Solution Self-Assemblies of Sequence-Defined Ionic Peptoid Block Copolymers

Sternhagen, Garrett L.; Gupta, Sudipta; Zhang, Yueheng; John, Vijay; Schneider, Gerald J.; Zhang, Donghui

doi:10.1021/jacs.8b00461

Title: Solution Self-Assemblies of Sequence-Defined Ionic Peptoid Block Copolymers

Journal Article · 04 March 2018 · Journal of the American Chemical Society

DOI: https://doi.org/10.1021/jacs.8b00461 · OSTI ID:1510666

Sternhagen, Garrett L. ^[1];

^[2]; Zhang, Yueheng ^[3];

^[3]; Schneider, Gerald J. ^[2];

^[2]

Louisiana State Univ., Baton Rouge, LA (United States); Louisiana State University
Louisiana State Univ., Baton Rouge, LA (United States)
Tulane Univ., New Orleans, LA (United States)

A series of amphiphilic ionic peptoid block copolymers where the total number (1 or 3) and position of ionic monomers along the polymer chain are precisely controlled have been synthesized by the submonomer method. Upon dissolution in water at pH = 9, the amphiphilic peptoids self-assemble into small spherical micelles having hydrodynamic radius in ~5–10 nm range and critical micellar concentration (CMC) in the 0.034–0.094 mg/mL range. Small-angle neutron scattering (SANS) analysis of the micellar solutions revealed unprecedented dependence of the micellar structure on the number and position of ionic monomers along the chain. It was found that the micellar aggregation number (N_agg) and the micellar radius (R_m) both increase as the ionic monomer is positioned progressively away from the junction of the hydrophilic and hydrophobic segments along the polymer chain. By defining an ionic monomer position number (n) as the number of monomers between the junction and the ionic monomer, N_agg exhibited a power law dependence on n with an exponent of ~1/3 and ~3/10 for the respective singly and triply charged series. On the other hand, R_m exhibited a weaker dependence on the ionic monomer position by a power law relationship with an exponent of ~1/10 and ~1/20 for the respective singly and triply charged series. Moreover, R_m was found to scale with N_agg in a power-law relationship with an exponent of 0.32 for the singly charged series, consistent with a weakly charged ionic star-like polymer model in the unscreened regime. This study demonstrated a unique method to precisely tailor the structure of small spherical micelles based on ionic block copolymers through controlling the sequence and position of the ionic monomer.

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Research Organization:: Louisiana State Univ., Baton Rouge, LA (United States); Univ. of California, Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Biological and Environmental Research (BER) (SC-23); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Scientific User Facilities Division

Grant/Contract Number:: SC0012432; AC02-05CH11231

OSTI ID:: 1510666

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 11 Vol. 140; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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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
Towards a coarse-grained model of the peptoid backbone: the case of N , N -dimethylacetamide Du, Pu; Rick, Steven W.; Kumar, Revati Physical Chemistry Chemical Physics, Vol. 20, Issue 36 https://doi.org/10.1039/c8cp03283a	journal	January 2018
A versatile strategy for the synthesis of sequence-defined peptoids with side-chain and backbone diversity via amino acid building blocks Wang, Shixue; Tao, Yue; Wang, Jianqun Chemical Science, Vol. 10, Issue 5 https://doi.org/10.1039/c8sc03415j	journal	January 2019
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Influence factors on the critical micelle concentration determination using pyrene as a probe and a simple method of preparing samples Li, Hao; Hu, Danna; Liang, Feiqing Royal Society Open Science, Vol. 7, Issue 3 https://doi.org/10.1098/rsos.192092	journal	March 2020
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

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