Electrochemical detection of glycoproteins using boronic acid-modified metal–organic frameworks as dual-functional signal reporters

The sensitive analysis of glycoproteins is of great importance for early diagnosis and prognosis of diseases. In this work, a sandwich-type electrochemical aptasensor was developed for the detection of glycoproteins using 4-formylphenylboric acid (FPBA)-modified Cu-based metal-organic frameworks (FPBA-Cu-MOFs) as dual-functional signal probes. The target captured by the aptamer-modified electrode allowed the attachment of FPBA-Cu-MOFs based on the interaction between boronic acid and glycan on glycoproteins. Large numbers of Cu²⁺ ions in FPBA-Cu-MOFs produced an amplified signal for the direct voltammetric detection of glycoproteins. The electrochemical aptasensor showed a detection limit as low as 6.5 pg mL^-1 for prostate specific antigen detection. The method obviates the use of antibody and enzymes for molecular recognition and signal output. The dual-functional MOFs can be extended to the design of other biosensors for the determination of diol-containing biomolecules in clinical diagnosis.