Search Results (38)

In this study, we examine the cooperative effect between vitamins C and E that mitigates oxidative stress by using experimental and computational methods. We performed superoxide scavenging experiments on each vitamin individually and their combination using rotating ring–disk electrode voltammetry. The results indicate that vitamins E and C together produce more effective scavenging of superoxide as evaluated by a steeper slope in the efficiency graph, −7.2 × 10⁴, compared to that of vitamin E alone, −1.8 × 10³, or vitamin C alone, −1.3 × 10⁴. Density Functional Theory calculations agree with our experimental results, and we describe a mechanism for the antioxidant action of individual vitamins E and C, plus the synergistic action when both vitamins interact. This process involves the restoration of vitamin E by vitamin C and includes π-π interactions between superoxide and scavengers. The overall result produces an increase in scavenging superoxide radicals when both vitamins act together. Full article

The development of efficient and low-cost non-metallic catalysts is of great significance for the oxygen reduction reaction (ORR) in fuel cells. Heteroatom-doped carbon-based catalysts are one of the popular candidates, although their preparation method is still under exploration. In this work, single (CS)-, double (NCS)-, and triple (NBCS)-heteroatom-doped carbon-based catalysts were successfully prepared by a “cook-off” process. The morphology, elemental composition, and bonding structure of the catalysts were investigated by SEM, TEM, Raman spectra, BET, and XPS. ORR catalytic performance measurements suggested an activity trend of CS < NCS < NBCS, and NBCS demonstrated better methanol resistance and slightly higher stability than the commercial Pt/C catalyst, as evaluated with both rotating disk electrode (RDE) and rotating ring-disk electrode (RRDE) systems. The mechanism for the promoted performance was also proposed based on the conductivity of the catalysts. In this paper, the heteroatoms N, B, and S were co-doped into activated carbon using a simple, fast, and efficient preparation method with high electrical conductivity and also increased active sites, showing high electrocatalytic activity and good stability. This work provides a new approach to preparing highly active non-Pt catalysts for oxygen reduction reactions. Full article

Pimpinella anisum L., or anise, is a plant that, besides its nutritional value, has been used in traditional medical practices and described in many cultures in the Mediterranean region. A possible reason for anise’s therapeutic value is that it contains coumarins, which are known to have many biomedical and antioxidant properties. HPLC analysis in our laboratory of the anise extract shows the presence of the coumarin esculetin. We used a hydrodynamic voltammetry rotating ring–disk electrode (RRDE) method to measure the superoxide scavenging abilities of anise seeds and esculetin, which has marked scavenging activity. A related coumarin, 4-methyl-esculetin, also showed strong antioxidant activity as measured by RRDE. Moreover, this study includes the X-ray crystal structure of esculetin and 4-methyl-esculetin, which reveal the H-bond and the stacking intermolecular interactions of the two coumarins. Coordinates of esculetin crystal structure were used to perform a DFT study to arrive at the mechanism of superoxide scavenging. Besides performing a H(hydroxyl) abstraction in esculetin position 6 by superoxide, the scavenging also includes the presence of a second superoxide radical in a π–π approach. Both rings of esculetin were explored for this attack, but only the pyrone ring was effective. As a result, one product of esculetin scavenging is H₂O₂ formation, while the second superoxide remains π–π trapped within the pyrone ring to form an esculetin-η-O₂ complex. Comparison with other coumarins shows that subtle structural differences in the coumarin framework can imply marked differences in scavenging. For instance, when the catechol moiety of esculetin (position 6,7) is shifted to position 7,8 in 4-methyl-7,8-dihydroxy coumarin, that coumarin shows a superoxide dismutase action, which, beside H₂O₂ formation, includes the formation and elimination of a molecule of O₂. This is in contrast with the products formed through esculetin superoxide scavenging, where a second added superoxide remains trapped, and forms an esculetin-η-O₂ complex. Full article

