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Crystallization in sequence-defined peptoid diblock copolymers induced by microphase separation.

Jing Sun¹, Alexander A Teran, Xunxun Liao

¹Molecular Foundry, ‡Materials Sciences Division, §Environmental Energy Technologies Division, and ∥National Center for Electron Microscopy, Lawrence Berkeley National Laboratory , Berkeley, California 94720, United States.

Journal of the American Chemical Society

|January 16, 2014

Summary

Sequence-defined peptoid block copolymers exhibit induced crystallization in normally amorphous blocks. This discovery offers new insights into polymer crystallization kinetics and self-assembly driven by side chain structure.

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Solid-phase Submonomer Synthesis of Peptoid Polymers and their Self-Assembly into Highly-Ordered Nanosheets

Solid-phase Submonomer Synthesis of Peptoid Polymers and their Self-Assembly into Highly-Ordered Nanosheets

Published on: November 2, 2011

Area of Science:

Polymer Chemistry
Materials Science
Crystallography

Background:

Atomic-level control over polymer structure is key to understanding block copolymer crystallization kinetics.
Peptoid diblock copolymers offer a tunable platform for exploring structure-property relationships.

Purpose of the Study:

To investigate the impact of side chain structure on the crystallization behavior of sequence-defined peptoid diblock copolymers.
To explore the phenomenon of induced crystallization in amorphous polymer blocks.

Main Methods:

Synthesis of sequence-defined, highly monodisperse peptoid diblock copolymers (poly-N-decylglycine-block-poly-N-2-(2-(2-methoxyethoxy)ethoxy)ethylglycine).
Characterization using X-ray scattering and calorimetry to analyze self-assembly and crystallization.
Systematic variation of block copolymer composition (volume fraction of pNte).

Main Results:

All synthesized block copolypeptoids self-assembled into lamellar microphases, driven by the crystallization of the poly-N-decylglycine (pNdc) block.
The normally amorphous poly-N-2-(2-(2-methoxyethoxy)ethoxy)ethylglycine (pNte) block exhibited induced crystallization.
Induced crystallization of pNte was dependent on the crystalline pNdc block, suggesting lattice spacing matching is crucial.

Conclusions:

Block copolypeptoids demonstrate a unique platform for studying the influence of side chain organization on thermodynamic properties.
Induced crystallization of an amorphous block by a crystalline block due to microphase separation is a novel finding.
This work opens new avenues for designing polymers with controlled crystalline behavior.