Autooxidation Reactions Research Articles

The study of antioxidant activity of white tea

Antioxidants protect the organism from the harmful effects of free radicals. High content of antioxidants is characteristic for red wine, olive oil, tea. Today in Russia is well studied the antioxidant activity of black and green tea, but the choice of teas found in the sale, much wider. The aim of the work was to study antioxidant activity of white tea, as well as its comparison with the parameters of green tea and rooibos. Spectrophotometrically compared the antioxidant activity of aqueous extracts white, green tea, drink rooibos using the adrenaline autooxidation reaction in alkaline medium (pH 10.65). The correctness of the spectrophotometric determination was confirmed on the device “Tsvet Yauza-01-AA” (Russia). As a standard used quercetin. In the initial period of time (up to 5 min) tea extracts “Java”, «Elixir immortality» and rooibos are equally affect the values of optical density. After 10 min the optical density takes different values for different extracts, however this time is recommended to determine antioxidant activity. The highest antioxidant activity of the extract has white tea «Greenfield». Rooibos extract antioxidant activity could be compared with “Elixir of immortality” white tea аctivity. The lowest value of antioxidant activity of green tea “Princess JAVA”. The effect of water temperature on the antioxidant activity of extracts was investigated. The highest value was found in tea «Greenfield» at a brewing temperature of 70 °C, which decreases with increasing temperature to 100 °C. The water temperature has a minimal effect on the antioxidant activity of the rooibos extract, but a small maximum at 80 °C is observed. The minimum value of antioxidant activity is the extract of green tea «Princess JAVA», but it increases with the temperature rise up to 100 °C. The study was conducted according to the content of antioxidants from the brewing time. For this, the device “Tsvet Yauza-01-AA” was used. To determine the selected white tea extract «Elixir of Immortality». The temperature was maintained at 100 °C. It is found that the recommended brewing time is two minutes.

Unraveling the structure and chemical mechanisms of highly oxygenated intermediates in oxidation of organic compounds

Decades of research on the autooxidation of organic compounds have provided fundamental and practical insights into these processes; however, the structure of many key autooxidation intermediates and the reactions leading to their formation still remain unclear. This work provides additional experimental evidence that highly oxygenated intermediates with one or more hydroperoxy groups are prevalent in the autooxidation of various oxygenated (e.g., alcohol, aldehyde, keto compounds, ether, and ester) and nonoxygenated (e.g., normal alkane, branched alkane, and cycloalkane) organic compounds. These findings improve our understanding of autooxidation reaction mechanisms that are routinely used to predict fuel ignition and oxidative stability of liquid hydrocarbons, while also providing insights relevant to the formation mechanisms of tropospheric aerosol building blocks. The direct observation of highly oxygenated intermediates for the autooxidation of alkanes at 500-600 K builds upon prior observations made in atmospheric conditions for the autooxidation of terpenes and other unsaturated hydrocarbons; it shows that highly oxygenated intermediates are stable at conditions above room temperature. These results further reveal that highly oxygenated intermediates are not only accessible by chemical activation but also by thermal activation. Theoretical calculations on H-atom migration reactions are presented to rationalize the relationship between the organic compound's molecular structure (n-alkane, branched alkane, and cycloalkane) and its propensity to produce highly oxygenated intermediates via extensive autooxidation of hydroperoxyalkylperoxy radicals. Finally, detailed chemical kinetic simulations demonstrate the influence of these additional reaction pathways on the ignition of practical fuels.

Stable and solubilized active Au atom clusters for selective epoxidation of cis-cyclooctene with molecular oxygen

The ability of Au catalysts to effect the challenging task of utilizing molecular oxygen for the selective epoxidation of cyclooctene is fascinating. Although supported nanometre-size Au particles are poorly active, here we show that solubilized atomic Au clusters, present in ng ml−1 concentrations and stabilized by ligands derived from the oxidized hydrocarbon products, are active. They can be formed from various Au sources. They generate initiators and propagators to trigger the onset of the auto-oxidation reaction with an apparent turnover frequency of 440 s−1, and continue to generate additional initiators throughout the auto-oxidation cycle without direct participation in the cycle. Spectroscopic characterization suggests that 7–8 atom clusters are effective catalytically. Extension of work based on these understandings leads to the demonstration that these Au clusters are also effective in selective oxidation of cyclohexene, and that solubilized Pt clusters are also capable of generating initiators for cyclooctene epoxidation.

