Electron Paramagnetic Resonance Measurements of Reactive Oxygen Species by Cyclic Hydroxylamine Spin Probes

Dikalov, Sergey; Polienko, Yuliya F.; Kirilyuk, Igor A.

doi:10.1089/ars.2017.7396

Cited by 90 publications

(64 citation statements)

References 94 publications

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“…Spin trapping in cellular systems.-Spin traps have not only been applied in artificial sytems but also in biological and medical studies in vitro and in vivo. [426][427][428][429][430][431][432][433][434][435] Due to the complex composition of solutions and low radical production in such experiments, careful control and calibration experiments need to be performed for a quantitative interpretation of spin trapping ESR measurements. Particularly, when working with cells in physiological buffer solutions, Fenton type reactions often have to be controlled by using metal chelators to avoid strong background signals and artefacts.…”

Section: Applications Of Spin Traps and Spin Probes-h 2 Omentioning

confidence: 99%

“…After reduction of • O 2t o H 2 O 2 the formation of the nitroxide radical signal was monitored over time and was quantified. 11,427,429,437,438 These spin probes are inert to reaction with H 2 O 2 , and the nitroxide is sufficiently stable in the presence of H 2 O 2 or compounds of physiological buffer solutions.…”

Section: Applications Of Spin Traps and Spin Probes-h 2 Omentioning

confidence: 99%

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Review—Quantification of Hydrogen Peroxide by Electrochemical Methods and Electron Spin Resonance Spectroscopy

Gulaboski

Mirčeski

Kappl

et al. 2019

J. Electrochem. Soc.

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Reactive oxygen species (ROS) exhibit different spatial and temporal distributions as well as concentrations in-and outside the cell, thereby functioning as signaling or pathogen-destroying molecules. Especially the ROS H 2 O 2 is important for the patho/physiological status of an organism. Electrochemistry (EM) and electron spin resonance (ESR)-based techniques allow quantification of H 2 O 2 in artificial and living systems, coping a concentration range from low nM up to mM. Working electrodes for EM are optimized by diverse modifications and, additionally, redox mediators are used. Ultramicroelectrodes allow scanning of single cells to spatially resolve and quantify extracellular H 2 O 2 in real-time. With ESR spectroscopy, • O 2¯, but not H 2 O 2 , can be directly determined by spin probes in-and outside of cells in suspensions. Monitoring H 2 O 2 requires formation of intermediate radicals, detectable with spin probes. Low μM [H 2 O 2 ] can thus be assessed specifically. Using suitable spin traps, in-vivo ESR and immuno-spin trapping can visualize different radicals at their respective production sites in small animals, organs and tissues. Here, the redox reaction cascades may interfere with cell metabolism. Optimization of all methods established for H 2 O 2 determination would be favorable to finally combine them for mutual validation. Thus, a deeper insight into cellular ROS metabolism can be obtained.

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Section: Applications Of Spin Traps and Spin Probes-h 2 Omentioning

confidence: 99%

Section: Applications Of Spin Traps and Spin Probes-h 2 Omentioning

confidence: 99%

Review—Quantification of Hydrogen Peroxide by Electrochemical Methods and Electron Spin Resonance Spectroscopy

Gulaboski

Mirčeski

Kappl

et al. 2019

J. Electrochem. Soc.

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“…Another approach consists of using cyclic hydroxylamines as molecular probes for oxidative stress [42][43][44][45]. In this case, the EPR signal appears along with nitroxide formation in the tissue following oxidation of the probe by RONS ( Figure 5).…”

Section: Probe Reactivitymentioning

confidence: 99%

“…Different factors decrease the sensitivity of the technique. Most commonly used hydroxylamine spin probes exist in equilibrium with high proportions of their unreactive protonated forms at a physiological pH (pKa ≈ 7) [45]. Because the product of oxidation of the hydroxylamine spin probe is a nitroxide, it is susceptible to bioreduction, which leads to loss of the EPR signal.…”

