Electrical Wiring of Malarial Parasite Intermediate Hematin on a Tailored N-Doped Carbon Nanomaterial Surface and Its Bioelectrocatalytic Hydrogen Peroxide Reduction and Sensing.

Hematin, an iron-containing porphyrin compound, plays a crucial role in various biological processes, including oxygen transport, storage, and functionality of the malarial parasite. Specifically, hematin-Fe interacts with the nitrogen atom of antimalarial drugs, forming an intermediate step crucial for their function. The electron transfer functionality of hematin in biological systems has been scarcely investigated. In this study, we developed a biomimicking electrical wiring of hematin-Fe with a model N-drug system, represented as {hematin-Fe---N-drug}. We achieved this by immobilizing hematin on a multiwalled carbon nanotube (MWCNT)/N-graphene quantum dot (N-GQD) modified electrode (MWCNT/N-GQD@Hemat). N-GQD serves as a model molecular drug system containing nitrogen atoms to mimic the {hematin-Fe---N-drug} interaction. The prepared bioelectrode exhibited a distinct redox peak at a measured potential (E _1/2 ) of -0.410 V vs Ag/AgCl, accompanied by a surface excess value of 3.54 × 10 ^-9 mol cm ^-2 . This observation contrasts significantly with the weak or electroinactive electrochemical responses documented in literature-based hematin systems. We performed a comprehensive set of physicochemical and electrochemical characterizations on the MWCNT/N-GQD@Hemat system, employing techniques including FESEM, TEM, Raman spectroscopy, IR spectroscopy, and AFM. To evaluate the biomimetic electrode's electroactivity, we investigated the selective-mediated reduction of H ₂ O ₂ as a model system. As an important aspect of our research, we demonstrated the use of scanning electrochemical microscopy to visualize the in situ electron transfer reaction of the biomimicking electrode. In an independent study, we showed enzyme-less electrocatalytic reduction and selective electrocatalytic sensing of H ₂ O ₂ with a detection limit of 319 nM. We achieved this using a batch injection analysis-coupled disposable screen-printed electrode system in physiological solution.