Au-complex containing phosphino and imidazolyl moieties as a bi-functional catalyst for one-pot synthesis of pyridine derivatives

The complex of Au-L1 containing imidazolyl ring and the phosphine-ligated-Au moiety was synthesized and applied as the efficient bi-functional catalyst for the one-pot sequential condensation/annulation reaction for the synthesis of pyridine derivatives. It was found that, as for Au-L1, the involved imidazolyl group acted as a Lewis base to catalyze the condensation of carbonyl compounds with propargylamine to form the imino intermediate, and the involved Au+-complex species with alkynophilicity corresponded to the subsequent activation of imino-tailed alkynyl to afford dehydropyridine intermediate. The latter proceeded auto-oxidation reaction to afford the pyridine derivatives. The observed sequential catalysis over Au-L1 proved more efficient than that over the mechanical mixtures of the Au-complex (Au-L2) and N-methylimidazole, because the free N-methylimidazole as an N-containing donor competed with the alkyne substrate to coordinate to Au-center. Moreover, Au-L1 exhibited good generality to a wide range of the substrates for the synthesis of 2,3-fused pyridine derivatives and 2-aryl(heteroaryl)-substituted pyridines.

A novel chiral stationary phase HPLC-MS/MS method to discriminate between enzymatic oxidation and auto-oxidation of phosphatidylcholine.

To elucidate the role of enzymatic lipid peroxidation in disease pathogenesis and in food deterioration, we recently achieved stereoselective analysis of phosphatidylcholine hydroperoxide (PCOOH) possessing 13S-hydroperoxy-9Z,11E-octadecadienoic acid (13(S)-9Z,11E-HPODE) using HPLC-MS/MS with a CHIRALPAK OP (+) column. Because enzymatic oxidation progresses concurrently with auto-oxidation, we need to distinguish them further. Here, we attempted such an analysis. First, we used lipoxygenase, linoleic acid, and lysophosphatidylcholine (LPC) to synthesize the enzymatic oxidation product 13(S)-9Z,11E-HPODE PC, and the auto-oxidation products 13(RS)-9Z,11E-HPODE PC and 13(RS)-9E,11E-HPODE PC, which were used as standards to test the ability of various columns to separate the enzymatic oxidation product from auto-oxidation products. Separation was achieved by connecting in series two columns with different properties: CHIRALPAK OP (+) and CHIRALPAK IB-3. The CHIRALPAK OP (+) column separated 13(R)-9Z,11E-HPODE PC and 13(S)-9Z,11E-HPODE PC, whereas CHIRALPAK IB-3 enabled separation of 13(S)-9Z,11E-HPODE PC and 13(RS)-9E,11E-HPODE PC. The results for the analysis of both enzymatically oxidized and auto-oxidized lecithin (an important phospholipid mixture in vivo and in food) indicate that our method would be useful for distinguishing enzymatic oxidation and auto-oxidation reactions. Such information will be invaluable for elucidating the involvement of PCOOH in disease pathogenesis and in food deterioration.

Deposition Kinetics of Bioinspired Phenolic Coatings on Titanium Surfaces.

Polyphenols can form functional coatings on a variety of different materials through auto-oxidative surface polymerization in a manner similar to polydopamine coatings. However, the mechanisms behind the coating deposition are poorly understood. We report the coating deposition kinetics of the polyphenol tannic acid (TA) and the simple phenolic compound pyrogallol (PG) on titanium surfaces. The coating deposition was followed in real time over a period of 24 h using a quartz crystal microbalance with dissipation monitoring (QCM-D). TA coatings revealed a multiphasic layer formation: the deposition of an initial rigid layer was followed by the buildup of an increasingly dissipative layer, before mass adsorption stopped after approximately 5 h of coating time. The PG deposition was biphasic, starting with the adsorption of a nonrigid viscoelastic layer which was followed by layer stiffening upon further mass adsorption. Coating evaluation by ellipsometry and AFM confirmed the deposition kinetics determined by QCM-D and revealed maximum coating thicknesses of approximately 50 and 75 nm for TA and PG, respectively. Chemical characterization of the coatings and polymerized polyphenol particles indicated the involvement of both physical and chemical interactions in the auto-oxidation reactions.

Drying activity of oxovanadium(IV) 2-ethylhexanoate in solvent-borne alkyd paints

Oxovanadium(IV) 2-ethylhexanoate was established as a new primary drier for alkyd-based paints. A series of experiments has demonstrated an excellent drying activity toward solvent-borne alkyd resins of different oil length at considerably lower metal concentration than optimal for commercial cobalt(II) 2-ethylhexanoate. The behavior in real paint was simulated on formulations bearing inhibitor of autooxidation. The detailed studies of the drying process have shown that the relatively slow initial step of autooxidation reaction, when compared with cobalt compounds, is compensated for by the absence of the induction times. Furthermore, the active oxovanadium(IV) species are not consumed during the drying processes as evidenced by EPR spectroscopic measurements.

