Search Results (9)

The 6-electron electrochemical reduction of IO₃⁻ to I⁻ represents a breakthrough for the development of next-generation redox flow batteries, offering substantially higher energy densities for oxidizer storage. Our study reveals that on a glassy carbon (GC) electrode in acidic electrolytes, HIO₃ undergoes an autocatalyzed electrochemical reduction to I⁻. This process is mediated by the formation of a thin iodine layer on the electrode, acting as an intermediate and a catalyst. Under steady-state conditions, the iodine layer forms via a comproportionation reaction (HIO₃ + I⁻ + 5H⁺ = I_2 (s) + 3H₂O). Initially, the iodine layer is generated through the slow direct electrochemical reduction of HIO₃ on pristine GC. Once established, this layer significantly enhances the rate of iodate reduction. On voltammetry curves, it is clearly observable as a step-wise current surge to reach a plateau. The limiting current density on the GC seemingly aligns with the Levich equation, varying with the RDE rotation rate. Earlier, we demonstrated the electrochemical oxidation of I⁻ back to HIO₃ using an H₂/HIO₃ flow cell, showcasing a full cycle that underpins the feasibility of this approach for energy storage. This study advances the understanding of iodate electroreduction and underscores its role in enhancing the capacity of next-generation energy storage systems. Full article

2-Phenyl-4,4,5,5-tetramethylimidazoline-1-oxyl 3-oxide (PTIO^•), a persistent nitronyl nitroxide radical, has been used for the detection and trapping of nitric oxide, as a redox mediator for batteries, for the activity estimation of antioxidants, and so on. However, there is no report on the reactivity of PTIO^• in the presence of redox-inactive metal ions. In this study, it is demonstrated that the addition of scandium triflate, Sc(OTf)₃ (OTf = OSO₂CF₃), to an acetonitrile (MeCN) solution of PTIO^• resulted in an electron-transfer disproportionation to generate the corresponding cation (PTIO⁺) and anion (PTIO⁻), the latter of which is suggested to be stabilized by Sc³⁺ to form [(PTIO)Sc]²⁺. The decay of the absorption band at 361 nm due to PTIO^•, monitored using a stopped-flow technique, obeyed second-order kinetics. The second-order rate constant for the disproportionation, thus determined, increased with increasing the Sc(OTf)₃ concentration to reach a constant value. A drastic change in the cyclic voltammogram recorded for PTIO^• in deaerated MeCN containing 0.10 M Bu₄NClO₄ was also observed upon addition of Sc(OTf)₃, suggesting that the large positive shift of the one-electron reduction potential of PTIO^• (equivalent to the one-electron oxidation potential of PTIO⁻) in the presence of Sc(OTf)₃ may result in the disproportionation. When H₂O was added to the PTIO^•–Sc(OTf)₃ system in deaerated MeCN, PTIO^• was completely regenerated. It is suggested that the complex formation of Sc³⁺ with H₂O may weaken the interaction between PTIO⁻ and Sc³⁺, leading to electron-transfer comproportionation to regenerate PTIO^•. The reversible disproportionation of PTIO^• was also confirmed by electron paramagnetic resonance (EPR) spectroscopy. Full article

A neutral, stable radical, 2,2-diphenyl-1-picrylhydrazyl radical (DPPH^•), has been frequently used to estimate the activity of antioxidants for more than 60 years. However, the number of reports about the effect of metal ions on the reactivity of DPPH^• is quite limited. We have recently reported a unique electron-transfer disproportionation of DPPH^• to produce the DPPH cations (DPPH⁺) and anions (DPPH⁻) upon the addition of scandium triflate [Sc(OTf)₃ (OTf = OSO₂CF₃)] to an acetonitrile (MeCN) solution of DPPH^•. The driving force of this reaction is suggested to be an interaction between DPPH^– and Sc³⁺. In this study, it is demonstrated that the addition of H₂O to the DPPH^•–Sc(OTf)₃ system in MeCN resulted in an increase in the absorption band at 519 nm due to DPPH^•. This indicated that an electron-transfer comproportionation occurred to regenerate DPPH^•. The regeneration of DPPH^• was also confirmed by electron paramagnetic resonance (EPR) spectroscopy. The amount of DPPH^• increased with an increasing amount of added H₂O to reach a constant value. The detailed mechanism of regeneration of DPPH^• was proposed based on the detailed spectroscopic and kinetic analyses, in which the reaction of DPPH⁺ with [(DPPH)₂Sc(H₂O)₃]⁺ generated upon the addition of H₂O to [(DPPH)₂Sc]⁺ is the rate-determining step. Full article

