Indirect electrochemical oxidation of aliphatic alcohols to carboxylic acids by active oxygen forms in aqueous media

Chaenko, N. V.; Kornienko, G. V.; Kosheleva, A. M.; Maksimov, N. G.; Kornienko, V. L.

doi:10.1134/s102319351110003x

Cited by 11 publications

(7 citation statements)

References 9 publications

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“…For example, direct electron transfer peroxidation coupled with electrospray ionization mass spectrometry has been shown to be a promising technique for the study of peroxidation processes and the stability of organic molecules in liquid samples, and indirect peroxidation of molecules by ROS and hydrogen peroxide . Electrochemical reduction of molecular oxygen has been shown to lead to the oxidation of various organic substrates and indirect electrochemical oxidation has been used recently in combination with liquid chromatography/mass spectrometry . Note that free radicals can be studied in real time using ESRor electrochemical sensors .…”

Section: Introductionmentioning

confidence: 99%

“…The instrument does so by passing the necessary current between the working electrode and the third counter electrode (C). The current driven between R and W depends upon the potential difference between them . The potentials needed for electrochemical ROS production depend on the electrode materials.…”

Section: Introductionmentioning

confidence: 99%

“…Two‐electron reduction of oxygen to hydrogen peroxide, H 2 O 2 , is effected at the cathode (reaction (1)). At the anode, water oxidation proceeds to form the OH • radicals as intermediates (reaction (2))

O_{2} + 2 e^{-} + 2 H^{+} \to H_{2} O_{2}

2 H_{2} normalO \to 2 {OH}^{•} + 2 H^{+} + 2 e^{-}

…”

Section: Introductionmentioning

confidence: 99%

“…HO 2 • radicals, which can contribute to the oxidation of organic compounds, are also produced at the anode:

H_{2} O_{2} \to {HO}_{2}^{•} + H^{+} + e^{-}

H_{2} O_{2} + {OH}^{•} \to {HO}_{2}^{•} + H_{2} normalO

…”

Section: Introductionmentioning

confidence: 99%

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Evaluation of peroxidative stress of cancer cells in vitro by real‐time quantification of volatile aldehydes in culture headspace

Shestivská

Rutter

Sulé-Suso

et al. 2017

Rapid Comm Mass Spectrometry

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RATIONALE: Peroxidation of lipids in cellular membranes results in the release of volatile organic compounds (VOCs), including saturated aldehydes. The real-time quantification of trace VOCs produced by cancer cells during peroxidative stress presents a new challenge to non-invasive clinical diagnostics, which we have met with some success, as described in this paper. METHODS: A combination of selected ion flow tube mass spectrometry (SIFT-MS), a technique that allows rapid, reliable quantification of VOCs in humid air and liquid headspace, and electrochemistry to generate reactive oxygen species (ROS) in vitro has been used. Thus, VOCs present in the headspace of CALU-1 cancer cell line cultures exposed to ROS have been monitored and quantified in real time using SIFT-MS. RESULTS: The CALU-1 lung cancer cells were cultured in 3D collagen to mimic in vivo tissue. Real time SIFT-MS analyses focused on the volatile aldehydes, propanal, butanal, pentanal, hexanal, heptanal and malondialdehyde (propanedial), that are expected to be products of cellular membrane peroxidation. All six aldehydes were identified in the culture headspace, each reaching peak concentrations during the time of exposure to ROS and eventually reducing as the reactants were depleted in the culture. Pentanal and hexanal were the most abundant, reaching concentrations of a few hundred parts-per-billion by volume, ppbv, in the culture headspace. CONCLUSIONS: The results of these experiments demonstrate that peroxidation of cancer cells in vitro can be monitored and evaluated by direct real time analysis of the volatile aldehydes produced. The combination of adopted methodology potentially has value for the study of other types of VOCs that may be produced by cellular damage. Keywords: Selected ion flow tube mass spectrometry, SIFT-MS; volatile organic compounds; electrochemical peroxidation; aldehydes; CALU-1 cancer cells.Lipid peroxidation of cellular membranes results in the release of different volatile organic compounds (VOCs) such as aldehydes, alkenes and hydrocarbons. [1,2] Their appearance in plasma, exhaled breath, saliva and sweat may act as biomarkers of diseases that involve increased oxidative stress of cells. [3][4][5][6] A comprehensive metabolomic investigation of trace VOCs produced when cells are exposed to peroxidative stress represents a challenge to noninvasive clinical diagnostics. [7,8] Such is the focus of the present study.The chosen approach was to perform real-time quantification of volatile aldehydes produced by the action of reactive oxygen species (ROS) on cancer cell lines in vitro. The ROS are produced electrochemically and the VOCs analysis is by selected ion flow tube mass spectrometry, SIFT-MS, a combination of techniques that could be used for real-time observations of VOCs released by other organisms exposed to ROS such as bacteria, mammalian cells and model membranes. The immortal lung cancer cell line CALU-1 has been used to test and develop this combination of techniques. We have given considerable...

