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Hatzipanayioti, Despina; Karaliota, Alexandra; Kamariotaki, Mary; Veneris, Antony; Falaras, P.

doi:10.1023/a:1006940614035

Cited by 16 publications

(6 citation statements)

References 23 publications

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“…This observation suggests that 2,3-DHBA might bind to the Mn-oxo core in ad ifferent binding mode than the typical carboxylate binding mode known for Mn 12 clusters. The ligand 2,3-DHBA has several possible binding modes resulting from the structural proximity of the ÀOH substituent to the carboxylic acid; these include the typical bridging binding mode present in Mn 12 clusters, whichi nvolves the carboxylic edge only, [27] and the salicylate binding mode that involves bindingt hrough the acid and the adjacent ÀOH substituent, as studied for various metals complexese mploying such ligand [33][34][35][36][37][38][39] (Scheme 2). The bindingm ode of 2,3-DHBAtom etal centers should be pH controlled because it depends on the abstraction of the proton from the ortho ÀOH group.…”

Section: Resultsmentioning

confidence: 99%

The Role of the −OH Groups within Mn₁₂Clusters in Electrocatalytic Water Oxidation

Gluz

Christou

Maayan

2021

Chemistry A European J

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The formidable reactivity of the oxygen‐evolving center near photosystem II is largely based on its protein environment that stabilizes it during catalysis. Inspired by this concept, the water‐soluble Mn12 clusters Mn12O12(O2CC6H3(OH)2)16(H2O)4 (3,5DHMn12) and Mn12O12(O2CC6H3(OH)3)16(H2O)4 (3,4,5THMn12) were developed as efficient electrocatalysts for water oxidation. In this work, the role of the −OH groups in the electrocatalytic process was explored by describing the structural and electrocatalytic properties of two new Mn12 clusters, 3,4DHMn12 and 2,3DHMn12, having one −OH group in the meta position relative to the benzoate‐Mn moiety, and one at the para or ortho position, respectively. The Mn centers in 3,4DHMn12 were discovered to have lower oxidation potential compared with those in 2,3DHMn12, and thus, 3,4DHMn12 can catalyze water oxidation with higher rate and TON than 2,3DHMn12. Hence, the role of the −OH groups in the electrocatalysis was established, being involved in electronic stabilization of the Mn centers or in proton shuttling.

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Section: Resultsmentioning

confidence: 99%

The Role of the −OH Groups within Mn₁₂Clusters in Electrocatalytic Water Oxidation

Gluz

Christou

Maayan

2021

Chemistry A European J

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“…In particular, this technique offers rapid measure ment of the redox potentials of electroactive species and convenient evaluation of the effect of environmental parameters upon redox processes (). Cyclic voltammetry has been used to characterize the oxidation state and the type of binding between hydroquinones and metals ions in dimethyl sulfoxide (DMSO) solutions ( , ).…”

Section: Introductionmentioning

confidence: 99%

Electrochemical Study of 2,3-Dihydroxybenzoic Acid and Its Interaction with Cu(II) and H₂O₂ in Aqueous Solutions: Implications for Wood Decay

Liu

Goodell

Jellison

et al. 2004

Environ. Sci. Technol.

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The electrochemical behavior of 2,3-dihydroxybenzoic acid (2,3-DHBA) and the electron-transfer characteristics between Cu(II) and 2,3-DHBA were studied in aqueous solutions using cyclic voltammetry (CV). The overall electrochemical oxidation process of 2,3-DHBA by Cu(II) may be classified as a chemical reaction involving one-electron oxidation of 2,3-DHBA to its semiquinone radical in solution, followed by an electron-transfer reaction involving the oxidation of the semiquinone radical to a quinone at the electrode surface. In the presence of H2O2, oxidation of 2,3-DHBA by Cu(II) is enhanced due to the regeneration of Cu(II) by H2O2 oxidizing Cu(I). The redox cycling between Cu(I)/Cu(II) and H2O2 also produces hydroxyl radicals (OH). Even though the presence of OH may not be detected at the surface of a glassy carbon electrode, production of electroactive dissolved oxygen (O2) suggests the presence of OH. The production of O2 is dependent on Cu(II):H2O2 concentration ratio. At the electrode surface and when the initial Cu(II):H2O2 is less than 1, O2 is produced, suggesting that H2O2 may act as a scavenger for OH; at initial Cu(II):H2O2 > 1, the production of O2 is not favored, and OH will be involved in the oxidation of Cu(I) and the organic ligand. The reaction mechanisms proposed in this study indicate that OH production by chelator-mediated Fenton reactions is favorable under conditions found in the wood cell wall.

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“…In the literature, the polarographic waves of aromatic acids are assigned to reduction of the carboxylic acid proton to molecular hydrogen (pathway 1 in Scheme 1) [20,21]. On the other hand, it has also been found that the signal is due to reduction of the carboxylic acid through the pathways 2, 3, or 4 (Scheme 1) [17,22].…”

Section: Introductionmentioning

confidence: 99%

On reduction of the drug diflunisal in non-aqueous media

et al. 2015

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The electrochemical reduction of diflunisal was studied in dimethyl sulfoxide on static mercury drop electrode. Diflunisal yields one irreversible wave at -1.2 V (vs. Ag | AgCl | 1 M LiCl electrode) due to the reduction of the carboxylic functional group in the molecule. The electrochemical properties of the drug were compared with the ones of the chlorinated analogue. The study is based on cyclic voltammetry, tast polarography, and constant potential electrolysis. The experimental findings are supported by molecular orbital calculations. The mechanism of reduction of the carboxylic moiety was found to involve two electrons and two protons. The reduction pathway leads to formation of an aldehyde derivative. Graphical Abstract

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Cited by 16 publications

References 23 publications

The Role of the −OH Groups within Mn₁₂Clusters in Electrocatalytic Water Oxidation

The Role of the −OH Groups within Mn₁₂Clusters in Electrocatalytic Water Oxidation

Electrochemical Study of 2,3-Dihydroxybenzoic Acid and Its Interaction with Cu(II) and H₂O₂ in Aqueous Solutions: Implications for Wood Decay

On reduction of the drug diflunisal in non-aqueous media

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Untitled

Cited by 16 publications

References 23 publications

The Role of the −OH Groups within Mn12Clusters in Electrocatalytic Water Oxidation

The Role of the −OH Groups within Mn12Clusters in Electrocatalytic Water Oxidation

Electrochemical Study of 2,3-Dihydroxybenzoic Acid and Its Interaction with Cu(II) and H2O2 in Aqueous Solutions: Implications for Wood Decay

On reduction of the drug diflunisal in non-aqueous media

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The Role of the −OH Groups within Mn₁₂Clusters in Electrocatalytic Water Oxidation

The Role of the −OH Groups within Mn₁₂Clusters in Electrocatalytic Water Oxidation

Electrochemical Study of 2,3-Dihydroxybenzoic Acid and Its Interaction with Cu(II) and H₂O₂ in Aqueous Solutions: Implications for Wood Decay