1,4-Napththoquinones (NQs) are clinically relevant therapeutics that affect cell function through production of reactive oxygen species (ROS) and formation of adducts with regulatory protein thiols. Reactive sulfur species (RSS) are chemically and biologically similar to ROS and here we examine RSS production by NQ oxidation of hydrogen sulfide (H₂S) using RSS-specific fluorophores, liquid chromatography-mass spectrometry, UV-Vis absorption spectrometry, oxygen-sensitive optodes, thiosulfate-specific nanoparticles, HPLC-monobromobimane derivatization, and ion chromatographic assays. We show that NQs, catalytically oxidize H₂S to per- and polysulfides (H₂S_n, n = 2–6), thiosulfate, sulfite and sulfate in reactions that consume oxygen and are accelerated by superoxide dismutase (SOD) and inhibited by catalase. The approximate efficacy of NQs (in decreasing order) is, 1,4-NQ ≈ juglone ≈ plumbagin > 2-methoxy-1,4-NQ ≈ menadione >> phylloquinone ≈ anthraquinone ≈ menaquinone ≈ lawsone. We propose that the most probable reactions are an initial two-electron oxidation of H₂S to S⁰ and reduction of NQ to NQH₂. S⁰ may react with H₂S or elongate H₂S_n in variety of reactions. Reoxidation of NQH₂ likely involves a semiquinone radical (NQ^·−) intermediate via several mechanisms involving oxygen and comproportionation to produce NQ and superoxide. Dismutation of the latter forms hydrogen peroxide which then further oxidizes RSS to sulfoxides. These findings provide the chemical background for novel sulfur-based approaches to naphthoquinone-directed therapies. Full article

Vitamin E, a collection of lipophilic phenolic compounds based on chroman-6-ol, has a rich and fascinating oxidative chemistry involving a range of intermediate forms, some of which are proposed to be important in its biological functions. In this review, the available electrochemical and spectroscopic data on these oxidized intermediates are summarized, along with a discussion on how their lifetimes and chemical stability are either typical of similar phenolic and chroman-6-ol derived compounds, or atypical and unique to the specific oxidized isomeric form of vitamin E. The overall electrochemical oxidation mechanism for vitamin E can be summarized as involving the loss of two-electrons and one-proton, although the electron transfer and chemical steps can be controlled to progress along different pathways to prolong the lifetimes of discreet intermediates by modifying the experimental conditions (applied electrochemical potential, aqueous or non-aqueous solvent, and pH). Depending on the environment, the electrochemical reactions can involve single electron transfer (SET), proton-coupled electron transfer (PCET), as well as homogeneous disproportionation and comproportionation steps. The intermediate species produced via chemical or electrochemical oxidation include phenolates, phenol cation radicals, phenoxyl neutral radicals, dications, diamagnetic cations (phenoxeniums) and para–quinone methides. The cation radicals of all the tocopherols are atypically long-lived compared to the cation radicals of other phenols, due to their relatively weak acidity. The diamagnetic cation derived from α–tocopherol is exceptionally long-lived compared to the diamagnetic cations from the other β–, γ– and δ–isomers of vitamin E and compared with other phenoxenium cations derived from phenolic compounds. In contrast, the lifetime of the phenoxyl radical derived from α–tocopherol, which is considered to be critical in biological reactions, is typical for what is expected for a compound with its structural features. Over longer times via hydrolysis reactions, hydroxy para–quinone hemiketals and quinones can be formed from the oxidized intermediates, which can themselves undergo reduction processes to form intermediate anion radicals and dianions. Methods for generating the oxidized intermediates by chemical, photochemical and electrochemical methods are discussed, along with a summary of how the final products vary depending on the method used for oxidation. Since the intermediates mainly only survive in solution, they are most often monitored using UV-vis spectroscopy, FTIR or Raman spectroscopies, and EPR spectroscopy, with the spectroscopic techniques sometimes combined with fast photoinitiated excitation and time-resolved spectroscopy for detection of short-lived species. Full article

