A three-dimensional CoNi-MOF nanosheet array-based immunosensor for sensitive monitoring of human chorionic gonadotropin with core-shell ZnNi-MOF@Nile Blue nanotags

A CoNi-based metal-organic framework (CoNi-MOF) nanosheet array is synthesized by the treatment of a CoNi layered double hydroxide nanosheet array on Ni foam with 3,5-diaminobenzoic acid. The CoNi-MOF nanosheet array with amino and carboxyl groups can be used to capture the human chorionic gonadotropin (HCG) primary antibody (HCG Ab1). Nile Blue decorated ZnNi-MOF (NB@ZnNi-MOF) spheres immobilized with HCG secondary antibodies (HCG Ab2) are used for signal amplification. When HCG exists in an analytical sample, a sandwich structure is formed and an electrochemical signal is produced. The analytical signal generated during the detection is caused by the conversion of Co( ii ) and Co( iii ) in the CoNi-MOF nanosheet array. The Nile Blue of the NB@ZnNi-MOF sphere, as a kind of redox-active species, is responsible for the electrochemical signal amplification in the immunosensor. On the basis of the above advantages, the HCG immunosensor exhibits a lower limit of detection (1.85 × 10 −3 mIU mL −1 ) and a wide linear range from 0.005 mIU mL −1 to 250 mIU mL −1 . Additionally, this immunosensor is used to quantitatively detect HCG in human blood serum and shows good correlations with the standard enzyme-linked immunosorbent assay (ELISA), providing a high value on clinical diagnosis. A sandwich-type electrochemical immunosensor for HCG detection based on a CoNi-MOF nanosheet-array and Nile Blue@ZnNi-MOF spheres is successfully exploited.