Hydrogen Bonding Stiffens Peptide Amphiphile Supramolecular Filaments by Aza-Glycine Residues
Abstract
Peptide amphiphiles (PAs) are a class of molecules comprised of short amino acid sequences conjugated to hydrophobic moieties that may exhibit self-assembly in water into supramolecular structures. Here, we investigate here how mechanical properties of hydrogels formed by PA supramolecular nanofibers are affected by hydrogen bond densities within their internal structure by substituting glycine for aza-glycine (azaG) residues. We found that increasing the number of PA molecules that contain azaG up to 5 mol% in PA supramolecular nanofibers increases their persistence length fivefold and decreases their diffusion coefficients as measured by fluorescence recovery after photobleaching. When these PAs are used to create hydrogels, their bulk storage modulus (G') was found to increase as azaG PA content in the supramolecular assemblies increases up to a value of 10 mol% and beyond this value a decrease was observed, likely due to diminished levels of nanofiber entanglement in the hydrogels as a direct result of increased supramolecular rigidity. Interestingly, we found that the bioactivity of the scaffolds toward dopaminergic neurons derived from induced pluripotent stem cells can be enhanced directly by persistence length independently of storage modulus. We hypothesize that this is due to interactions between the cells and the extracellular environment acrossmore »
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Bio-Inspired Energy Science (CBES); Northwestern Univ., Evanston, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1866091
- Alternate Identifier(s):
- OSTI ID: 1846596
- Grant/Contract Number:
- SC0000989
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Acta Biomaterialia
- Additional Journal Information:
- Journal Volume: 135; Journal ID: ISSN 1742-7061
- Publisher:
- Acta Materialia, Inc.
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 59 BASIC BIOLOGICAL SCIENCES; aza-Glycine; hydrogen bonding; nanofibers; peptide amphiphiles; β-sheet; 99 GENERAL AND MISCELLANEOUS; Aza-Glycine
Citation Formats
Godbe, Jacqueline M., Freeman, Ronit, Lewis, Jacob A., Sasselli, Ivan R., Sangji, M. Hussain, and Stupp, Samuel I. Hydrogen Bonding Stiffens Peptide Amphiphile Supramolecular Filaments by Aza-Glycine Residues. United States: N. p., 2021.
Web. doi:10.1016/j.actbio.2021.08.044.
Godbe, Jacqueline M., Freeman, Ronit, Lewis, Jacob A., Sasselli, Ivan R., Sangji, M. Hussain, & Stupp, Samuel I. Hydrogen Bonding Stiffens Peptide Amphiphile Supramolecular Filaments by Aza-Glycine Residues. United States. https://doi.org/10.1016/j.actbio.2021.08.044
Godbe, Jacqueline M., Freeman, Ronit, Lewis, Jacob A., Sasselli, Ivan R., Sangji, M. Hussain, and Stupp, Samuel I. Thu .
"Hydrogen Bonding Stiffens Peptide Amphiphile Supramolecular Filaments by Aza-Glycine Residues". United States. https://doi.org/10.1016/j.actbio.2021.08.044. https://www.osti.gov/servlets/purl/1866091.
@article{osti_1866091,
title = {Hydrogen Bonding Stiffens Peptide Amphiphile Supramolecular Filaments by Aza-Glycine Residues},
author = {Godbe, Jacqueline M. and Freeman, Ronit and Lewis, Jacob A. and Sasselli, Ivan R. and Sangji, M. Hussain and Stupp, Samuel I.},
abstractNote = {Peptide amphiphiles (PAs) are a class of molecules comprised of short amino acid sequences conjugated to hydrophobic moieties that may exhibit self-assembly in water into supramolecular structures. Here, we investigate here how mechanical properties of hydrogels formed by PA supramolecular nanofibers are affected by hydrogen bond densities within their internal structure by substituting glycine for aza-glycine (azaG) residues. We found that increasing the number of PA molecules that contain azaG up to 5 mol% in PA supramolecular nanofibers increases their persistence length fivefold and decreases their diffusion coefficients as measured by fluorescence recovery after photobleaching. When these PAs are used to create hydrogels, their bulk storage modulus (G') was found to increase as azaG PA content in the supramolecular assemblies increases up to a value of 10 mol% and beyond this value a decrease was observed, likely due to diminished levels of nanofiber entanglement in the hydrogels as a direct result of increased supramolecular rigidity. Interestingly, we found that the bioactivity of the scaffolds toward dopaminergic neurons derived from induced pluripotent stem cells can be enhanced directly by persistence length independently of storage modulus. We hypothesize that this is due to interactions between the cells and the extracellular environment across different size scales: from filopodia adhering to individual nanofiber bundles to cell adhesion sites that interact with the hydrogel as a bulk substrate. Fine tuning of hydrogen bond density in self-assembling peptide biomaterials such as PAs provides an approach to control nanoscale stiffness as part of an overall strategy to optimize bioactivity in these supramolecular systems. supramolecular biomaterials.},
doi = {10.1016/j.actbio.2021.08.044},
journal = {Acta Biomaterialia},
number = ,
volume = 135,
place = {United States},
year = {Thu Sep 02 00:00:00 EDT 2021},
month = {Thu Sep 02 00:00:00 EDT 2021}
}
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