Bimetallic Cu-Zn Zeolitic Imidazolate Frameworks as Peroxidase Mimics for the Detection of Hydrogen Peroxide: Electrochemical and Spectrophotometric Evaluation.

Abstract

A copper incorporated zeolitic imidazolate framework-8 (ZIF-8) has been synthesized and demonstrated to be a potential material for a peroxidase mimic. The resultant bimetallic Cu-Zn incorporated MOF is used for the dual mode sensing of hydrogen peroxide by following electrochemical as well as spectrophotometric methods. Using 3,3',5,5'-tetramethylbenzidine (TMB) as a chromogenic substrate, spectrophotometric studies are carried out, and the steady state kinetic parameters are determined for two different concentrations of Cu incorporated ZIF-8 (viz Cu@ZIF-8-1 and Cu@ZIF-8-2). It is found that both Cu@ZIF-8-1 and Cu@ZIF-8-2 exhibit more affinity toward the TMB substrate than the horseradish peroxidase (HRP) enzyme as indicated by the low Km values obtained for the substrate. Also, as the concentration of incorporated Cu increases, Vmax values are also found to be enhanced. Electrochemically, the Cu@ZIF-8 modified glassy carbon electrode (GCE) showed a good response for peroxide detection in the concentration range from 0.5 mM to 5 mM at a working potential of -0.25 V in PBS (pH 7.0) with a limit of detection (LOD) value of 0.46 mM and a sensitivity of 20.25 μA/mM. Further, the chromogenic substrate TMB is successfully immobilized on the electrode surface and subsequently used for the peroxide detection along with Cu@ZIF-8. Here, TMB acts as a mediator and shifted the working potential to 0.1 V in acetate buffer (pH 5.0) in the concentration range from 0.5 mM to 5 mM with an LOD value of 0.499 mM and a sensitivity of 0.097 μA/mM. Interestingly, the same electrode in PBS of pH 7.0 showed a response to peroxide at a working potential of -0.1 V in the concentration range from 0.5 mM to 5 mM with an LOD value of 0.143 mM and a sensitivity of 0.33 μA/mM. Moreover, the applicability of this material for peroxide sensing is evaluated using milk samples, and the proposed material is able to recover the peroxide present in milk. Thus, the bimetallic Cu-Zn MOF can be utilized for the dual mode sensing of peroxide and can be extended for various real time applications.