Свойства водорастворимых окси-полигидрокси фуллеренов в реакции автоокисления адреналина

Normal 0 false false false RU X-NONE X-NONE The studied of the influence of fullerenoles on adrenaline auto-oxidation reaction by optical and theoretical methods was carried out in this work. It was shown that fullerenols at concentrations from 0.0005 mg/ml to 0.5 mg/ml exhibits prooxidant activity and accelerates autoxidation reaction of adrenaline. The suggested scheme of auto-oxidation reaction, which explained by energy advantage under transferring electron from the molecule of adrenaline to fullerenol by density functional method B3LYP/6-31(p,d). /* Style Definitions */ table.MsoNormalTable {mso-style-name:Обычная таблица; mso-tstyle-rowband-size:0; mso-tstyle-colband-size:0; mso-style-noshow:yes; mso-style-priority:99; mso-style-qformat:yes; mso-style-parent:; mso-padding-alt:0cm 5.4pt 0cm 5.4pt; mso-para-margin:0cm; mso-para-margin-bottom:.0001pt; mso-pagination:widow-orphan; font-size:11.0pt; font-family:Calibri,sans-serif; mso-ascii-font-family:Calibri; mso-ascii-theme-font:minor-latin; mso-fareast-font-family:Times New Roman; mso-fareast-theme-font:minor-fareast; mso-hansi-font-family:Calibri; mso-hansi-theme-font:minor-latin; mso-bidi-font-family:Times New Roman; mso-bidi-theme-font:minor-bidi;}

Involvement of carbonate/bicarbonate ions in the superoxide-generating reaction of adrenaline autoxidation

An important role of carbonate/bicarbonate ions has been recognized in the superoxide generating reaction of adrenaline autooxidation in an alkaline buffer (a model of quinoid adrenaline oxidation in the body). It is suggested that these ions are directly involved not only in formation of superoxide anion radical (О(2)(-)) but also other radicals derived from the carbonate/bicarbonate buffer. Using various buffers it was shown that the rate of accumulation of adrenochrome, the end product of adrenaline oxidation, and the rate of О(2)(-)· formation depend on concentration of carbonate/bicarbonate ions in the buffer and that these ions significantly accelerate adrenaline autooxidation thus demonstrating prooxidant properties. The detectable amount of diformazan, the product of nitro blue tetrazolium (NBT) reduction, was significantly higher than the amount of adrenochrome formed; taking into consideration the literature data on О(2)(-)· detection by NBT it is suggested that adrenaline autooxidation is accompanied by one-electron reduction not only of oxygen dissolved in the buffer and responsible for superoxide formation but possible carbon dioxide also dissolved in the buffer as well as carbonate/bicarbonate buffer components leading to formation of corresponding radicals. The plots of the dependence of the inhibition of adrenochrome and diformazan formation on the superoxide dismutase concentration have shown that not only superoxide radicals are formed during adrenaline autooxidation. Since carbonate/bicarbonate ions are known to be universally present in the living nature, their involvement in free radical processes proceeding in the organism is discussed.

FTIR study of ageing of fast drying oil colour (FDOC) alkyd paint replicas

We propose ATR-FTIR spectroscopy for the characterization of the spectral changes in alkyd resin from the Griffin Alkyd Fast Drying Oil Colour range (Winsor & Newton), occurring over 550days (∼18months) of natural ageing and over six months of artificial ageing under an acetic acid atmosphere. Acetic acid is one of the atmospheric pollutants found inside museums in concentrations that can have a significant effect on the works exhibited. During natural ageing we observed an increase and broadening of the OH group band around 3300cm−1 and an increase in bands in the region 1730–1680cm−1 due to carbonyl stretching. We found a broad band around 1635cm−1 likely due to CO stretching vibrations of β dichetons. These spectral changes are the result of autooxidation reactions during natural ageing and crosslinking, which then form f alcohols and carbonyl species. The increase in absorbance at 1635cm−1 was selected as a parameter to monitor the ageing process of paintings prepared with FDOC, without the need for any extractive procedure. FTIR spectra of paint replicas kept under an acetic acid atmosphere indicated the chemical groups involved in the reaction with acid, thus suggesting which spectral FTIR regions could be investigated in order to follow any degradation in real paintings. A red paint sample from a hyper-realistic artwork (“Racconta storie”, 2003) by the Italian painter Patrizia Zara was investigated by FTIR in order to evaluate the effects of 10years natural ageing on alkyd colours. The results obtained suggested that after the end of chemical drying (autooxidation), alkyd colours are very stable.