Water oxidation is a multielectron complex reaction that produces molecular oxygen as the final product. The article addresses the lack of confirmation of oxygen product formation in electrochemical oxygen evolution reaction (OER) studies, despite the extensive research conducted on catalysts for water splitting. It critically evaluates the trend observed in many studies that solely rely on electrochemical methods for OER quantification without confirming the oxygen product via complementary analytical techniques. The omission of measuring evolved oxygen gas leaves a crucial gap in the quantification of the OER process and raises concerns about the validity and accuracy of reported results. Analytical techniques, such as gas chromatography, Rotating Ring-Disk Electrode (RRDE), fluorescence oxygen probes, Clark electrode, and volumetry are critically analyzed and described to ensure the reliability and credibility of voltammetry and bulk electrolysis to provide a more accurate assessment of the OER process. Full article

The neem tree, Azadirachta indica, belongs to the Meliaceae family, and its use in the treatment of medical disorders from ancient times to the present in the traditional medical practices of Asia, Africa and the Middle East is well-documented. Neem oil, extracted from the seeds of the fruit, is widely used, with promising medicinal benefits. Azadiradione, a principal antioxidant component of the seeds of A. indica, is known to reduce oxidative stress and has anti-inflammatory effects. To directly measure the antioxidant ability of neem oil, we used Rotating Ring Disk Electrode (RRDE) hydrodynamic voltammetry to quantify how it can scavenge superoxide radical anions. The results of these experiments show that neem oil is approximately 26 times stronger than other natural products, such as olive oil, propolis and black seed oil, which were previously measured using this method. Next, computational Density Functional Theory (DFT) methods were used to arrive at a mechanism for the scavenging of superoxide radical anions with azadiradione. Our work indicates that azadiradione is an effective antioxidant and, according to our DFT study, its scavenging of the superoxide radical anion occurs through a reaction mechanism in which azadiradione mimics the antioxidant action of superoxide dismutase (SOD). In this mechanism, analogous to the SOD enzymatic reaction, azadiradione is regenerated, along with the production of two products: hydrogen peroxide and molecular oxygen. This antioxidant process provides an explanation for azadiradione’s more general and protective biochemical effects. Full article

The relationship between oxidative stress and inflammation is well known, and exogenous antioxidants, primarily phytochemical natural products, may assist the body’s endogenous defense systems in preventing diseases due to excessive inflammation. In this study, we evaluated the antioxidant properties of ethnomedicines from Peru that exhibit anti-inflammatory activity by measuring the superoxide scavenging activity of ethanol extracts of Maytenus octogona aerial parts using hydrodynamic voltammetry at a rotating ring-disk electrode (RRDE). The chemical compositions of these extracts are known and the interactions of three methide-quinone compounds found in Maytenus octogona with caspase-1 were analyzed using computational docking studies. Caspase-1 is a critical enzyme triggered during the activation of the inflammasome and its actions are associated with excessive release of cytokines. The most important amino acid involved in active site caspase-1 inhibition is Arg341 and, through docking calculations, we see that this amino acid is stabilized by interactions with the three potential methide-quinone Maytenus octogona inhibitors, hydroxytingenone, tingenone, and pristimerin. These findings were also confirmed after more rigorous molecular dynamics calculations. It is worth noting that, in these three compounds, the methide-quinone carbonyl oxygen is the preferred hydrogen bond acceptor site, although tingenone’s other carbonyl group also shows a similar binding energy preference. The results of these calculations and cyclovoltammetry studies support the effectiveness and use of anti-inflammatory ethnopharmacological ethanol extract of Maytenus octogona (L’Héritier) DC. Full article

