A pre-oxidized Eu-probe doped into bio-MOF-1 for ascorbic acid emission "off-on" detection in human serum

Ascorbic acid (or widely known as vitamin C, VC) is an essential antioxidant and a free radical scavenger in human body. The appeal for reliable fluorescent nanosensors always promotes the development of VC probe. In this work, a pre-oxidized Eu-probe (denoted as Eu-NO₉) was synthesized. Without VC, Eu-NO₉ was nearly non-emissive owing to the inefficient ligand energy transfer (ET) to Eu ion (caused by mismatched ligand level and long distance to Eu, as revealed by single crystal analysis and emissive parameters). By adding VC, the pre-oxidized ligand was deoxidized and its ET to Eu ion became efficient (confirmed by electrochemical analysis), with Eu(III) red emission intensity obviously increased. Then Eu-NO₉ was doped into a porous host bio-MOF-1 for ascorbic acid detection (denoted as Eu-NO₉@MOF). The molecular sieving effect of bio-MOF-1 improved sensing selectivity, and bio-MOF-1 blue emission (421 nm) was applied as a reference for Eu(III) red emission. Linear working curves were obtained within a wide working region of 0-100 μM, with LOD of 1.7 μM. A short response time of 192 s at 25 °C was confirmed. Practical sensing plates were prepared and found applicable for VC detection in fresh human serum. The advantage of this work was the combination of a pre-oxidized probe and a porous host which gave emission "turn on" fluorescence sensing for VC with good selectivity, linear calibration curve and wide working region.