Amyloid‐inspired Peptide Self‐assembly/Disassembly as Intervened by Gold Nanoparticles and Polydopamine Coating to Dictate Spatiotemporal Organization

Abstract

Spatiotemporal control for supramolecular polymerization has rendered a paradigm shift towards designing complex multi‐component supramolecular materials and derived nanocomposites. In this paper, we demonstrate self‐assembly/disassembly of amyloid‐inspired peptide nanostructures from Fmoc‐VFFAKK, 1 using gold nanoparticles (AuNPs)/cysteine mediated coupled equilibrium. We report the use of AuNPs to disaggregate the β‐sheets of the peptide nanofibers 1NF and twisted bundles 1TB to furnish dormant metastable nanoparticles. Upon cysteine mediated sequestration of the AuNPs the peptide fibers are regenerated. Such self‐assembly/disassembly of the fibers shows implication in tuning the mechanical strength of the resulting hydrogels. Further, a conformal coating of polydopamine (PDA) over the peptide fibers using the lysine amines furnishes rather robust fibers and orthogonally safeguard itself from AuNPs mediated disassembly of the fibers. Finally, such active coating with PDA having amine/quinone moieties allows selective attachment of AuNPs to furnish 1‐D organization of AuNPs over the coated peptide fibers.

Thermo-Chemical Cues-Mediated Strategy to Control Peptide Self-Assembly and Charge Transfer Complexation

“…In this regard, the minimalist peptide sequence has emerged as a versatile building block owing to their sequence-specific interactions and the ability to respond to external stimuli − such as pH, light, temperature, redox, enzyme activation, and ionic strength to render excellent control over peptide self-assembly/disassembly toward specific and smart applications in piezoelectronics, drug delivery, and catalysis. − In this regard, we demonstrated the pathway-dependent self-assembly of the amyloid-inspired peptide amphiphiles to precisely control the size and shape of one-dimensional nanofibers and two-dimensional nanosheets that further dictated the mechanical stiffness and molecular recognition of the resulting hydrogel. , Such a controlled self-assembly of stimuli-responsive peptide amphiphiles has also been exploited in making stiff and interpenetrating hydrogels toward designing biomimetic materials tissue engineering. − …”

“…37−42 In this regard, we demonstrated the pathway-dependent self-assembly of the amyloid-inspired peptide amphiphiles to precisely control the size and shape of one-dimensional nanofibers and two-dimensional nanosheets that further dictated the mechanical stiffness and molecular recognition of the resulting hydrogel. 43,44 Such a controlled self-assembly of stimuliresponsive peptide amphiphiles has also been exploited in making stiff and interpenetrating hydrogels toward designing biomimetic materials tissue engineering. 45−47 Further, the fluorophore tethered peptide provides excellent opportunities for designing charge transfer (CT) complexes with high conductivity and charge carrier densities toward organic nanowires in electronic and optoelectronic nanodevices.…”

Topochemical polymerization in phenylalanine anchored chiral diacetylenes for chiroptical properties and tunable thermo-, halo-, solvatochromism

“…Our group has been working in the frontier areas of peptide self-assembly [38][39][40] and has recently demonstrated interesting examples of amyloid-inspired peptide amphiphiles that showed chiral recognition of the building blocks and self-sorting fidelity. 41 Such molecular recognition is of paramount importance in creating next-generation biocatalysts and biomaterials.…”

In Situ Insights into the Nucleation and Growth Mechanisms of Gold Nanoparticles on Tobacco Mosaic Virus

“…5,6 In that regard, biomolecules have been used as a biotemplate to design uniform nanostructure assemblies, thanks to the functional groups on their surface which allow the NP organizations by chemical conjugation or biomineralization. 1D and 2D Au NP assemblies were formed on microtubules proteins, 7 amyloid fibers, 8 and DNA origami. 9,10 DNA origami also offered the possibility to fabricate 3D NP superlattices or large-size nanoarchitectures.…”

“…Controlling the three-dimensional spatial distribution of plasmonic nanostructures at the nanoscale has been a major challenge to developing efficient nanotechnologies for biomedical and sensing applications. − Indeed, the proximity of Au nanoparticles (NPs) generates plasmonic hot spots with a high enhancement factor, and a red-shift and broadening of the plasmon resonance band leading to better light-response sensitivity in the biological window (i.e., Near Infra-Red (NIR)). , In that regard, biomolecules have been used as a biotemplate to design uniform nanostructure assemblies, thanks to the functional groups on their surface which allow the NP organizations by chemical conjugation or biomineralization. 1D and 2D Au NP assemblies were formed on microtubules proteins, amyloid fibers, and DNA origami. , DNA origami also offered the possibility to fabricate 3D NP superlattices or large-size nanoarchitectures. − More recently, viruses have been used as scaffolds in nanobiotechnology, because of their variety in size, symmetry and shape, their low cost of production, and their ability to self-assemble. − These virus-based approaches allow the fabrication of nanomaterials with many applications, such as biomedicine, catalysis, and energy storage. − Cowpea mosaic virus has been decorated by quantum dots for fluorescence applications, and gold NPs for SERS and electronic nanosensors. − Recently, we have also obtained in-solution SERS sensors by grafting Au NPs onto the Turnip yellow mosaic virus capsid …”