Fabrication of Cu-hemin metal-organic-frameworks nanoflower supported on three-dimensional reduced graphene oxide for the amperometric detection of H₂O₂

A novel electrochemical sensor based on Cu-hemin metal-organic-frameworks nanoflower/three-dimensional reduced graphene oxide (Cu-hemin MOFs/3D-RGO) was constructed to detect H₂O₂ released from living cells. The nanocomposite was synthesized via a facile co-precipitation method using hemin as the ligand, then decorated with 3D-RGO. The prepared Cu-hemin MOFs showed a 3D hollow spherical flower-like structure with a large specific surface area and mesoporous properties, which could load more biomolecules and greatly enhance the stability by protecting the activity of hemin. In addition, the introduction of 3D-RGO effectively enhanced the conductivity of Cu-hemin MOFs. Thus, the proposed sensor (Cu-hemin MOFs/3D-RGO/GCE) showed excellent electrochemical performances towards H₂O₂ with a wide linear range (10–24,400 μM), high sensitivity (207.34 μA mM⁻¹ cm⁻²), low LOD (0.14 μM), and rapid response time (less than 3 s). Most importantly, we prepared a Cu-hemin MOFs/3D-RGO/ITO electrode with cells growing on it. Compared with detecting H₂O₂ in cell suspension by GCE-based electrode, adhesion of cells on ITO could shorten the diffusion distance of H₂O₂ from solution to the surface of the electrode and achieve in situ and a real-time monitor of H₂O₂ released by living cells. This self-supported sensing electrode showed great potential applications in monitoring the pathological and physiological dynamics of cancer cells. Graphical abstract: