Understanding mol. recognition is of fundamental importance in applications such as therapeutics, chem. catalysis and sensor design. The most common recognition motifs involve biol. macromols. such as antibodies and aptamers. The key to biorecognition consists of a unique three-dimensional structure formed by a folded and constrained bioheteropolymer that creates a binding pocket, or an interface, able to recognize a specific mol. Here, we show that synthetic heteropolymers, once constrained onto a single-walled carbon nanotube by chem. adsorption, also form a new corona phase that exhibits highly selective recognition for specific mols. To prove the generality of this phenomenon, we report three examples of heteropolymer-nanotube recognition complexes for riboflavin, L-thyroxine and oestradiol. In each case, the recognition was predicted using a two-dimensional thermodn. model of surface interactions in which the dissocn. consts. can be tuned by perturbing the chem. structure of the heteropolymer. Moreover, these complexes can be used as new types of spatiotemporal sensors based on modulation of the carbon nanotube photoemission in the near-IR, as we show by tracking riboflavin diffusion in murine macrophages. [on SciFinder(R)]