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Title: Nanocrystalline Oligo(ethylene sulfide)- b-poly(ethylene glycol) Micelles: Structure and Stability

Abstract

Micelle formation generally relies on hydrophobic or electrostatic interactions between distinct regions of amphiphilic molecules. In this work, a different mechanism is considered in which nanocrystalline domains are formed from short ethylene sulfide oligomers at the core of the micelles, leading to exceptionally stable, uniform micellar structures. The structure and thermodynamic properties of the resulting micelles are examined through a combination of experiments, theory, and simulations. It is found that in oligo(ethylene sulfide)- b-poly(ethylene glycol) amphiphiles as few as three ethylene sulfide monomers are sufficient to form a highly crystalline core, surrounded by a water-soluble ethylene glycol corona of arbitrary size. Sulfur-sulfur interactions induce formation of rhombohedral lattice crystalline regions, which exhibit well-defined intramolecular and intermolecular order. An atomistic model is used to determine the free energy of the micelles; the critical micelle concentration (CMC) is found to be extremely small, on the order of 10 -8 mol/L. The size distribution of these micelles is nearly monodisperse. The crystalline core also includes amorphous regions that could serve as hosts for other molecules. Taken together, these properties serve to underscore that controlled crystallization provides a useful and underexploited mechanism for assembly of ultrastable micelles for applications in a variety of settings,more » including drug delivery and immunology.« less

Authors:
 [1];  [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Chicago State Univ., IL (United States). Inst. for Molecular Engineering
  2. Chicago State Univ., IL (United States). Inst. for Molecular Engineering; Argonne National Lab. (ANL), Argonne, IL (United States). Materials Science Division
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1558003
Grant/Contract Number:  
AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Macromolecules
Additional Journal Information:
Journal Volume: 51; Journal Issue: 23; Journal ID: ISSN 0024-9297
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English

Citation Formats

Sevgen, Emre, Dolejsi, Moshe, Nealey, Paul F., Hubbell, Jeffrey A., and de Pablo, Juan J. Nanocrystalline Oligo(ethylene sulfide)-b-poly(ethylene glycol) Micelles: Structure and Stability. United States: N. p., 2018. Web. doi:10.1021/acs.macromol.8b01812.
Sevgen, Emre, Dolejsi, Moshe, Nealey, Paul F., Hubbell, Jeffrey A., & de Pablo, Juan J. Nanocrystalline Oligo(ethylene sulfide)-b-poly(ethylene glycol) Micelles: Structure and Stability. United States. doi:10.1021/acs.macromol.8b01812.
Sevgen, Emre, Dolejsi, Moshe, Nealey, Paul F., Hubbell, Jeffrey A., and de Pablo, Juan J. Mon . "Nanocrystalline Oligo(ethylene sulfide)-b-poly(ethylene glycol) Micelles: Structure and Stability". United States. doi:10.1021/acs.macromol.8b01812. https://www.osti.gov/servlets/purl/1558003.
@article{osti_1558003,
title = {Nanocrystalline Oligo(ethylene sulfide)-b-poly(ethylene glycol) Micelles: Structure and Stability},
author = {Sevgen, Emre and Dolejsi, Moshe and Nealey, Paul F. and Hubbell, Jeffrey A. and de Pablo, Juan J.},
abstractNote = {Micelle formation generally relies on hydrophobic or electrostatic interactions between distinct regions of amphiphilic molecules. In this work, a different mechanism is considered in which nanocrystalline domains are formed from short ethylene sulfide oligomers at the core of the micelles, leading to exceptionally stable, uniform micellar structures. The structure and thermodynamic properties of the resulting micelles are examined through a combination of experiments, theory, and simulations. It is found that in oligo(ethylene sulfide)-b-poly(ethylene glycol) amphiphiles as few as three ethylene sulfide monomers are sufficient to form a highly crystalline core, surrounded by a water-soluble ethylene glycol corona of arbitrary size. Sulfur-sulfur interactions induce formation of rhombohedral lattice crystalline regions, which exhibit well-defined intramolecular and intermolecular order. An atomistic model is used to determine the free energy of the micelles; the critical micelle concentration (CMC) is found to be extremely small, on the order of 10-8 mol/L. The size distribution of these micelles is nearly monodisperse. The crystalline core also includes amorphous regions that could serve as hosts for other molecules. Taken together, these properties serve to underscore that controlled crystallization provides a useful and underexploited mechanism for assembly of ultrastable micelles for applications in a variety of settings, including drug delivery and immunology.},
doi = {10.1021/acs.macromol.8b01812},
journal = {Macromolecules},
number = 23,
volume = 51,
place = {United States},
year = {2018},
month = {11}
}

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