Construction of Electrochemical and Photoelectrochemical Sensing Platform Based on Porphyrinic Metal-Organic Frameworks for Determination of Ascorbic Acid

Highly sensitive and specific detection of biomolecular markers is of great importance to the diagnosis and treatment of related diseases. Herein, Cu-TCPP@MOFs thin films were synthesized with tetrakis(4-carboxyphenyl) porphyrin (H2TCPP) as organic ligands and copper ions as metal nodes. The as-synthesized Cu-TCPP@MOFs thin films as electrode modifiers were used to modify the pre-treated glassy carbon electrode (GCE) and the electrochemical performances of Cu-TCPP@MOFs/GCE were evaluated by electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). Furthermore, as the working electrode, the constructed Cu-TCPP@MOFs/GCE was used for the investigation of ascorbic acid (AA) due to its outstanding electrocatalytic activities towards AA by several electrochemical methods, including cyclic voltammetry (CV), differential pulse voltammetry (DPV), and chronoamperometry (CA). The well-linear relationship was established based on different AA concentration ranges and the ideal detection limits (LOD) were obtained in the above-mentioned electrochemical methods, respectively. Furthermore, a Cu-TCPP MOFs@GCE sensing platform was used as a photoelectrochemical (PEC) sensor to quantitatively detect AA based on the strong absorption properties of Cu-TCPP ingredients in Cu-TCPP MOFs in a visible light band of 400~700 nm. PEC sensing platform based on Cu-TCPP@MOFs exhibited a more extensive linear concentration range, more ideal detection limit, and better sensitivity relative than the other electrochemical methods for AA. The well linear regression equations were established between the peak current intensity and AA concentrations in different electrochemical technologies, including CV, DPV, and CA, and PEC technology. AA concentration ranges applicable to various electrochemical equations were as follows: 0.45~2.10 mM of CV, 0.75~2.025 mM of DPV, 0.3~2.4 mM of CA, 7.5~480 μM of PEC, and the corresponding detection limits for AA were 1.08 μM (S/N = 3), 0.14 μM (S/N = 3), 0.049 μM (S/N = 3), and 0.084 nA/μM. Moreover, the proposed Cu-TCPP MOFs@GCE electrochemical and photoelectrochemical sensing platform was applied to determine the AA concentration of a real human serum sample; the results reveal that Cu-TCPP MOFs@GCE sensing platform could accurately determine the concentration of AA of the human serum under other potential interferences contained in the human serum samples.