Self‐assembly of Natural and Unnatural Nucleobases at Surfaces and Interfaces

Abstract

The self-assembly of small organic molecules interacting via non-covalent forces is a viable approach towards the construction of highly ordered nanostructured materials. Among various molecular components, natural and unnatural nucleobases can undergo non-covalent self-association to form supramolecular architectures with ad hoc structural motifs. Such structures, when decorated with appropriate electrically/optically active units, can be used as scaffolds to locate such units in pre-determined positions in 2D on a surface, thereby paving the way towards a wide range of applications, e.g., in optoelectronics. This review discusses some of the basic concepts of the supramolecular engineering of natural and unnatural nucleobases and derivatives thereof as well as self-assembly processes on conductive solid substrates, as investigated by scanning tunnelling microscopy in ultra-high vacuum and at the solid/liquid interface. By unravelling the structure and dynamics of these self-assembled architectures with a sub-nanometer resolution, a greater control over the formation of increasingly sophisticated functional systems is achieved. The ability to understand and predict how nucleobases interact, both among themselves as well as with other molecules, is extremely important, since it provides access to ever more complex DNA- and RNA-based nanostructures and nanomaterials as key components in nanomechanical devices.

Three-Dimensional Uracil Network with Sodium as a Linker

“…59 A tetrameric configuration also allows the generation of 2D periodic structures that can be themselves stable prior the cation addition. We have in the following restricted our exploration to tetrameric structures, i.e.…”

Self-assembly of diphenylalanine with preclick components as capping groups

“…[1][2][3][4][5] As these interactions are ubiquitous in biological systems, nature has inspired artificial building blocks amenable to self-assemble into supramolecular structures. [6][7][8][9] With respect to biological building blocks, peptides are of great interest for materials science due to their structural simplicity, functional versatility, cost effectiveness, and widespread applications.…”

“…16 Due to these characteristics, extensive research efforts have been devoted to expand this class of peptide-based materials. 17,18 More specifically, a large number of FF-based biomaterials has been engineered considering, individually or in combination, the following general approaches: (1) increment the number of F residues in the peptide sequence (i.e. growing from FF to capping group at the N-terminus enhances the already important role played by - stacking interactions.…”

Two-Component Self-Assemblies: Investigation of a Synergy between Bisurea Stickers

“…On surfaces, self-assembled monolayers allow to create functional nanosystems with implications for surface chirality, nanoporous surfaces, optoelectronics or surface reactivity. 6,7,8 Control of the self-assembly process in 3D can lead to composite crystals 9 or to porous frameworks. 10,11,12 While some of these systems may involve a single component bearing a selfcomplementary sticker that is designed to self-assemble into large objects, it is clearly of interest to develop two-component systems for added flexibility in the design of the properties and to be able to trigger the assembly at will.…”