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Scrolled Poly(L‐Lactic Acid) Single Crystals via Chain End‐Induced Symmetry‐Breaking
Journal article   Open access   Peer reviewed

Scrolled Poly(L‐Lactic Acid) Single Crystals via Chain End‐Induced Symmetry‐Breaking

Shichen Yu, Seyong Kim, Kingsley O. Ojima, Bin Zhao and Christopher Y. Li
Angewandte Chemie, v 137(6)
03 Feb 2025
url
https://doi.org/10.1002/ange.202420137View
Published, Version of Record (VoR) Open

Abstract

Chiral crystals crystal engineering polymer single crystals scrolled crystals sustainable polymers
Single crystals that do not obey translational symmetry have been reported in various material systems. In polymers, twisted crystals are typically formed in banded spherulites, while a class of non‐flat polymer single crystals (PSCs) has been observed. Herein, we report the formation of scrolled single crystals of biodegradable polymer poly(L‐lactic acid) (PLLA). While classical 2‐dimensional single crystals formed in solution‐crystallized PLLA are flat, we show that PLLA crystals bend into scrolls when the polymer molecular weight is low. The formation of these unique scrolled PLLA single crystals depends on polymer chain ends and the polymer molecular weight. This work, therefore, demonstrates a new mechanism to break translational symmetry in PSC growth. Scrolled single crystals of biodegradable poly(L‐lactic acid) with broken translational symmetry were obtained using solution crystallization. The scrolling mechanism was attributed to the imbalance of the fold surfaces arising from the asymmetrical distribution of the polymer chain ends, experimentally confirmed by nanoparticle decoration. This work demonstrates a new strategy for breaking crystal translational symmetry in polymer single crystals.

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