Calcium-cation-doped polydopamine-modified 2D black phosphorus nanosheets as a robust platform for sensitive and specific biomolecule sensing.

Many polymer decorated/modified 2D nanomaterials have been developed as enhanced drug delivery systems and photothermal theranostic nanoagents. However, few reports describe the use of these novel nanomaterials as nanoplatforms for biomolecule sensing. Herein, we used calcium-cation-doped polydopamine-modified (PDA-modified) 2D black phosphorus (BP) nanosheets (BP@PDA) as a sensing nanoplatform for the detection of nucleic acids and proteins in complex biological samples. Fluorescent-dye-labeled single-strand DNA aptamer/probes are adsorbed by the Ca-doped BP@PDA mediated by calcium-cation coordination. The PDA coating enhances the stability of the inner BP, provides binding sites to DNA nucleobases, and quenches fluorescence. Without any chemical conjugation, this sensing nanoplatform selectively and specifically detects protein (human thrombin, linear range: 10-25 nM, detection limit: 0.02 nM), single-strand DNA (linear range: 1-10 nM, detection limit: 0.52 nM) in 1% serum diluted samples, and senses intracellular mRNAs (C-myc, and actin) in living cells. The nanoplatform exhibits the advantages of both the 2D nanomaterial (BP) and the coating polymer (PDA), naturally enters living cells unaided by transfection agents, resists enzymatic lysis and shows high biocompatibility. This nanoplatform design contributes towards future biomolecule analytical method development based on polymer decorated/modified 2D nanomaterials.