Control of Peptide Amphiphile Supramolecular Nanostructures by Isosteric Replacements
Abstract
Supramolecular nanostructures with tunable properties can have applications in medicine, pharmacy, and biotechnology. In this work, we show that the self-assembly behavior of peptide amphiphiles (PAs) can be effectively tuned by replacing the carboxylic acids exposed to the aqueous media with isosteres, functionalities that share key physical or chemical properties with another chemical group. Transmission electron microscopy, atomic force microscopy, and small-angle X-ray scattering studies indicated that the nanostructure’s morphologies are responsive to the ionization states of the side chains, which are related to their pKa values. Circular dichroism studies revealed the effect of the isosteres on the internal arrangement of the nanostructures. The interactions between diverse surfaces and the nanostructures and the effect of salt concentration and temperature were assessed to further understand the properties of these self-assembled systems. These results indicate that isosteric replacements allow the pH control of supramolecular morphology by manipulating the pKa of the charged groups located on the nanostructure’s surface. Theoretical studies were performed to understand the morphological transitions that the nanostructures underwent in response to pH changes, suggesting that the transitions result from alterations in the Coulomb forces between PA molecules. Furthermore, this work provides a strategy for designing biomaterials that can maintainmore »
- Authors:
-
- Univ. of Nebraska Medical Center, Omaha, NE (United States)
- Northwestern Univ., Evanston, IL (United States)
- Univ. of Nebraska Medical Center, Omaha, NE (United States); Univ. of Nebraska, Omaha, NE (United States)
- Univ. Nacional de General San Martín, Buenos Aires (Argentina)
- Inst. de Investigaciones Fisicoquímicas Teóricas y Aplicadas (INIFTA), La Plata (Argentina)
- Ciudad Univ. (Argentina)
- Creighton Univ., Omaha, NE (United States)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Bio-Inspired Energy Science (CBES)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1865064
- Grant/Contract Number:
- SC0000989
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Biomacromolecules
- Additional Journal Information:
- Journal Volume: 22; Journal Issue: 8; Journal ID: ISSN 1525-7797
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 99 GENERAL AND MISCELLANEOUS; Transmission electron microscopy; Chemical structure; Nanostructures; Morphology, X-ray scattering
Citation Formats
Xing, Huihua, Chin, Stacey M., Udumula, Venkata Reddy, Krishnaiah, Maddeboina, Rodrigues de Almeida, Nathalia, Huck-Iriart, Cristián, Picco, Agustín S., Lee, Sieun Ruth, Zaldivar, Gervasio, Jackson, Kelsey A., Tagliazucchi, Mario, Stupp, Samuel I., and Conda-Sheridan, Martin. Control of Peptide Amphiphile Supramolecular Nanostructures by Isosteric Replacements. United States: N. p., 2021.
Web. doi:10.1021/acs.biomac.1c00379.
Xing, Huihua, Chin, Stacey M., Udumula, Venkata Reddy, Krishnaiah, Maddeboina, Rodrigues de Almeida, Nathalia, Huck-Iriart, Cristián, Picco, Agustín S., Lee, Sieun Ruth, Zaldivar, Gervasio, Jackson, Kelsey A., Tagliazucchi, Mario, Stupp, Samuel I., & Conda-Sheridan, Martin. Control of Peptide Amphiphile Supramolecular Nanostructures by Isosteric Replacements. United States. https://doi.org/10.1021/acs.biomac.1c00379
Xing, Huihua, Chin, Stacey M., Udumula, Venkata Reddy, Krishnaiah, Maddeboina, Rodrigues de Almeida, Nathalia, Huck-Iriart, Cristián, Picco, Agustín S., Lee, Sieun Ruth, Zaldivar, Gervasio, Jackson, Kelsey A., Tagliazucchi, Mario, Stupp, Samuel I., and Conda-Sheridan, Martin. Thu .
"Control of Peptide Amphiphile Supramolecular Nanostructures by Isosteric Replacements". United States. https://doi.org/10.1021/acs.biomac.1c00379. https://www.osti.gov/servlets/purl/1865064.
@article{osti_1865064,
title = {Control of Peptide Amphiphile Supramolecular Nanostructures by Isosteric Replacements},
author = {Xing, Huihua and Chin, Stacey M. and Udumula, Venkata Reddy and Krishnaiah, Maddeboina and Rodrigues de Almeida, Nathalia and Huck-Iriart, Cristián and Picco, Agustín S. and Lee, Sieun Ruth and Zaldivar, Gervasio and Jackson, Kelsey A. and Tagliazucchi, Mario and Stupp, Samuel I. and Conda-Sheridan, Martin},
abstractNote = {Supramolecular nanostructures with tunable properties can have applications in medicine, pharmacy, and biotechnology. In this work, we show that the self-assembly behavior of peptide amphiphiles (PAs) can be effectively tuned by replacing the carboxylic acids exposed to the aqueous media with isosteres, functionalities that share key physical or chemical properties with another chemical group. Transmission electron microscopy, atomic force microscopy, and small-angle X-ray scattering studies indicated that the nanostructure’s morphologies are responsive to the ionization states of the side chains, which are related to their pKa values. Circular dichroism studies revealed the effect of the isosteres on the internal arrangement of the nanostructures. The interactions between diverse surfaces and the nanostructures and the effect of salt concentration and temperature were assessed to further understand the properties of these self-assembled systems. These results indicate that isosteric replacements allow the pH control of supramolecular morphology by manipulating the pKa of the charged groups located on the nanostructure’s surface. Theoretical studies were performed to understand the morphological transitions that the nanostructures underwent in response to pH changes, suggesting that the transitions result from alterations in the Coulomb forces between PA molecules. Furthermore, this work provides a strategy for designing biomaterials that can maintain or change behaviors based on the pH differences found within cells and tissues.},
doi = {10.1021/acs.biomac.1c00379},
journal = {Biomacromolecules},
number = 8,
volume = 22,
place = {United States},
year = {Thu Jul 22 00:00:00 EDT 2021},
month = {Thu Jul 22 00:00:00 EDT 2021}
}
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