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

Abstract

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 (Nagg) and the micellar radius (Rm) 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, Nagg 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, Rm exhibited a weaker dependence on the ionic monomer position by a power law relationship with an exponent of ~1/10 and ~1/20more » for the respective singly and triply charged series. Moreover, Rm was found to scale with Nagg 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.« less

Authors:
 [1]; ORCiD logo [1];  [2]; ORCiD logo [2];  [1]; ORCiD logo [1]
  1. Louisiana State Univ., Baton Rouge, LA (United States)
  2. Tulane Univ., New Orleans, LA (United States)
Publication Date:
Research Org.:
Louisiana State Univ., Baton Rouge, LA (United States); Univ. of California, Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER); USDOE Office of Science (SC), Basic Energy Sciences (BES). Scientific User Facilities Division
OSTI Identifier:
1510666
Grant/Contract Number:  
SC0012432; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Volume: 140; Journal Issue: 11; Related Information: Supporting information for the manuscript; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; Sequence-defined polymers; ionic peptoid block copolymers; solution self-assembly; electrostatic interactions

Citation Formats

Sternhagen, Garrett L., Gupta, Sudipta, Zhang, Yueheng, John, Vijay, Schneider, Gerald J., and Zhang, Donghui. Solution Self-Assemblies of Sequence-Defined Ionic Peptoid Block Copolymers. United States: N. p., 2018. Web. doi:10.1021/jacs.8b00461.
Sternhagen, Garrett L., Gupta, Sudipta, Zhang, Yueheng, John, Vijay, Schneider, Gerald J., & Zhang, Donghui. Solution Self-Assemblies of Sequence-Defined Ionic Peptoid Block Copolymers. United States. https://doi.org/10.1021/jacs.8b00461
Sternhagen, Garrett L., Gupta, Sudipta, Zhang, Yueheng, John, Vijay, Schneider, Gerald J., and Zhang, Donghui. Mon . "Solution Self-Assemblies of Sequence-Defined Ionic Peptoid Block Copolymers". United States. https://doi.org/10.1021/jacs.8b00461. https://www.osti.gov/servlets/purl/1510666.
@article{osti_1510666,
title = {Solution Self-Assemblies of Sequence-Defined Ionic Peptoid Block Copolymers},
author = {Sternhagen, Garrett L. and Gupta, Sudipta and Zhang, Yueheng and John, Vijay and Schneider, Gerald J. and Zhang, Donghui},
abstractNote = {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 (Nagg) and the micellar radius (Rm) 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, Nagg 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, Rm 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, Rm was found to scale with Nagg 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.},
doi = {10.1021/jacs.8b00461},
journal = {Journal of the American Chemical Society},
number = 11,
volume = 140,
place = {United States},
year = {2018},
month = {3}
}

Journal Article:
Free Publicly Available Full Text
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Cited by: 11 works
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Figures / Tables:

Figure 1 Figure 1: (A) Chemical structures of representative sequences of ionic peptoid block copolymers (1 or 6) and (B) the sequence library showing the singly charged (1-5), triply charged series (6-8) and the charge-neutral sequence (9).

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