Title: Self-Repair of Structure and Bioactivity in a Supramolecular Nanostructure

Abstract

Supramolecular nanostructures formed through self-assembly can have energy landscapes, which determine their structures and functions depending on the pathways selected for their synthesis and processing and on the conditions they are exposed to after their initial formation. We report here on the structural damage that occurs in supramolecular peptide amphiphile nanostructures, during freezing in aqueous media, and the self-repair pathways that restore their functions. We found that freezing converts long supramolecular nanofibers into shorter ones, compromising their ability to support cell adhesion, but a single heating and cooling cycle reverses the damage and rescues their bioactivity. Thermal energy in this cycle enables noncovalent interactions to reconfigure the nanostructures into the thermodynamically preferred long nanofibers, a repair process that is impeded by kinetic traps. In addition, we found that nanofibers disrupted during freeze-drying also exhibit the ability to undergo thermal self-repair and recovery of their bioactivity, despite the extra disruption caused by the dehydration step. Following both freezing and freeze-drying, which shorten the 1D nanostructures, their self-repair capacity through thermally driven elongation is inhibited by kinetically trapped states, which contain highly stable noncovalent interactions that are difficult to rearrange. These states decrease the extent of thermal nanostructure repair, an observation wemore » hypothesize applies to supramolecular systems in general and is mechanistically linked to suppressed molecular exchange dynamics.« less

Authors:

Chen, Charlotte H.  ^[1];

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• Search OSTI.GOV for ORCID "0000-0002-3119-9919"
• Search orcid.org for ORCID "0000-0002-3119-9919"

Palmer, Liam C.  ^[2];

• Search OSTI.GOV for author "Palmer, Liam C."
• Search OSTI.GOV for ORCID "0000-0003-0804-1168"
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Stupp, Samuel I.  ^[2]

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• Search OSTI.GOV for ORCID "0000-0002-5491-7442"
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+ Show Author Affiliations

1. Northwestern Univ., Evanston, IL (United States)
2. Northwestern Univ., Evanston, IL (United States); Northwestern Univ., Chicago, IL (United States)

Publication Date:

Wed Oct 31 00:00:00 EDT 2018

Research Org.:

Energy Frontier Research Centers (EFRC) (United States). Center for Bio-Inspired Energy Science (CBES); Argonne National Lab. (ANL), Argonne, IL (United States); Northwestern Univ., Evanston, IL (United States)

Sponsoring Org.:

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

OSTI Identifier:

1566549

Alternate Identifier(s):

OSTI ID: 1822210; OSTI ID: 1846775

Grant/Contract Number:  

AC02-06CH11357; SC0000989

Resource Type:

Journal Article: Accepted Manuscript

Journal Name:

Nano Letters

Additional Journal Information:

Journal Volume: 18; Journal Issue: 11; Journal ID: ISSN 1530-6984

Publisher:

American Chemical Society

Country of Publication:

United States

Language:

English

Subject:

36 MATERIALS SCIENCE; 99 GENERAL AND MISCELLANEOUS; 77 NANOSCIENCE AND NANOTECHNOLOGY; catalysis (homogeneous); solar (photovoltaic); bio-inspired; charge transport; mesostructured materials; materials and chemistry by design; synthesis (novel materials); synthesis (self-assembly); supramolecular nanostructures; self-assembly; self-repair; biomaterials; regenerative medicine; cell−nanostructure interactions; Nanostructures, Nanofibers, Freezing, Peptides and proteins, Viscosity; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY