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

On-surface synthesis is a modern technique for the preparation of atomically low-dimensional molecular nanostructures. However, most nanomaterials grow horizontally on the surface, and the step-by-step longitudinally controllable covalent bonding reaction on the surface is rarely reported. Here, we successfully achieved bottom-up on-surface synthesis by using coiled-coil homotetrameric peptide bundles called 'bundlemers' as building blocks. Rigid nano-cylindrical bundlemer with two click-reactive functionalities at each end can be grafted vertically onto the surface or another bundlemer with complementary clickable groups by click reaction at one end, thus enabling the longitudinal bottom-up synthesis of rigid rods with an exact number of bundlemers (up to 6) on the surface. Moreover, we can graft linear poly(ethylene glycol) (PEG) to one terminal of rigid rods to obtain rod-PEG hybrid nanostructures that can be released from the surface under specific conditions. Interestingly, rod-PEG nanostructures consisting of different numbers of bundles can self-assemble in water into different nano-hyperstructures. In general, the bottom-up on-surface synthesis strategy presented here can provide a simple and accurate method to manufacture a variety of nanomaterials.