Calcium-based functionalization of carbon nanostructures for peptide immobilization in aqueous media

We predict a covalent functionalization strategy for precise immobilization of peptides on carbon nanostructures immersed in water, based on atomistic first-principles simulations. The proposed strategy consists of straightforward decoration of the carbon nanosurfaces (CNS, e.g. graphene and nanotubes) with calcium atoms. This approach presents a series of improvements with respect to customary covalent CNS functionalization techniques: (i) intense and highly selective biomolecule-CNS interactions are accomplished while preserving atomic CNS periodicity, (ii) under ambient conditions calcium-decorated CNS and their interactions with biomolecules remain strongly attractive both in vacuum and aqueous environment, and (iii) calcium coatings already deplete the intrinsic hydrophobicity of CNS thus additional functionalization for CNS water miscibility is not required. The observed biomolecule-CNS binding enhancement can be explained in terms of large electronic transfers from calcium to the oxygen atoms in the carboxyl and side-chain groups of the peptide. The kind of electronic, structural and thermodynamic properties revealed in this work strongly suggest the potential of Ca-decorated CNS for applications in drug delivery and biomaterials engineering.