Calculation of the two-step reduction potentials of some quinones in acetonitrile

Alizadeh, Kamal; Shamsipur, Mojtaba

doi:10.1016/j.theochem.2008.04.021

Cited by 27 publications

(17 citation statements)

References 39 publications

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“…(12) where the ∆G (ref) is the experimental redox free energy of the reference complex used as isodesmic model. This method had been successfully applied not only to organic compounds [38][39][40][41] but also for transition metal complexes and reproduced experimentally determined redox potentials accurately within ~0.1 eV [42][43][44]. Moreover, this isodesmic method was employed to predict the redox potentials of actinyl (VI/V) in solution and calculated redox potentials were in good agreement with the experimentally determined redox potentials [45].…”

Section: Isodesmic Methodsmentioning

confidence: 90%

“…The calculated reduction potentials of the IIDs compounds showed a linear correlation to the Hammett constant values of the ring substituents [104,105]. In addition, two-electron redox potentials for eight substituted quinones in acetonitrile solvent were also accurately calculated by using the B3LYP method including the PCM solvation model for solvation effects [40]. Recently, IPs and HOMO orbital energies were calculated for a number of substituted aryl imidazoles using the B3LYP method and plotted against the experimental oxidation potentials.…”

Section: Organicsmentioning

confidence: 99%

See 1 more Smart Citation

Computational Redox Potential Predictions: Applications to Inorganic and Organic Aqueous Complexes, and Complexes Adsorbed to Mineral Surfaces

Arumugam

Becker

2014

Minerals

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Abstract:Applications of redox processes range over a number of scientific fields. This review article summarizes the theory behind the calculation of redox potentials in solution for species such as organic compounds, inorganic complexes, actinides, battery materials, and mineral surface-bound-species. Different computational approaches to predict and determine redox potentials of electron transitions are discussed along with their respective pros and cons for the prediction of redox potentials. Subsequently, recommendations are made for certain necessary computational settings required for accurate calculation of redox potentials. This article reviews the importance of computational parameters, such as basis sets, density functional theory (DFT) functionals, and relativistic approaches and the role that physicochemical processes play on the shift of redox potentials, such as hydration or spin orbit coupling, and will aid in finding suitable combinations of approaches for different chemical and geochemical applications. Identifying cost-effective and credible computational approaches is essential to benchmark redox potential calculations against experiments. Once a good theoretical approach is found to model the chemistry and thermodynamics of the redox and electron transfer process, this knowledge can be incorporated into models of more complex reaction mechanisms that include diffusion in the solute, surface diffusion, and dehydration, to name a few. This knowledge is important to fully understand the nature of redox processes be it a geochemical process that dictates natural redox reactions or one that is being used for the optimization of a chemical process in industry. In addition, it will help identify materials that will be useful to design catalytic OPEN ACCESSMinerals 2014, 4 346 redox agents, to come up with materials to be used for batteries and photovoltaic processes, and to identify new and improved remediation strategies in environmental engineering, for example the reduction of actinides and their subsequent immobilization. Highly under-investigated is the role of redox-active semiconducting mineral surfaces as catalysts for promoting natural redox processes. Such knowledge is crucial to derive process-oriented mechanisms, kinetics, and rate laws for inorganic and organic redox processes in nature. In addition, molecular-level details still need to be explored and understood to plan for safer disposal of hazardous materials. In light of this, we include new research on the effect of iron-sulfide mineral surfaces, such as pyrite and mackinawite, on the redox chemistry of actinyl aqua complexes in aqueous solution.

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Section: Isodesmic Methodsmentioning

confidence: 90%

Section: Organicsmentioning

confidence: 99%

Computational Redox Potential Predictions: Applications to Inorganic and Organic Aqueous Complexes, and Complexes Adsorbed to Mineral Surfaces

Arumugam

Becker

2014

Minerals

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“…The values of heterogeneous electron transfer rate constants for the reduction of different quinones in nonaqueous solvents at different electrodes have been measured by cyclic voltammetry [217]. Theoretically, the redox potentials have been calculated including solvent effect, for a series of anthraquinone and few other quinone derivatives by Alizadeh and Shamsipur [218] and compared with the available experimental electrode potentials [122] in two consecutive electron transfer steps in acetonitrile solution. The theoretical values of redox potentials in the two successive one-electron steps in most cases show a relatively good agreement with the corresponding experimental electrode potentials [218].…”

Section: Role Of Cations and Anions Of Supporting Electrolytesmentioning

confidence: 99%

Electrochemical Reduction of Quinones in Different Media: A Review

Guin

Das

Mandal

2011

International Journal of Electrochemistry

346

246

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The electron transfer reactions involving quinones, hydroquinones, and catechols are very important in many areas of chemistry, especially in biological systems. The therapeutic efficiency as well as toxicity of anthracycline anticancer drugs, a class of anthraquinones, is governed by their electrochemical properties. Other quinones serve as important functional moiety in various biological systems like electron-proton carriers in the respiratory chain and their involvement in photosynthetic electron flow systems. The present paper summarizes literatures on the reduction of quinones in different solvents under various conditions using different electrochemical methods. The influence of different reaction conditions including pH of the media, nature of supporting electrolytes, nature of other additives, intramolecular or intermolecular hydrogen bonding, ion pair formation, polarity of the solvents, stabilization of the semiquinone and quinone dianion, catalytic property, and adsorption at the electrode surface, are discussed and relationships between reaction conditions and products formed have been presented.

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“…Predictions of thermodynamic functions of the formation of the radical anion intermediate, as the first step of quinone reduction, using quantum chemical (QC) methods, have been more frequently reported. Often, the redox potential is predicted as a function of Gibbs free energy of oxidized and reduced forms, calculated by either Hartree–Fock and DFT calculations, or faster but less precise semiempirical methods. The influence of solvent on redox potentials of quinones was established as an MLR model, based on QC descriptors and solvent properties (Guttmann acceptor number, dipole moment).…”

Section: Introductionmentioning

confidence: 99%

Redox Polypharmacology as an Emerging Strategy to Combat Malarial Parasites

et al. 2016

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3-Benzylmenadiones are potent antimalarial agents that are thought to act through their 3-benzoylmenadione metabolites as redox cyclers of two essential targets: the NADPH-dependent glutathione reductases (GRs) of Plasmodium-parasitized erythrocytes and methemoglobin. Their physicochemical properties were characterized in a coupled assay using both targets and modeled with QSPR predictive tools built in house. The substitution pattern of the west/east aromatic parts that controls the oxidant character of the electrophore was highlighted and accurately predicted by QSPR models. The effects centered on the benz(o)yl chain, induced by drug bioactivation, markedly influenced the oxidant character of the reduced species through a large anodic shift of the redox potentials that correlated with the redox cycling of both targets in the coupled assay. Our approach demonstrates that the antimalarial activity of 3-benz(o)ylmenadiones results from a subtle interplay between bioactivation, fine-tuned redox properties, and interactions with crucial targets of P. falciparum. Plasmodione and its analogues give emphasis to redox polypharmacology, which constitutes an innovative approach to antimalarial therapy.

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Calculation of the two-step reduction potentials of some quinones in acetonitrile

Cited by 27 publications

References 39 publications

Computational Redox Potential Predictions: Applications to Inorganic and Organic Aqueous Complexes, and Complexes Adsorbed to Mineral Surfaces

Computational Redox Potential Predictions: Applications to Inorganic and Organic Aqueous Complexes, and Complexes Adsorbed to Mineral Surfaces

Electrochemical Reduction of Quinones in Different Media: A Review

Redox Polypharmacology as an Emerging Strategy to Combat Malarial Parasites

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