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Title: pH-Dependent Solution Micellar Structure of Amphoteric Polypeptoid Block Copolymers with Positionally Controlled Ionizable Sites

Abstract

While solution micellization of ionic block copolymers (BCP) with randomly distributed ionization sites along the hydrophilic segments has been extensively studied, the roles of positionally controlled ionization sites along the BCP chains in their micellization and resulting micellar structure remain comparatively less understood. Herein, three amphoteric polypeptoid block copolymers carrying two oppositely charged ionizable sites, with one fixed at the hydrophobic terminus and the other varyingly positioned along the hydrophilic segment, have been synthesized by sequential ring-opening polymerization method. The presence of the ionizable site at the hydrophobic segment terminus is expected to promote polymer association toward equilibrium micellar structures in an aqueous solution. The concurrent presence of oppositely charged ionizable sites on the polymer chains allows the polymer association to be electrostatically modulated in a broad pH range (ca. 2–12). Micellization of the amphoteric polypeptoid BCP in dilute aqueous solution and the resulting micellar structure at different solution pHs was investigated by a combination of scattering and microscopic methods. Negative-stain transmission-electron microscopy (TEM), small-angle neutron scattering (SANS), and small-angle X-ray scattering (SAXS) analyses revealed the dominant presence of core–shell-type spherical micelles and occasional rod-like micelles with liquid crystalline (LC) domains in the micellar core. The micellar structures (e.g., aggregationmore » number, radius of gyration, chain packing in the micelle) were found to be dependent on the solution pH and the position of the ionizable site along the chain. This study has highlighted the potential of controlling the position of ionizable sites along the BCP polymer to modulate the electrostatic and LC interactions, thus tailoring the micellar structure at different solution pH values in water.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [3]; ORCiD logo [4]; ORCiD logo [5];  [6];  [6]; ORCiD logo [1]
+ Show Author Affiliations
  1. Department of Chemistry and Macromolecular Studies Group, Louisiana State University, Baton Rouge, Louisiana 70803, United States
  2. Center for Neutron Research, National Institute of Standards and Technology, Gaithersburg, Maryland 20899, United States
  3. X-ray Science Division, Argonne National Laboratory, Lemont, Illinois 60439, United States
  4. Neutron Scattering Division and Second Target Station, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
  5. Neutron Scattering Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee 37831, United States
  6. MacCHESS (Macromolecular Diffraction Facility at CHESS), Cornell University, Ithaca, New York 14850, United States
Publication Date:
Research Org.:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). High Flux Isotope Reactor (HFIR); Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Louisiana State Univ., Baton Rouge, LA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER); National Science Foundation (NSF); USDOE Office of Science (SC), Basic Energy Sciences (BES); National Institute of General Medical Sciences (NIGMS)
OSTI Identifier:
1991980
Alternate Identifier(s):
OSTI ID: 1992715; OSTI ID: 1994948
Grant/Contract Number:  
FWP ERKP291; AC05-00OR22725; CHE 2003458; DMR-1829070; 1-P30-GM124166-01A1; AC02-06CH11357
Resource Type:
Published Article
Journal Name:
Biomacromolecules
Additional Journal Information:
Journal Name: Biomacromolecules Journal Volume: 24 Journal Issue: 8; Journal ID: ISSN 1525-7797
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
59 BASIC BIOLOGICAL SCIENCES; block copolymer micelles; charge pattern; liquid crystal; scattering; polypeptoid; monomers; polymers; solution chemistry; X-ray scattering

Citation Formats

Zhang, Meng, Liu, Yun, Zuo, Xiaobing, Qian, Shuo, Pingali, Sai Venkatesh, Gillilan, Richard E., Huang, Qingqiu, and Zhang, Donghui. pH-Dependent Solution Micellar Structure of Amphoteric Polypeptoid Block Copolymers with Positionally Controlled Ionizable Sites. United States: N. p., 2023. Web. doi:10.1021/acs.biomac.3c00407.
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Zhang, Meng, Liu, Yun, Zuo, Xiaobing, Qian, Shuo, Pingali, Sai Venkatesh, Gillilan, Richard E., Huang, Qingqiu, & Zhang, Donghui. pH-Dependent Solution Micellar Structure of Amphoteric Polypeptoid Block Copolymers with Positionally Controlled Ionizable Sites. United States. https://doi.org/10.1021/acs.biomac.3c00407
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Zhang, Meng, Liu, Yun, Zuo, Xiaobing, Qian, Shuo, Pingali, Sai Venkatesh, Gillilan, Richard E., Huang, Qingqiu, and Zhang, Donghui. Fri . "pH-Dependent Solution Micellar Structure of Amphoteric Polypeptoid Block Copolymers with Positionally Controlled Ionizable Sites". United States. https://doi.org/10.1021/acs.biomac.3c00407.
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@article{osti_1991980,
title = {pH-Dependent Solution Micellar Structure of Amphoteric Polypeptoid Block Copolymers with Positionally Controlled Ionizable Sites},
author = {Zhang, Meng and Liu, Yun and Zuo, Xiaobing and Qian, Shuo and Pingali, Sai Venkatesh and Gillilan, Richard E. and Huang, Qingqiu and Zhang, Donghui},
abstractNote = {While solution micellization of ionic block copolymers (BCP) with randomly distributed ionization sites along the hydrophilic segments has been extensively studied, the roles of positionally controlled ionization sites along the BCP chains in their micellization and resulting micellar structure remain comparatively less understood. Herein, three amphoteric polypeptoid block copolymers carrying two oppositely charged ionizable sites, with one fixed at the hydrophobic terminus and the other varyingly positioned along the hydrophilic segment, have been synthesized by sequential ring-opening polymerization method. The presence of the ionizable site at the hydrophobic segment terminus is expected to promote polymer association toward equilibrium micellar structures in an aqueous solution. The concurrent presence of oppositely charged ionizable sites on the polymer chains allows the polymer association to be electrostatically modulated in a broad pH range (ca. 2–12). Micellization of the amphoteric polypeptoid BCP in dilute aqueous solution and the resulting micellar structure at different solution pHs was investigated by a combination of scattering and microscopic methods. Negative-stain transmission-electron microscopy (TEM), small-angle neutron scattering (SANS), and small-angle X-ray scattering (SAXS) analyses revealed the dominant presence of core–shell-type spherical micelles and occasional rod-like micelles with liquid crystalline (LC) domains in the micellar core. The micellar structures (e.g., aggregation number, radius of gyration, chain packing in the micelle) were found to be dependent on the solution pH and the position of the ionizable site along the chain. This study has highlighted the potential of controlling the position of ionizable sites along the BCP polymer to modulate the electrostatic and LC interactions, thus tailoring the micellar structure at different solution pH values in water.},
doi = {10.1021/acs.biomac.3c00407},
journal = {Biomacromolecules},
number = 8,
volume = 24,
place = {United States},
year = {Fri Jul 21 00:00:00 EDT 2023},
month = {Fri Jul 21 00:00:00 EDT 2023}
}
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https://doi.org/10.1021/acs.biomac.3c00407
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