The determination of the oxygen consumption in autoxidation studies by means of EPR spectroscopy

Pedulli, Gian Franco; Lucarini, Marco; Pedrielli, Pamela; Sagrini, Monica; Cipollone, Marta

doi:10.1163/156856796x00322

Cited by 20 publications

(20 citation statements)

References 20 publications

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“…63 The method has been successfully applied to organic solvents using the persistent nitroxyl radical 2,2,6,6-tetramethylpiperidin-1-oxyl (TEMPO) [62][63][64] and in aqueous media, using coal-derived fusinite particles in suspension. 62,63 Another popular method to measure the rate of oxygen consumption during an autoxidation is based on its polarographic detection using a Clark-type microelectrode. This approach requires a platinum cathode polarized to approximately +0.8 V with respect to an anode of Ag • /AgCl, both immersed in the same KCl solution inside a glass chamber, and separated from a small (∼0.6 ml) isolated sample chamber by a polyethylene septum that is porous to oxygen.…”

Section: Inhibited Autoxidationsmentioning

confidence: 99%

Antioxidants in Chemistry and Biology

Valgimigli

Pratt

2012

Encyclopedia of Radicals in Chemistry, Biology and Materials

109

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Antioxidants are omnipresent in nature and industry; they are used to slow down the autoxidative degradation of both organic tissues and petroleum‐derived products. Various mechanisms by which antioxidants can act are known, the most common of which are introduced here. Since autoxidation is a radical chain reaction, radical‐trapping antioxidants play a particularly important role; therefore, we will discuss these compounds in most detail. To introduce and develop central concepts relating to this topic, we present kinetic and thermodynamic data obtained for the reactions of phenols, the archetypical radical‐trapping antioxidants, with chain‐carrying peroxyl radicals, and describe the means to obtain these data. We then extend our discussion to other important classes of radical‐trapping antioxidants, beginning with the closely related polyphenols and newly developed pyridinol and pyrimidinol antioxidants, and then further to aromatic amines, organosulfur compounds, and their derivatives. We go on to touch upon the synergistic behavior in antioxidant combinations, and the effects of the medium on these interactions, and finally round things up with a few more important biological examples: ascorbate and β‐carotene. A few comments on the state of the field and areas requiring further research and development are included.

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Section: Inhibited Autoxidationsmentioning

confidence: 99%

Antioxidants in Chemistry and Biology

Valgimigli

Pratt

2012

Encyclopedia of Radicals in Chemistry, Biology and Materials

109

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“…[54] The ESR spectra of TEMPO in both hydrogen-bond-accepting and non-hydrogenbonding solvents at predetermined concentrations were recorded in air and in nitrogen atmosphere as standards for measuring the line width of the spin label TEMPO aerobically and anaerobically. Subsequently, the O 2 consumption rate in both solvents was measured via ESR spin label oximetry, which could effectively indicate the apparent inhibition rate of autoxidation.…”

Section: à1/2mentioning

confidence: 99%

“…studied a model oxidation of methyl linoleate initiated by α,α′‐azoisobutyronitrile . In the ESR spectrum of spin label 2,2,6,6‐tetramethyl‐1‐piperidinyloxyl (TEMPO), the reciprocal of the square root of the signal height, I −1/2 , of the central line was measured as the line width and the former is more accurate than the latter in the presence of high O 2 concentrations . The ESR spectra of TEMPO in both hydrogen‐bond‐accepting and non‐hydrogen‐bonding solvents at predetermined concentrations were recorded in air and in nitrogen atmosphere as standards for measuring the line width of the spin label TEMPO aerobically and anaerobically.…”

Section: Effective Applications Of Esr Spin Label Oximetrymentioning

confidence: 99%

Application of ESR spin label oximetry in food science

Zhou

Yin

2011

Magnetic Reson in Chemistry

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Lipid oxidation attributed to the presence of oxygen has long been a focal area for food science research due in early years mainly to its broad impact on the quality and shelf stability. The need to effectively strategize interventions to detect and eventually eliminate lipid oxidation in food remains as evidence on nutritional and health implications continue to accumulate. Electron spin resonance (ESR) spin label oximetry has been shown capable of detecting dissolved oxygen concentration in both liquid and gaseous phases based on the collision between oxygen and stable free radicals. This review aimed to summarize not just the principles and rationale of ESR spin label oximetry but also the wide spectrum of ESR spin label oximetry applications to date. The feasibility to identify in very early stage oxygen generation and consumption offers a promising tool for controlling lipid oxidation in food and biological systems.

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“…Actually the width of these lines is related to the concentration of oxygen, which produces a strong broadening of the EPR spectral lines of radicals due to Heisenberg spin exchange. 9,10 Another spectral parameter, sensitive to the oxygen concentration, but much easier to measure than the width, is the peak to peak height of the EPR line, I. This is proportional to both the radical concentration and the reciprocal of line width.…”

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confidence: 99%

2-Cyano-2-phenylpropanoic Acid Triggers the Back and Forth Motions of an Acid–Base-Operated Paramagnetic Molecular Switch

et al. 2019

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The back and forth motions of a crown-ether based wheel along the axis of a bistable rotaxane are triggered by the decarboxylation of 2-cyano-2-phenylpropanoic acid and detected by the oscillation of the EPR nitrogen splitting of a dialkyl nitroxide function mounted within the macrocyclic ring. When the p-Cl derivative of the acid is used, back and forth motions are accelerated. Conversely, with p-CH 3 and p-OCH 3 derivatives, the back motion is strongly inhibited by the insurgence of collateral radical reactions.

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The determination of the oxygen consumption in autoxidation studies by means of EPR spectroscopy

Cited by 20 publications

References 20 publications

Antioxidants in Chemistry and Biology

Antioxidants in Chemistry and Biology

Application of ESR spin label oximetry in food science

2-Cyano-2-phenylpropanoic Acid Triggers the Back and Forth Motions of an Acid–Base-Operated Paramagnetic Molecular Switch

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