Cyclic Topology Enhancing Structural Ordering and Stability of Comb-Shaped Polypeptoid Thin Films against Melt-Induced Dewetting

Jiang, Naisheng; Chen, Jianxia; Yu, Tianyi; Chao, Albert; Kang, Liying; Wu, Ying; Niu, Kangmin; Li, Ruipeng; Fukuto, Masafumi; Zhang, Donghui

doi:10.1021/acs.macromol.0c01205

Title: Cyclic Topology Enhancing Structural Ordering and Stability of Comb-Shaped Polypeptoid Thin Films against Melt-Induced Dewetting

Journal Article · Tue Aug 25 00:00:00 EDT 2020 · Macromolecules

DOI:https://doi.org/10.1021/acs.macromol.0c01205· OSTI ID:1673626

^[1]; Chen, Jianxia ^[2]; Yu, Tianyi ^[3]; Chao, Albert ^[3]; Kang, Liying ^[2]; Wu, Ying ^[2]; Niu, Kangmin ^[2]; Li, Ruipeng ^[4]; Fukuto, Masafumi ^[4];

^[3]

Louisiana State Univ., Baton Rouge, LA (United States); Univ. of Science and Technology, Beijing (China)
Univ. of Science and Technology, Beijing (China)
Louisiana State Univ., Baton Rouge, LA (United States)
Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

We investigated the effect of cyclic chain topology on the molecular ordering and thermal stability of comb-shaped polypeptoid thin films on silicon (Si) substrates. Cyclic and linear poly(N-decylglycine) (PNDG) bearing long n-decyl side chains were synthesized by ring-opening polymerization of N-decylglycine-derived N-carboxyanhydrides. When the spin-coated thin films were subjected to thermal annealing at temperatures above the melting temperature (T > T_m), the cyclic PNDG films exhibited significantly enhanced stability against melt-induced dewetting than the linear counterparts (l-PNDG). When recrystallized at temperatures below the crystallization temperature (T < T_c), the homogeneous c-PNDG films exhibit enhanced crystalline ordering relative to the macroscopically dewetted l-PNDG films. Both cyclic and linear PNDG molecules adopt cis-amide conformations in the crystalline film, which transition into trans-amide conformations upon melting. A top-down solvent leaching treatment of both l/c-PNDG films revealed the formation of an irreversibly physisorbed monolayer with similar thickness (ca. 3 nm) on the Si substrate. The physisorbed monolayers are more disordered relative to the respective thicker crystalline films for both cyclic and linear PNDGs. Upon heating above T_m, the adsorbed c-PNDG chains adopt trans-amide backbone conformation identical with the free c-PNDG molecules in the molten film. By contrast, the backbone conformations of l-PNDG chains in the adsorbed layers are notably different from those of the free chains in the molten film. We postulate that the conformational disparity between the chains in the physically adsorbed layers versus the free chains in the molten film is an important factor to account for the difference in the thermal stability of PNDG thin films. These findings highlight the use of cyclic chain topology to suppress the melt-induced dewetting in polymer thin films.

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Research Organization:: Louisiana State Univ., Baton Rouge, LA (United States); Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); Fundamental Research Funds for the Central Universities

Grant/Contract Number:: SC0012432; SC0012704; FRF-TP-17-001A1

OSTI ID:: 1673626

Alternate ID(s):: OSTI ID: 1677653

Report Number(s):: BNL-219942-2020-JAAM; TRN: US2203957

Journal Information:: Macromolecules, Vol. 53, Issue 17; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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