Bottom-up on-surface synthesis based on click-functionalized peptide bundles.

Area of Science:

• Molecular Nanotechnology
• Supramolecular Chemistry
• Surface Science

Background:

• On-surface synthesis is key for atomically low-dimensional nanostructures.
• Longitudinal, step-by-step controllable covalent bonding for nanomaterial growth is challenging.
• Existing methods often result in horizontal growth, limiting precise structural control.

Purpose of the Study:

• To develop a bottom-up on-surface synthesis strategy for longitudinal nanostructure assembly.
• To utilize peptide bundles ('bundlemers') as building blocks for controlled nanorod formation.
• To create tunable hybrid nanostructures with potential for self-assembly.

Main Methods:

• Employing coiled-coil homotetrameric peptide bundles ('bundlemers') with terminal click-reactive functionalities.
• Grafting bundlemer units vertically onto surfaces or other bundlemer units via click chemistry.
• Synthesizing rigid rods with a defined number of bundlemer units (up to 6).
• Attaching linear poly(ethylene glycol) (PEG) to form rod-PEG hybrid nanostructures.

Main Results:

• Successful longitudinal, bottom-up synthesis of rigid nanorods with precise bundlemer incorporation.
• Creation of rod-PEG hybrid nanostructures that can be released from the surface.
• Demonstration of self-assembly of rod-PEG nanostructures into diverse nano-hyperstructures in water.

Conclusions:

• The presented strategy offers a simple and accurate method for manufacturing various on-surface nanomaterials.
• This approach enables precise control over nanostructure length and composition.
• The developed technique opens avenues for designing complex nano-architectures with tunable properties.