CDs-MnO₂-TPPS Ternary System for Ratiometric Fluorescence Detection of Ascorbic Acid and Alkaline Phosphatase

Manganese dioxide (MnO₂) nanosheet-based fluorescence sensors often use oxidase-like activity or wide absorption spectrum for detection of antioxidants. In those strategies, MnO₂ nanosheets were reduced to Mn²⁺ by antioxidants. However, few strategies emphasize the role of Mn²⁺ obtained from MnO₂ reduction in the design of the fluorescence sensor. Herein, we expanded the application of a MnO₂ nanosheet-based fluorescence sensor by involving Mn²⁺ in the detection process using ascorbic acid (AA) as a model target. In this strategy, carbon dots (CDs), MnO₂ nanosheets, and tetraphenylporphyrin tetrasulfonic acid (TPPS) comprise a ternary system for ratiometric fluorescence detection of AA. Initially, CDs were quenched by MnO₂ nanosheets based on the inner filter effect, while TPPS maintained its fluorescence intensity. After the addition of AA, MnO₂ nanosheets were reduced to Mn²⁺ so that the fluorescence intensity of CDs was recovered and TTPS was quenched by coordination with Mn²⁺. Overall, AA triggered an emission intensity increase at 440 nm for CDs and a decrease at 640 nm for TPPS. The ratio intensity of CDs to TPPS (F ₄₄₀/F ₆₄₀) showed a good linear relationship from 0.5 to 40 μM, with a low detection limit of 0.13 μM for AA detection. By means of the alkaline phosphatase (ALP)-triggered generation of AA, this strategy can be applied for the detection of ALP in the range of 0.1-100 mU/mL, with a detection limit of 0.04 mU/mL. Furthermore, this sensor was applied to detect AA and ALP in real, complex samples with ideal recovery. This novel platform extended the application of MnO₂ nanosheet-based fluorescence sensors.