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 (E1/2) 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 H2O2 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 H2O2 with a detection limit of 319 nM. We achieved this using a batch injection analysis-coupled disposable screen-printed electrode system in physiological solution.

Edge and Basal Plane Anisotropy of a Preanodized Pencil Graphite Electrode Surface Revealed Using Scanning Electrochemical Microscopy and Electrocatalytic Dopamine Oxidation as a Molecular Probe.

Pencil graphite (PGE), an ultralow-cost and ready-to-use disposable-type electrode, has been used for various electrochemical and electroanalytical applications after its surface anodization (PGE*, * means preanodized surface). Indeed, systematic studies on mechanistic and surface features of PGE* have not yet been explored. Herein, we report anodized pencil graphite as a model system to study molecular level insights into the surface using a scanning electrochemical microscopy (SECM) technique and dopamine (DA) electrocatalytic oxidation reaction as a molecular probe. The as-prepared PGE* showed an appreciable electronic conductivity similar to the edge-plane graphitic sites (EPPG) of the highly pyrolytic graphitic electrode (HOPG) but without any surface deterioration that occurs with HOPG due to the instability of the EPPG. Physicochemical characterizations by FESEM, FTIR, Raman, and XPS techniques revealed a flake-like exfoliated PGE* surface with higher contents of carbon-oxygen especially phenolic/alcoholic functional groups than the PGE surface. Based on the chronocoulometric experiment, the number of functional groups formed on the PGE* was calculated as 10.9 × 10-10 mol cm-2. An independent SECM technique using ferricyanide as a redox probe showed the existence of a heterogeneous surface and exhibited an improved electron transfer activity due to the flake-like graphitic island on the PGE* surface. Investigated DA electrochemical oxidation on PGE* yielded about three times enhancement in the peak current signal and about 200 mV reduction in the oxidation potential over the PGE without any serious surface fouling feature that is related to the intermediate polydopamine formation on the basal-plane graphitic surface of the underlying electrode. As an independent electroanalytical study, a prototype electrochemical sensor using PGE* as a working electrode for instant detection of DA-containing pharmaceutical samples in a 1 mL Eppendorf vial has been demonstrated.

Surface-Activated Pencil Graphite Electrode for Dopamine Sensor Applications: A Critical Review.

Pencil graphite electrode (PGE) is an alternative, commercially available, ready-to-use, screen-printed electrode for a wide range of electroanalytical applications. Due to the complex-matrix composition and unpredictable electro-inactive nature of PGE in its native form, a surface pre-treatment/activation procedure is highly preferred for using it as an electroactive working electrode for electroanalytical applications. In this article, we review various surface pre-treatment and modification procedures adopted in the literature with respect to the sensitive and selective detection of dopamine as a model system. Specific generation of the carbon-oxygen functional group, along with partial surface exfoliation of PGE, has been referred to as a key step for the activation. Based on the Scopus® index, the literature collection was searched with the keywords "pencil and dopamine". The obtained data were segregated into three main headings as: (i) electrochemically pre-treated PGE; (ii) polymer-modified PGEs; and (iii) metal and metal nanocomposite-modified PGE. This critical review covers various surface activation procedures adopted for the activation for PGE suitable for dopamine electroanalytical application.

A prototype device of microliter volume voltammetric pH sensor based on carbazole-quinone redox-probe tethered MWCNT modified three-in-one screen-printed electrode.

As an alternate for the conventional glass-based pH sensor which is associated with problems like fragile nature, alkaline error, and potential drift, the development of a new redox-sensitive pH probe-modified electrode that could show potential, current-drift and surface-fouling free voltammetric pH sensing is a demanding research interest, recently. Herein, we report a substituted carbazole-quinone (Car-HQ) based new redox-active pH-sensitive probe that contains benzyl and bromo-substituents, immobilized multiwalled carbon nanotube modified glassy carbon (GCE/MWCNT@Car-HQ) and screen-printed three-in-one (SPE/MWCNT@Car-HQ) electrodes for selective, surface-fouling free pH sensor application. This new system showed a well-defined surface-confined redox peak at an apparent standard electrode potential, Eo' = - 0.160 V versus Ag/AgCl with surface-excess value, Γ = 47 n mol cm-2 in pH 7 phosphate buffer solution. When tested with various electroactive chemicals and biochemicals such as cysteine, hydrazine, NADH, uric acid, and ascorbic acid, MWCNT@Car-HQ showed an unaltered redox-peak potential and current values without mediated oxidation/reduction behavior unlike the conventional hydroquinone, anthraquinone and other redox mediators based voltammetry sensors with serious electrocatalytic effects and in turn potential and current drifts. A strong π-π interaction, nitrogen-atom assisted surface orientation and C-C bond formation on the graphitic structure of MWCNT are the plausible reasons for stable and selective voltammetric pH sensing application of MWCNT@Car-HQ system. Using a programed/in-built three-in-one screen printed compatible potentiostat system, voltammetric pH sensing of 3 µL sample of urine, saliva, and orange juice samples with pH values comparable to that of milliliter volume-based pH-glass electrode measurements has been demonstrated.