Black cumin seeds and seed oil have long been used in traditional foods and medicine in South Asian, Middle Eastern and Mediterranean countries and are valuable flavor ingredients. An important ingredient of black cumin is the small molecule thymoquinone (TQ), which manifests low toxicity and potential therapeutic activity against a wide number of diseases including diabetes, cancer and neurodegenerative disorders. In this study, the antioxidant activities of black seed oil, TQ and a related molecule found in black cumin, thymohydroquinone (THQ), were measured using a direct electrochemical method to experimentally evaluate their superoxide scavenging action. TQ and the black seed oil showed good superoxide scavenging ability, while THQ did not. Density Functional Theory (DFT) computational methods were applied to arrive at a chemical mechanism describing these results, and confirmed the experimental Rotating Ring Disk Electrode (RRDE) findings that superoxide oxidation to O₂ by TQ is feasible, in contrast with THQ, which does not scavenge superoxide. Additionally, a thorough inquiry into the unusual cyclic voltammetry pattern exhibited by TQ was studied and was associated with formation of a 1:1 TQ-superoxide radical species, [TQ-O₂]⁻•. DFT calculations reveal this radical species to be involved in the π-π mechanism describing TQ reactivity with superoxide. The crystal structures of TQ and THQ were analyzed, and the experimental data reveal the presence of stacking intermolecular interactions that can be associated with formation of the radical species, [TQ-O₂]⁻•. All three of these methods were essential for us to arrive at a chemical mechanism that explains TQ antioxidant activity, that incorporates intermolecular features found in the crystal structure and which correlates with the measured superoxide scavenging activity. Full article

Isoflavones are plant-derived natural products commonly found in legumes that show a large spectrum of biomedical activities. A common antidiabetic remedy in traditional Chinese medicine, Astragalus trimestris L. contains the isoflavone formononetin (FMNT). Literature reports show that FMNT can increase insulin sensitivity and potentially target the peroxisome proliferator-activated receptor gamma, PPARγ, as a partial agonist. PPARγ is highly relevant for diabetes control and plays a major role in Type 2 diabetes mellitus development. In this study, we evaluate the biological role of FMNT, and three related isoflavones, genistein, daidzein and biochanin A, using several computational and experimental procedures. Our results reveal the FMNT X-ray crystal structure has strong intermolecular hydrogen bonding and stacking interactions which are useful for antioxidant action. Cyclovoltammetry rotating ring disk electrode (RRDE) measurements show that all four isoflavones behave in a similar manner when scavenging the superoxide radical. DFT calculations conclude that antioxidant activity is based on the familiar superoxide σ-scavenging mode involving hydrogen capture of ring-A H7(hydroxyl) as well as the π–π (polyphenol–superoxide) scavenging activity. These results suggest the possibility of their mimicking superoxide dismutase (SOD) action and help explain the ability of natural polyphenols to assist in lowering superoxide concentrations. The SOD metalloenzymes all dismutate O₂^•− to H₂O₂ plus O₂ through metal ion redox chemistry whereas these polyphenolic compounds do so through suitable hydrogen bonding and stacking intermolecular interactions. Additionally, docking calculations suggest FMNT can be a partial agonist of the PPARγ domain. Overall, our work confirms the efficacy in combining multidisciplinary approaches to provide insight into the mechanism of action of small molecule polyphenol antioxidants. Our findings promote the further exploration of other natural products, including those known to be effective in traditional Chinese medicine for potential drug design in diabetes research. Full article

Sluggish oxygen reduction reaction (ORR) of electrodes is one of the main challenges in fuel cell systems. This study explored the kinetics of the ORR reaction mechanism, which enables us to understand clearly the electrochemical activity of the electrode. In this research, electrocatalysts were synthesized from platinum (Pt) catalyst with multi-walled carbon nanotubes (MWCNTs) coated by three polymers (polybenzimidazole (PBI), sulfonated tetrafluoroethylene (Nafion), and polytetrafluoroethylene (PTFE)) as the supporting materials by the polyol method while hexachloroplatinic acid (H₂PtCl₆) was used as a catalyst precursor. The oxygen reduction current of the synthesized electrocatalysts increased that endorsed by linear sweep voltammetry (LSV) curves while increasing the rotation rates of the disk electrode. Additionally, MWCNT-PBI-Pt was attributed to the maximum oxygen reduction current densities at −1.45 mA/cm² while the minimum oxygen reduction current densities of MWCNT-Pt were obtained at −0.96 mAcm². However, the ring current densities increased steadily from potential 0.6 V to 0.0 V due to their encounter with the hydrogen peroxide species generated by the oxygen reduction reactions. The kinetic limiting current densities (J_K) increased gradually with the applied potential from 1.0 V to 0.0 V. It recommends that the ORR consists of a single step that refers to the first-order reaction. In addition, modified MWCNT-supported Pt electrocatalysts exhibited high electrochemically active surface areas (ECSA) at 24.31 m²/g of MWCNT-PBI-Pt, 22.48 m²/g of MWCNT-Nafion-Pt, and 20.85 m²/g of MWCNT-PTFE-Pt, compared to pristine MWCNT-Pt (17.66 m²/g). Therefore, it can be concluded that the additional ionomer phase conducting the ionic species to oxygen reduction in the catalyst layer could be favorable for the ORR reaction. Full article

