Carbon-dots-referenced metal-organic frameworks for chemical sensing of tumor/mood biomarker 5-hydroxyindoleacetic acid in human urine: Covalent grafting blue-emitting carbon dots onto red-emitting MOF

Abstract

5-HIAA (5-hydroxyindoleacetic acid) is a metabolite for 5-hydroxytryptamine which is excreted in urine and reflects human homeostatic sate. Thus, its monitoring is of great important for clinical diagnosis. In this work, blue-emitting carbon dots (BCD) were firstly synthesize and then covalently grafted onto red-emitting MOF (EuBTC), resulting in a composite sensing platform (BCD@EuBTC) with two emission bands (blue emission peaking at 441 nm and red emission peaking at 616 nm). This composite structure was characterized by means of XRD, IR, TGA, N2 adsorption/desorption, and SEM/TEM. It was found that BCD was grafted on EuBTC surface, not loaded in its micropores, with doping level of 5.02 wt%. 5-HIAA replaced and released the BCD in BCD@EuBTC. The released BCD showed strong blue emission. In the meanwhile, EuBTC red emission was quenched by 5-HIAA thermal relaxation. As a consequence, a ratiometric sensing signal was observed for 5-HIAA. A linear working calibration curve was fitted as F/F0 = 0.588 + 1.598*[5-HIAA], R2 = 0.999, with detection of limit (LOD) determined as 0.3 μM, working region of 0.3–70 μM, and good selectivity. The practical sensing performance of BCD@EuBTC for 5-HIAA in human urine was confirmed, with recovery of 103%.