Modulating Water Distribution and the Intramicellar Assembly of Sequence-Defined Ionic Peptoid Block Copolymers by the Ionic Monomer Position

Bailee N. Barrett; Chi Huan Tung; Guan Rong Huang; Istiak Hossain; Chang Woo Do; Vijay T. John; Wei Ren Chen; Donghui Zhang

doi:10.1021/acs.macromol.3c00646

Modulating Water Distribution and the Intramicellar Assembly of Sequence-Defined Ionic Peptoid Block Copolymers by the Ionic Monomer Position

Bailee N. Barrett, Chi Huan Tung, Guan Rong Huang, Istiak Hossain, Chang Woo Do, Vijay T. John, Wei Ren Chen, Donghui Zhang

SANS & Spin Echo

Research output: Contribution to journal › Article › peer-review

1 Scopus citations

Abstract

The intramicellar mass heterogeneity of a series of sequence-defined ionic peptoid block copolymers carrying a single charged monomer has been determined through contrast variation small-angle neutron scattering analysis. We observe that the internal micellar structure, namely, the number density radial distributions of invasive water and peptoid polymer, is significantly impacted by the location of the ionic monomer. By positioning the ionic monomer progressively closer to the hydrophilic/hydrophobic block junction, the micelles become less compact with increasing levels of chain folding and invasive water to accommodate electrostatic repulsion among the ionic monomers via solvation. This results in increasingly smaller micellar aggregates with aggregation numbers (N_agg) ranging from 15.6 to 44 and micellar radii (R_b) ranging from 61 to 94 Å. This study highlights the potential of using ionic monomer position as a design parameter to control the internal structures of nanoscale micellar assemblies.

Original language	English
Pages (from-to)	5306-5313
Number of pages	8
Journal	Macromolecules
Volume	56
Issue number	14
DOIs	https://doi.org/10.1021/acs.macromol.3c00646
State	Published - Jul 25 2023

Funding

This research used resources at the High Flux Isotope Reactor (HFIR) and the Spallation Neutron Source (SNS), supported by the Office of Basic Energy Science, U.S. Department of Energy. SANS studies performed on the Bio-SANS are also funded by the office of Biological and Environmental Research, U. S. Department of Energy under Contract FWP ERKP291. We thank Dr. Sai V. Pingali and Dr. Luke Heroux from the Bio-SANS instrument for assisting the SANS experiments and Jibao He from the Coordinated Instrumentation Facility (CIF) at Tulane University for assisting the CryoTEM characterization. G.R.H. is supported by the National Science and Technology Council (NSTC) in Taiwan with Grant No. NSTC 111-2112-M-110-021-MY3. This work was supported by the National Science Foundation (CHE 2003458).

Funders	Funder number
National Science Foundation	CHE 2003458
U.S. Department of Energy	FWP ERKP291
Basic Energy Sciences
Biological and Environmental Research
Tulane University
National Science and Technology Council	NSTC 111-2112-M-110-021-MY3

Access to Document

10.1021/acs.macromol.3c00646

Cite this

@article{010164068abf4ca68d6405a9a01e9023,

title = "Modulating Water Distribution and the Intramicellar Assembly of Sequence-Defined Ionic Peptoid Block Copolymers by the Ionic Monomer Position",

abstract = "The intramicellar mass heterogeneity of a series of sequence-defined ionic peptoid block copolymers carrying a single charged monomer has been determined through contrast variation small-angle neutron scattering analysis. We observe that the internal micellar structure, namely, the number density radial distributions of invasive water and peptoid polymer, is significantly impacted by the location of the ionic monomer. By positioning the ionic monomer progressively closer to the hydrophilic/hydrophobic block junction, the micelles become less compact with increasing levels of chain folding and invasive water to accommodate electrostatic repulsion among the ionic monomers via solvation. This results in increasingly smaller micellar aggregates with aggregation numbers (Nagg) ranging from 15.6 to 44 and micellar radii (Rb) ranging from 61 to 94 {\AA}. This study highlights the potential of using ionic monomer position as a design parameter to control the internal structures of nanoscale micellar assemblies.",

author = "Barrett, {Bailee N.} and Tung, {Chi Huan} and Huang, {Guan Rong} and Istiak Hossain and Do, {Chang Woo} and John, {Vijay T.} and Chen, {Wei Ren} and Donghui Zhang",

note = "Publisher Copyright: {\textcopyright} 2023 American Chemical Society",

year = "2023",

month = jul,

day = "25",

doi = "10.1021/acs.macromol.3c00646",

language = "English",

volume = "56",

pages = "5306--5313",

journal = "Macromolecules",

issn = "0024-9297",

publisher = "American Chemical Society",

number = "14",

}

TY - JOUR

T1 - Modulating Water Distribution and the Intramicellar Assembly of Sequence-Defined Ionic Peptoid Block Copolymers by the Ionic Monomer Position

AU - Barrett, Bailee N.

AU - Tung, Chi Huan

AU - Huang, Guan Rong

AU - Hossain, Istiak

AU - Do, Chang Woo

AU - John, Vijay T.

AU - Chen, Wei Ren

AU - Zhang, Donghui

PY - 2023/7/25

Y1 - 2023/7/25

N2 - The intramicellar mass heterogeneity of a series of sequence-defined ionic peptoid block copolymers carrying a single charged monomer has been determined through contrast variation small-angle neutron scattering analysis. We observe that the internal micellar structure, namely, the number density radial distributions of invasive water and peptoid polymer, is significantly impacted by the location of the ionic monomer. By positioning the ionic monomer progressively closer to the hydrophilic/hydrophobic block junction, the micelles become less compact with increasing levels of chain folding and invasive water to accommodate electrostatic repulsion among the ionic monomers via solvation. This results in increasingly smaller micellar aggregates with aggregation numbers (Nagg) ranging from 15.6 to 44 and micellar radii (Rb) ranging from 61 to 94 Å. This study highlights the potential of using ionic monomer position as a design parameter to control the internal structures of nanoscale micellar assemblies.

AB - The intramicellar mass heterogeneity of a series of sequence-defined ionic peptoid block copolymers carrying a single charged monomer has been determined through contrast variation small-angle neutron scattering analysis. We observe that the internal micellar structure, namely, the number density radial distributions of invasive water and peptoid polymer, is significantly impacted by the location of the ionic monomer. By positioning the ionic monomer progressively closer to the hydrophilic/hydrophobic block junction, the micelles become less compact with increasing levels of chain folding and invasive water to accommodate electrostatic repulsion among the ionic monomers via solvation. This results in increasingly smaller micellar aggregates with aggregation numbers (Nagg) ranging from 15.6 to 44 and micellar radii (Rb) ranging from 61 to 94 Å. This study highlights the potential of using ionic monomer position as a design parameter to control the internal structures of nanoscale micellar assemblies.

UR - http://www.scopus.com/inward/record.url?scp=85165672821&partnerID=8YFLogxK

U2 - 10.1021/acs.macromol.3c00646

DO - 10.1021/acs.macromol.3c00646

M3 - Article

AN - SCOPUS:85165672821

SN - 0024-9297

VL - 56

SP - 5306

EP - 5313

JO - Macromolecules

JF - Macromolecules

IS - 14

ER -

Modulating Water Distribution and the Intramicellar Assembly of Sequence-Defined Ionic Peptoid Block Copolymers by the Ionic Monomer Position

Abstract

Funding

Access to Document

Other files and links

Fingerprint

Cite this