Bimetallic catalysts containing platinum and transition metals (PtM, M = Mo, Ni, CoCr) were synthesized on carbon nanotubes (CNTs) functionalized in an alkaline medium. Their platinum content is 10–15% by mass. PtM/CNT_NaOH are active in both the hydrogen oxidation reaction (HOR) and the oxygen reduction reaction (ORR) in alkaline electrolytes. Although catalysts based on a single transition metal are inactive in the HOR, their activity in the cathode process of ORR increases relative to CNT_NaOH. When using the rotating ring-disk electrode method for ORR, PtM/CNT showed a high selectivity in reducing oxygen directly to water. In HOR, the PtM/CNT catalyst had an activity comparable to that of a commercial monoplatinum catalyst. The results obtained show that it is possible to use the PtM/CNT catalyst in an alkaline fuel cell both as an anode and as a cathode. Full article

We measured the ring collection coefficient of bromide anion oxidation products in a neutral and slightly alkaline medium on a rotating ring-disk electrode (glassy carbon disk, platinum ring) varying the following parameters: disk electrode rotation velocity, sodium bromide concentration, pH of the medium (in the range of 6–12), anode current on the disk, and the electroreduction potential of the bromide anion oxidation products on the ring. The data obtained are presented via dependences of the cathode ring current on the disk current ratio vs. the ring electrode potential. The analysis of the results was carried out by comparing the experimental polarization curves of the ring electrode with the data of cyclic voltammetry in model solutions to determine the electrical activities of various bromine compounds in positive oxidation states. We claim that the RRDE method could be used to obtain quantitative and qualitative data on the electrooxidation of bromide ions in neutral and alkaline solutions. For the most effective regeneration of the spent oxidizer, the values of pH > 10 and moderate concentrations of NaBr should be used. Full article

Detailed studies of the electrochemical oxygen reduction reaction (ORR) on catalyst materials are crucial to improving the performance of different electrochemical energy conversion and storage systems (e.g., fuel cells and batteries), as well as numerous chemical synthesis processes. In the effort to reduce the loading of expensive platinum group metal (PGM)-based catalysts for ORR in the electrochemical systems, many carbon-based catalysts have already shown promising results and numerous investigations on those catalysts are in progress. Most of these studies show the catalyst materials’ ORR performance as current density data obtained through the rotating disk electrode (RDE), rotating ring-disk electrode (RRDE) experiments taking cyclic voltammograms (CV) or linear sweep voltammograms (LSV) approaches. However, the provided descriptions or interpretations of those data curves are often ambiguous and recondite which can lead to an erroneous understanding of the ORR phenomenon in those specific systems and inaccurate characterization of the catalyst materials. In this paper, we presented a study of ORR on a newly developed carbon-based catalyst, the nitrogen-doped graphene/metal-organic framework (N-G/MOF), through RDE and RRDE experiments in both alkaline and acidic mediums, taking the LSV approach. The functions and crucial considerations for the different parts of the RDE/RRDE experiment such as the working electrode, reference electrode, counter electrode, electrolyte, and overall RDE/RRDE process are delineated which can serve as guidelines for the new researchers in this field. Experimentally obtained LSV curves’ shapes and their correlations with the possible ORR reaction pathways within the applied potential range are discussed in depth. We also demonstrated how the presence of hydrogen peroxide (H₂O₂), a possible intermediate of ORR, in the alkaline electrolyte and the concentration of acid in the acidic electrolyte can maneuver the ORR current density output in compliance with the possible ORR pathways. Full article

