Control of Peptide Amphiphile Supramolecular Nanostructures by Isosteric Replacements

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

doi:10.1021/acs.biomac.1c00379

Control of Peptide Amphiphile Supramolecular Nanostructures by Isosteric Replacements

Journal Article · Thu Jul 22 00:00:00 EDT 2021 · Biomacromolecules

DOI:https://doi.org/10.1021/acs.biomac.1c00379· OSTI ID:1865064

Xing, Huihua ^[1]; ^[2]; ^[3]; Krishnaiah, Maddeboina ^[3]; ^[4]; ^[5]; Picco, Agustín S. ^[6]; Lee, Sieun Ruth ^[2]; Zaldivar, Gervasio ^[7]; Jackson, Kelsey A. ^[8]; ^[7]; ^[2]; ^[3]

Univ. of Nebraska Medical Center, Omaha, NE (United States); CBES
Northwestern Univ., Evanston, IL (United States)
Univ. of Nebraska Medical Center, Omaha, NE (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)

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 pK_a 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 pK_a 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.

View Accepted Manuscript (DOE)

Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Bio-Inspired Energy Science (CBES)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0000989

OSTI ID:: 1865064

Alternate ID(s):: OSTI ID: 1820457

Journal Information:: Biomacromolecules, Journal Name: Biomacromolecules Journal Issue: 8 Vol. 22; ISSN 1525-7797

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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