Eumelanin is a widespread biomacromolecule pigment in the biosphere and has been widely investigated for numerous bioelectronics and energetic applications. Many of these applications depend on eumelanin’s ability to conduct proton current at various levels of hydration. The origin of this behavior is connected to a comproportionation reaction between oxidized and reduced monomer moieties and water. A hydration-dependent FTIR spectroscopic study on eumelanin is presented herein, which allows for the first time tracking the comproportionation reaction via the gradual increase of the overall aromaticity of melanin monomers in the course of hydration. We identified spectral features associated with the presence of specific “one and a half” C𝌁O bonds, typical for o-semiquinones. Signatures of semiquinone monomers with internal hydrogen bonds and that carboxylic groups, in contrast to semiquinones, begin to dissociate at the very beginning of melanin hydration were indicated. As such, we suggest a modification to the common hydration-dependent conductivity mechanism and propose that the conductivity at low hydration is dominated by carboxylic acid protons, whereas higher hydration levels manifest semiquinone protons. Full article

With the development of nanotechnology, gold nanoparticles (Au NPs) have attracted enormous attention due to their special properties. The green synthesis of Au NPs from lignin would inspire the utilization of lignin and its related functional materials. In this study, a rapid preparation process of Au NPs was investigated by utilizing lignin nanoparticles (LNPs) under room temperature without chemical addition. The LNPs acted as a reducing agent, stabilizing agent, and template for the preparation of LNPs@AuNPs. The obtained LNPs@AuNPs were characterized by UV-Vis spectrum, Transmission Electron Microscope (TEM), and X-ray photoelectron spectroscopy (XPS). The possible mechanism was illustrated by Fourier Transform Infrared Spectroscopy (FT-IR), ³¹P, XPS, and UV analyses. The abundant hydroxyl groups (24.96 mmol/g) favored the preparation of Au NPs. Au NPs diameters of 10–30 nm were well dispersed in the LNPs. The optimal reaction conditions were a ratio of 10 mg of LNPs to 0.05 mmol HAuCl₄, room temperature, and a reaction time of 30 min. The LNPs@AuNPs exhibited excellent stability in the suspension for more than seven days. The reduction process could be related to the disruption of side chains of lignin, hydroxyl group oxidation, and hydroquinones and quinones from the comproportionation reaction. The LNPs@AuNPs would open a door for the design of Au NP/lignin-derived novel functional materials. Full article

A research investigation of “ant nest” corrosion (ANC) on copper tube was conducted in terms of the variables of the corrosion potential and pH value in 10³ ppm copper formate solution over 20 days. The paper presents the surface and cross-sectional observations and examines Cu₂O and H₂O as the stable chemical species produced. A Cannizzaro reaction as a disproportionation reaction from formic acid and a comproportionation reaction from the metallic copper tube and copper formate solution critically influenced the ANC mechanism. The paper also categorizes the ANC attack as a rapid reaction system from the electrochemical point of view by using a polarization resistance curve. Full article

The new intermetallic compound Ru₁₁Lu₂₀ was obtained as black single crystals during an attempted comproportionation reaction of lutetium(III) chloride, LuCl₃, with metallic lutetium in the presence of ruthenium metal at 950 °C. Ru₁₁Lu₂₀ crystallizes with the trigonal space group R-3, Z = 6, a = 1255.1(1), c = 2973.0(4) pm, R₁ for all data: 0.0380. Ruthenium atoms center eight-, nine- and ten-vertex polyhedra of lutetium atoms which are connected in a complicated manner to a three-dimensional network. Full article