Liquid-Crystalline Phase Behavior in Polypeptoid Diblock Copolymers

Greer, Douglas R.; Stolberg, Michael A.; Xuan, Sunting; Jiang, Xi; Balsara, Nitash P.; Zuckermann, Ronald N.

doi:10.1021/acs.macromol.8b01952

Liquid-Crystalline Phase Behavior in Polypeptoid Diblock Copolymers

Journal Article · Mon Nov 19 04:00:00 EST 2018 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.8b01952· OSTI ID:1594903

^[1]; Stolberg, Michael A. ^[2]; Xuan, Sunting ^[2]; ^[2]; ^[1]; ^[2]

Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Polypeptoid homopolymers and block copolymers undergo thermal transitions in the solid state that can be detected by differential scanning calorimetry (DSC), but so far there is neither consensus on the underpinnings of the observed thermal transitions nor consensus on the expected number of transitions. We synthesized a series of polypeptoid diblock copolymers containing hydrophobic alkyl side chains and hydrophilic ethylene oxide side chains, systematically varying side-chain length (S), backbone main-chain length (N), block copolymer composition (n/m), and N-terminal group, and studied their thermal transitions by a combination of X-ray scattering and DSC. The thermal transitions are largely unaffected by S, N, and n/m but strongly affected by the N-terminal group. Block copolymers with an acetylated N-terminus exhibit two thermal transitions. The low temperature thermal transition is due to a transition from a crystalline phase to a sanidic liquid crystalline mesophase. The molecules adopt planar, boardlike conformations and are arranged in a rectangular crystal lattice with extended backbones that run parallel to each other. The side chains extend on either side and are located within the plane of the backbone. The liquid crystalline phase is characterized by conformational disorder in dimensions normal to the molecular plane. The high temperature thermal transition is due to melting of the liquid crystalline phase to give an isotropic phase. Block copolymers with a free N-terminus (non-acetylated) exhibit only one thermal transition and similar out-of-plane conformational disorder. Finally, this disorder appears to be due to a difference in the pendant side chain display angle of the terminal nitrogen atom.

View Accepted Manuscript (DOE)

Research Organization:: Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-05CH11231; AC02-76SF00515

OSTI ID:: 1594903

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 23 Vol. 51; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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Cited By (4)

Linking two worlds in polymer chemistry: The influence of block uniformity and dispersity in amphiphilic block copolypeptoids on their self‐assembly Gangloff, Niklas; Höferth, Marcel; Stepanenko, Vladimir Biopolymers, Vol. 110, Issue 4 https://doi.org/10.1002/bip.23259	journal	February 2019
Recent advances in crystallization and self‐assembly of polypeptoid polymers Zeng, Guangjian; Qiu, Lu; Wen, Tao POLYMER CRYSTALLIZATION, Vol. 2, Issue 3 https://doi.org/10.1002/pcr2.10065	journal	June 2019
Effect of processing and end groups on the crystal structure of polypeptoids studied by cryogenic electron microscopy at atomic length scales Jiang, Xi; Xuan, Sunting; Kundu, Joyjit Soft Matter, Vol. 15, Issue 23 https://doi.org/10.1039/c9sm00633h	journal	January 2019
Atomic-level engineering and imaging of polypeptoid crystal lattices Xuan, Sunting; Jiang, Xi; Spencer, Ryan K. Proceedings of the National Academy of Sciences, Vol. 116, Issue 45 https://doi.org/10.1073/pnas.1909992116	journal	October 2019

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