Sensitive Detection of Carcinoembryonic Antigen Using Stability-Limited Few-Layer Black Phosphorus as an Electron Donor and a Reservoir.

The instability of few-layer black phosphorus (FL-BP) hampers its further applications. Here, it can be demonstrated that the instability of FL-BP can also be the advantage for application in biosensor. First, gold nanoparticle/FL-BP (BP-Au) hybrid is facilely synthesized by mixing Au precursor with FL-BP. BP-Au shows outstanding catalytic activity (K = 1120 s-1 g-1 ) and low activation energy (17.53 kJ mol-1 ) for reducing 4-nitrophenol, which is attributed to the electron-reservoir and electron-donor properties of FL-BP, and synergistic interaction of Au nanoparticles and FL-BP. Oxidation of FL-BP after catalytic reaction is further confirmed by transmission electron microscope, X-ray photoelectron spectroscopy, and zeta potentials. Second, the catalytic activity of BP-Au can be reversibly switched from "inactive" to "active" upon treatment with antibody and antigen in solution, thus providing a versatile platform for label-free colorimetric detection of biomarkers. The sensor shows a wide detection range (1 pg mL-1 to -10 µg mL-1 ), high sensitivity (0.20 pg mL-1 ), and selectivity for detecting carcinoembryonic antigen (CEA). Finally, the biosensor has been used to detect CEA in colon and breast cancer clinical samples with satisfactory results. Therefore, the instability of BP can also be the advantage for application in detecting cancer biomarker in clinic.