Section: Probe Reactivitymentioning

confidence: 99%

“…Another problem is that for standard tetramethyl-substituted spin probes, the superoxide reacts faster with the nitroxide than with the corresponding hydroxylamine [46], leading to underestimation of the rate of superoxide production at a high level of probe conversion. Because they are susceptible to autoxidation, free hydroxylamines have almost never been used for in vivo EPR and ex vivo analysis is usually preferred [45]. The principle of using hydroxylamines as probes for RONS.…”

Section: Probe Reactivitymentioning

confidence: 99%

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Molecular Probes for Evaluation of Oxidative Stress by In Vivo EPR Spectroscopy and Imaging: State-of-the-Art and Limitations

Babić

Peyrot

2019

Magnetochemistry

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Oxidative stress, defined as a misbalance between the production of reactive oxygen species and the antioxidant defenses of the cell, appears as a critical factor either in the onset or in the etiology of many pathological conditions. Several methods of detection exist. However, they usually rely on ex vivo evaluation or reports on the status of living tissues only up to a few millimeters in depth, while a whole-body, real-time, non-invasive monitoring technique is required for early diagnosis or as an aid to therapy (to monitor the action of a drug). Methods based on electron paramagnetic resonance (EPR), in association with molecular probes based on aminoxyl radicals (nitroxides) or hydroxylamines especially, have emerged as very promising to meet these standards. The principles involve monitoring the rate of decrease or increase of the EPR signal in vivo after injection of the nitroxide or the hydroxylamine probe, respectively, in a pathological versus a control situation. There have been many successful applications in various rodent models. However, current limitations lie in both the field of the technical development of the spectrometers and the molecular probes. The scope of this review will mainly focus on the latter.

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Synthesis and Characterization of the Perthiatriarylmethyl Radical and Its Dendritic Derivatives with High Sensitivity and Selectivity to Superoxide Radical

Tan

Tao

Liu

et al. 2018

Chemistry A European J

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EPR spectroscopy, coupled with the use of tetrathiatriarylmethyl (TAM) radicals, has been a reliable method to detect the superoxide radical (O ). However, the specificity and biocompatibility of TAM radicals need to be further improved. Although derivatization may overcome the drawbacks of current TAM radicals, esterification or amidation through the carboxylic groups greatly changes their redox properties and makes them inert to O . Herein, the synthesis of a perthiatriarylmethyl (PST) radical and its dendritic derivatives, PST-TA and PST-NA, in which PST is covalently linked with dendrons containing three (TA) and nine (NA) carboxylic acids, respectively. The results show that PST rapidly reacts with O to yield a unique quinone methide product. Dendritic modification of PST slightly decreases the reactivities of PST-TA and PST-NA, but notably increases their biostability toward various oxidoreductants. The detection limit of PST-NA to O was estimated to be 2.1 nm min over 60 min of detection. Importantly, PST-NA shows threefold higher sensitivity to O in the presence and absence of ascorbic acid than that of the classic spin-trapping technique. In addition, the application of PST-NA to detect extracellular O generation in stimulated RAW 264.7 macrophages was also explored. This study demonstrates that PST-NA has great potential for specific detection and quantitation of O in extracellular sites.

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Electron Paramagnetic Resonance Measurements of Reactive Oxygen Species by Cyclic Hydroxylamine Spin Probes

Abstract: Additional studies to advance hydroxylamine spin probes from the "basic science" to biomedical applications are needed and could lead to better understanding of pathological conditions associated with oxidative stress. Antioxid. Redox Signal. 28, 1433-1443.

Cited by 90 publications

References 94 publications

Review—Quantification of Hydrogen Peroxide by Electrochemical Methods and Electron Spin Resonance Spectroscopy

Review—Quantification of Hydrogen Peroxide by Electrochemical Methods and Electron Spin Resonance Spectroscopy

Molecular Probes for Evaluation of Oxidative Stress by In Vivo EPR Spectroscopy and Imaging: State-of-the-Art and Limitations

Synthesis and Characterization of the Perthiatriarylmethyl Radical and Its Dendritic Derivatives with High Sensitivity and Selectivity to Superoxide Radical

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