Corona Chain-Controlled Transition from Ostwald Ripening-Grown Hexagonal Platelets to Screw-Dislocation Spirals in Liquid-Crystalline Polypeptoids.
basic_science · Level V
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- Record sourced from PubMed, PMID 42084391.
- Also identified by DOI 10.1021/acs.nanolett.6c00819.
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Abstract
Ostwald ripening is ubiquitous in colloidal growth yet is rarely recognized as a dominant pathway in polymer self-assembly. Herein, we investigate the solution self-assembly of liquid-crystalline polypeptoids based on poly(<i>N</i>-2-ethyl-1-hexyl glycine) (PNEHG) homopolymers and their amphiphilic block copolymers. Upon supersaturation, PNEHG homopolymers form micrometer-sized, highly symmetric hexagonal platelets primarily through Ostwald ripening. This behavior arises from rod-like PNEHG chains packing into a columnar hexagonal (Col<sub>hex</sub>) mesophase with long-range orientational order and short-range positional order, enabling continuous structural rearrangement during growth. Incorporation of a solvophilic poly(<i>N</i>-methyl glycine) (PNMG) block induces a morphological transition from flat platelets to hexagonal spirals with periodic screw dislocations and continuous helical ramps, which is driven by steric constraints at the core-corona interface that introduce packing frustration and redirect mesogenic growth. These findings identify Ostwald ripening as a key mechanism in mesogenic growth and establish the corona-forming block as an active regulator in liquid crystallization-driven self-assembly.