However, perturbations in the primary structure can markedly alter the assembly behavior and biological function. Inspired by nature, this study systematically elucidates how the stereoregularity of synthetic poly(methyl methacrylate) (PMMA) governs the formation of helical inclusion complexes (HICs) with fullerene (C60). High-resolution 1H NMR analysis reveals that the arrangement of m- and r-diad configurations follows Bernoulli statistics, indicative of a random distribution across the prepared PMMA samples (r-diad fractions range from 1% to 93%). Moreover, multiscale structural characterization reveals that extended syndiotactic segments enable continuous supramolecular encapsulation of C60 into one-dimensional arrays, forming long-range ordered cylindrical HICs with enhanced thermal stability. In contrast, m-diads interrupt consecutive syndiotactic sequences, leading to segment-dependent wrapping in which only syndiotactic-rich segments can sustain effective helical encapsulation. Consequently, a slight decrease in r-diad fraction from 93% to 60% results in a sharp reduction in the maximum C60 encapsulation ratio (E-ratio) from 21 to 4 wt %. These findings establish a clear sequence-assembly relationship that clarifies the role of stereoregularity in directing PMMA-based HICs and provides a molecular design principle for engineering stereoregular polymer hosts and programmable supramolecular architectures.
Source: Macromolecules
Authors: Wei-You Huang, Yu-Hao Wang, Wen-Tsung Tseng, Wei-Tsung Chuang, Kuan-Yi Wu
Language: English
Subfield: Organic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $4,500
Awards: G1662538391, G2895998233
OpenAlex ID: W7169052747