Journal
CHEMISTRY OF MATERIALS
Volume 34, Issue 10, Pages 4456-4470Publisher
AMER CHEMICAL SOC
DOI: 10.1021/acs.chemmater.2c00228
Keywords
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Funding
- Institute of Nano Science and Technology (INST)
- Department of Science & Technology (DST, SERB) [CRG/2020/004251]
- INST fellowship
- CSIR-JRF
- Lakshmi
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In this research, the active peptide self-assembly motifs are sequestered using chemical and photo strategies, and controlled seeded supramolecular polymerization is achieved upon activation. The results show that the amyloid-inspired peptide with a pendant azobenzene can form metastable nanoparticles under the influence of solvent and temperature, which can be transformed into kinetically controlled nanofibers and thermodynamically controlled twisted bundles. Using host-guest inclusion complex or photoisomerization leads to the formation of off-pathway metastable states that retard spontaneous supramolecular polymerization.
Supramolecular assemblies are essential for specific biologicalfunctions and mandate precise control over the mesoscopic scale for higherfunctional efficiency. Such well-defined biomimetic self-organization can beaccessed through kinetically controlled nonequilibrium transformationsrather than the typical downhill thermodynamically driven processes.Recently, spatiotemporal control for the living supramolecular polymer-ization has rendered a paradigm shift toward designing complex multi-component supramolecular active materials; however, directing the activemonomer toward predictive kinetically trapped materials still remains aconsiderable challenge as this necessitates circumventing spontaneousnucleation of the monomers during the self-assembly process. Herein, wedemonstrate dual strategies (chemical and photo) to sequester the activepeptide self-assembling motifs in dormant states that, upon judicious activation, engage in controlled seeded supramolecularpolymerization in aqueous milieu for thefirst time. Amyloid-inspired peptide1with a pendant azobenzene moiety demonstrates theformation of on-pathway metastable nanoparticles by the interplay of solvent and temperature that could be transformed intokinetically controlled nanofibers and thermodynamically controlled twisted bundles. Further, using coupled equilibrium such as thehost-guest inclusion complex with cyclodextrin or photoisomerization with UV light leads to the formation of two distinct off-pathway metastable states that retard the spontaneous supramolecular polymerization. A judicious manipulation of the free-energylandscapes in tandem with suitable chemical and photostimuli renders the activation of the dormant states for the peptide self-assembly through a seeded growth strategy. Finally, such photochemical sequestration of self-assembly pathways results in on-offpiezoresponsive peptide nanostructures. In summary, we demonstrated for thefirst time the nonequilibrium peptide self-assemblycoupled with dormant metastable states to allow access to an interesting repertoire of structural diversities and attenuatedpiezoresponse control in supramolecular peptide nanostructures.
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