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

O_{2} + 2 e^{-} + 2 H^{+} \to H_{2} O_{2}

2 H_{2} normalO \to 2 {OH}^{•} + 2 H^{+} + 2 e^{-}

…”

Section: Introductionmentioning

confidence: 99%

“…HO 2 • radicals, which can contribute to the oxidation of organic compounds, are also produced at the anode:

H_{2} O_{2} \to {HO}_{2}^{•} + H^{+} + e^{-}

H_{2} O_{2} + {OH}^{•} \to {HO}_{2}^{•} + H_{2} normalO

…”

Section: Introductionmentioning

confidence: 99%

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Evaluation of peroxidative stress of cancer cells in vitro by real‐time quantification of volatile aldehydes in culture headspace

Shestivská

Rutter

Sulé-Suso

et al. 2017

Rapid Comm Mass Spectrometry

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“…In addition, both alcohols are oxidized at BDD anodes directly or via • OH and other reactive oxygen species (Chang et al 2006, Chaenko et al 2011, which will limit their reactivity with SO4 •and • OH radicals. Therefore, addition of specific alcohol quenchers could not elucidate between sulfate and hydroxyl radicals' contributions to electrooxidation of diatrizoate.…”

Section: Effect Of Specific Radical Quenchers On Electrooxidation Of mentioning

confidence: 99%

Electrochemical Oxidation of Recalcitrant Organic Compounds using Electro-Generated Sulfate-based Oxidizing Agents

Farhat¹

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Sulfate ions have often been used as background electrolytes in electrochemical degradation of contaminants, and have generally been considered inert even when employing high oxidation power anodes such as boron-doped diamond. Boron-doped diamond (BDD) anodes are widely used in literature for investigating electrochemical oxidation of contaminants due to their excellent capability to form hydroxyl radicals as well as inorganic radicals such as chlorine, phosphate, and sulfate radicals, electrogenerated when their corresponding anions are present in the influent water. This study examined the role of sulfate ions and the potential electro-generation of sulfate-based oxidants by comparing electrooxidation rates for persistent organic contaminants at BDD anodes in the presence of sulfate or nitrate anolytes (considered as inert). The effect of the operating conditions governing this process such as anolyte concentration / conductivity, applied current density, as well as solution volume were explored in this work. The characteristics and the reactive life-time of these electro-chemically generated sulfatebased oxidizing agents were further explored by studying the oxidation extent occurring after the electric current has been switched off or via different modes of intermittent electric current as an option to improve energy efficiency. The effect of chloride ions on the sulfate-based electrooxidation processes for the removal of a natural organic matter surrogate, resorcinol, was also addressed in this work because the anodic oxidation of chloride yields oxidizing species such as chlorine / hypochlorous acid as well as chlorine/chloride radicals, and may compete with sulfate-based oxidizing species, leading to the formation of toxic organic and inorganic chlorinated compounds at higher applied potentials.The detailed investigations showed that sulfate yielded 10 -15 times higher electrooxidation rates of all target contaminants compared to the rates achieved with a nitrate anolyte at identical conductivities. The presence of specific radical quenchers (tert-butanol, methanol) reported a similar effect on diatrizoate electrooxidation rates, illustrating that hydroxyl radicals ( • OH) are most likely influencing the potential anodic formation of sulfate-based oxidizing species. Thus, these results indicate the formation of strong sulfate-derived oxidant species at BDD anodes, where the energy consumption required for a 10-fold removal of diatrizoate was reduced from 45.6 to 2.44 kWh m -3 by switching from nitrate to sulfate anolyte. This electrochemical activation of sulfate was also observed at low concentrations, relevant for many wastewaters, where even only 1.56 mM sulfate anolyte solution (3.5 mS cm -1 and 100 A m -2 ) achieved a higher removal rate than 60 mM nitrate with correspondingly higher conductivity (9.0 mS cm -1 ) and operated at double the current density (200 A m -2 ). Chloride addition to Na2SO4 inhibited the resorcinol oxidation and mineralization, unlike its addition to NaNO3 where it enhanced the ...

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Hydrogen peroxide-mediated tandem catalysis for electrifying chemical synthesis

Li,

Wu,

Chen

et al. 2024

Chem Catalysis

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Indirect electrochemical oxidation of aliphatic alcohols to carboxylic acids by active oxygen forms in aqueous media

Cited by 11 publications

References 9 publications

Evaluation of peroxidative stress of cancer cells in vitro by real‐time quantification of volatile aldehydes in culture headspace

Evaluation of peroxidative stress of cancer cells in vitro by real‐time quantification of volatile aldehydes in culture headspace

Electrochemical Oxidation of Recalcitrant Organic Compounds using Electro-Generated Sulfate-based Oxidizing Agents

Hydrogen peroxide-mediated tandem catalysis for electrifying chemical synthesis

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