CdSe/ZnS QDs and O170 Dye-Decorated Spider Silk for pH Sensing

Effective in situ pH sensing holds exciting prospects in environmental and biomedical applications, but still faces a great challenge. Until now, pH sensors with small size, high sensitivity, good stability and repeatability, great biosafety, wide detection range, and flexible structure have rarely been reported. Herein, we propose a novel dual-emission ratiometric fluorescent pH sensor by decorating ethyl cellulose (EC)-encapsulated CdSe/ZnS quantum dots (QDs) and oxazine 170 perchlorate (O170 dye) on the surface of the spider silk. When a 473 nm excitation light is coupled into the pH sensor, the evanescent wave transmitting along the surface of the spider silk will excite the CdSe/ZnS QDs and then the O170 dye based on the fluorescence resonance energy transfer (FRET) effect from the QDs; thus, the pH sensing of the surrounding liquid environment can be achieved in real time by collecting the photoluminescence (PL) spectra of the pH sensor and measuring the emission intensity ratio of the two fluorescent materials. The sensor has also demonstrated a high sensing sensitivity (0.775/pH unit) within a wide pH range of 1.92–12.11, as well as excellent reusability and reversibility, structure and time stability, biocompatibility, and biosafety. The proposed pH sensor has a potential application in an in situ monitor of water microenvironments, cellular metabolism, tumor microenvironments, etc.