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 »
- Authors:
-
- Louisiana State Univ., Baton Rouge, LA (United States)
- 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 = {Mon Mar 05 00:00:00 EST 2018},
month = {Mon Mar 05 00:00:00 EST 2018}
}
Web of Science
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