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Gupta, Deepika; Gupta, Varun; Nath, Debasish; Miglani, Chirag; Mandal, Dipankar; Pal, Asish
ACS applied materials & interfaces, 05/2023, Letnik: 15, Številka: 21Journal Article
Supramolecular assemblies with well-defined structural attenuation toward varied functional implications are an emerging area in mimicking natural biomaterials. In that regard, the redox stimuli-responsive ferrocene moiety can reversibly change between a nonpolar ferrocenyl and polar ferrocenium cation that endows interesting modular features to the building blocks with respect to self-assembly/disassembly. We design a series of ferrocene anchored peptide fragment N VFFAKK C using hydrophobic alkyl spacers of different chain lengths. Increasing the spacer length between the redox-responsive and self-assembling motifs increases the propensity to form robust nanofibers, which can be physically cross-linked to form hydrogels. The controlled redox response of the ferrocene moiety tandem with pH control provides access to structural control over the peptide nanostructures and tunable mechanical strengths. Further, such redox-sequestered dormant states hinder the spontaneous nucleation process that we exploit toward seeded supramolecular polymerization to form block cofibers composed of redox-responsive periphery and nonresponsive cores. Finally, such redox sequestration of peptide self-assembly renders an on–off piezoelectric response for potential utilization in peptide bioelectronics.
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