This work focuses on the development of an electrocatalytic material by annealing a composite of a transition metal coordination material, iron hexacyanoferrate (Prussian blue) immobilized on carboxylic-acid-functionalized reduced graphene oxide. Pyrolysis at 500 °C under a nitrogen atmosphere formed nanoporous core–shell structures with efficient activity, which mostly included iron carbide species capable of participating in the oxygen reduction reaction in alkaline media. The physicochemical properties of the iron-based catalyst were elucidated using transmission electron microscopy, X-ray diffraction, Mössbauer spectroscopy, and various electrochemical techniques, such as cyclic voltammetry and rotating ring–disk electrode (RRDE) voltammetry. To improve the electroreduction of oxygen over the studied catalytic material, an external magnetic field was utilized, which positively shifted the potential by ca. 20 mV. The formation of undesirable intermediate peroxide species was decreased compared with the ORR measurements without an external magnetic field. Full article

Hydrogen peroxide (H₂O₂) is a key chemical for many industrial applications, yet it is primarily produced by the energy-intensive anthraquinone process. As part of the Power-to-X scenario of electrosynthesis, the controlled oxygen reduction reaction (ORR) can enable the decentralized and renewable production of H₂O₂. We have previously demonstrated that self-supported electrocatalytic materials derived from polyaniline by chemical oxidative polymerization have shown promising activity for the reduction of H₂O to H₂ in alkaline media. Herein, we interrogate whether such materials could also catalyze the electro-conversion of O₂-to-H₂O₂ in an alkaline medium by means of a selective two-electron pathway of ORR. To probe such a hypothesis, nine sets of polyaniline-based materials were synthesized by controlling the polymerization of aniline in the presence or not of nickel (+II) and cobalt (+II), which was followed by thermal treatment under air and inert gas. The selectivity and faradaic efficiency were evaluated by complementary electroanalytical methods of rotating ring-disk electrode (RRDE) and electrolysis combined with spectrophotometry. It was found that the presence of cobalt species inhibits the performance. The selectivity towards H₂O₂ was 65–80% for polyaniline and nickel-modified polyaniline. The production rate was 974 ± 83, 1057 ± 64 and 1042 ± 74 µmol_H2O2 h⁻¹ for calcined polyaniline, calcined nickel-modified polyaniline and Vulcan XC 72R (state-of-the-art electrocatalyst), respectively, which corresponds to 487 ± 42, 529 ± 32 and 521 ± 37 mol kg⁻¹_cat h⁻¹ (122 ± 10, 132 ± 8 and 130 ± 9 mol kg⁻¹_cat cm⁻²) for faradaic efficiencies of 58–78%. Full article

The high activity of non-platinum electrocatalysts for oxygen reduction reaction (ORR) in alkaline media is necessary for applications in energy conversion devices such as fuel cells and metal-air batteries. Herein, we present the electrocatalytic activity of TaO_x/carbon black (CB) nanoparticles for the ORR in an alkaline atmosphere as well as in an acidic electrolyte. Ultrafine TaO_x nanoparticles 1–2 nm in size and uniformly dispersed on CB supports were prepared by potentiostatic electrodeposition in a nonaqueous electrolyte and subsequent annealing treatment in an H₂ flow. The TaO_x/CB nanoparticles largely catalyzed the ORR with an onset potential of 1.03 V_RHE in an O₂-saturated 0.1 M KOH solution comparable to that of a commercial Pt/CB catalyst. ORR activity was also observed in 0.1 M H₂SO₄ solution. According to the rotating ring disk electrode measurement results, the oxide nanoparticles partly produced H₂O₂ during the ORR in 0.1 M KOH, and the ORR process was dominated by both the two- and four-electron reductions of oxygen in a diffusion-limited potential region. The Tafel slope of −120 mV dec⁻¹ in low and high current densities revealed the surface stability of the oxide nanoparticles during the ORR. Therefore, these results demonstrated that the TaO_x/CB nanoparticles were electroactive for the ORR in both acidic and alkaline electrolytes. Full article