Self-Repair of Structure and Bioactivity in a Supramolecular Nanostructure
- Northwestern Univ., Evanston, IL (United States)
- Northwestern Univ., Evanston, IL (United States); Northwestern Univ., Chicago, IL (United States)
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 we hypothesize applies to supramolecular systems in general and is mechanistically linked to suppressed molecular exchange dynamics.
- Research Organization:
- 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 Organization:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- Grant/Contract Number:
- AC02-06CH11357; SC0000989
- OSTI ID:
- 1566549
- Alternate ID(s):
- OSTI ID: 1822210; OSTI ID: 1846775
- Journal Information:
- Nano Letters, Vol. 18, Issue 11; ISSN 1530-6984
- Publisher:
- American Chemical SocietyCopyright Statement
- Country of Publication:
- United States
- Language:
- English
Web of Science
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Related Subjects
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