Characterization of the Triplet State of Tanshinone IIA and its Reactivity by Laser Flash Photolysis

Tanshinone IIA (Tan IIA) has the properties of cardiovascular protection, anti-inflammation, antioxidation and anticancer. Its light-induced instability has drawn our interests in its photochemistry. Therefore, laser flash photolysis herein was used to investigate the transient photochemistry of Tan IIA. Our results show that direct photoexcitation by 355 nm laser pulses or photosensitization by energy transfer can lead to the formation of the triplet state of Tan IIA ((3)Tan IIA*). The triplet absorption spectrum and molar absorption coefficient, and ISC quantum yield were determined. Self-quenching of (3)Tan IIA* by its ground state was identified as an autooxidation reaction. (3)Tan IIA* was proved to react quickly with N, N-dimethylaniline, tert-butylhydroquinone and propyl gallate via electron transfer with the diffusion-controlled rate constants. One of the products with maximum absorption around 390 nm was assigned to the radical anion of Tan IIA. Our results indicate that (3)Tan IIA* is a reactive transient species and can be generated by photosensitization or direct photoexcitation. According to our results, the possible role of Tan IIA as a photosensitizer to induce potential phototoxicity via Type-II pathway in the presence of O2 can be predicted.

Decolourisation of Acid Orange 7 recalcitrant auto-oxidation coloured by-products using an acclimatised mixed bacterial culture

This study focuses on the biodegradation of recalcitrant, coloured compounds resulting from auto-oxidation of Acid Orange 7 (AO7) in a sequential facultative anaerobic-aerobic treatment system. A novel mixed bacterial culture, BAC-ZS, consisting of Brevibacillus panacihumi strain ZB1, Lysinibacillus fusiformis strain ZB2, and Enterococcus faecalis strain ZL bacteria were isolated from environmental samples. The acclimatisation of the mixed culture was carried out in an AO7 decolourised solution. The acclimatised mixed culture showed 98 % decolourisation within 2 h of facultative anaerobic treatment using yeast extract and glucose as co-substrate. Subsequent aerobic post treatment caused auto-oxidation reaction forming dark coloured compounds that reduced the percentage decolourisation to 73 %. Interestingly, further agitations of the mixed culture in the solution over a period of 48 h significantly decolourise the coloured compounds and increased the decolourisation percentage to 90 %. Analyses of the degradation compounds using UV-visible spectrophotometer, Fourier transform infrared spectroscopy (FTIR) and high performance liquid chromatography (HPLC) showed complete degradation of recalcitrant AO7 by the novel BAC-ZS. Phytotoxicity tests using Cucumis sativus confirmed the dye solution after post aerobic treatment were less toxic compared to the parent dye. The quantitative real-time PCR revealed that E. faecalis strain ZL was the dominant strain in the acclimatised mix culture.

Oxidative coupling of 2-aminophenol to 2-amino-phenoxazine-3-one catalyzed by organotin (IV)–copper (I) cyanide coordination polymers as heterogeneous catalysts

The activity of organotin (IV)–copper (I) cyanide coordination polymers [Ph3SnCu (CN)2·L] where L=1,2-bis(4-pyridyl)ethane (bpe) 1, 4,4′-bipyridine (bpy) 2, methylpyrazine (mepyz) 3 or trans-1,2-bis(4-pyridyl)ethene (tbpe) 4 has been investigated as heterogeneous catalysts for the biomimetic oxidative coupling of 2-aminophenol (OAP) to 2-aminophenoxazine-3-one (APX). The rate of OAP consumption was determined by measuring the amount of dioxygen consumed using a gas burette. All the coordination polymeric catalysts showed high activity for auto-oxidation of OAP. The coordination polymer 4 has been found to be the most reactive catalyst. The rate of auto-oxidation reaction of OAP catalyzed by the coordination polymer 4 has been found to increase with increasing the pH from 7 to 9 then decreased at higher pH. The rate of auto-oxidation reaction showed linear dependence on catalyst concentration and pressure of dioxygen. The rate of reaction has been found to fit a Michaelis–Menten kinetic model for saturation of catalyst sites with increasing OAP concentration. The catalyst 4 showed no deactivation after six runs.

Penetration and haptenation of p‐phenylenediamine

Although p-phenylenediamine (PPD) has been recognized as an extreme sensitizer for many years, the exact mechanism of sensitization has not been elucidated yet. Penetration and the ability to bind to proteins are the first two hurdles that an allergen has to overcome to be able to sensitize. This review is an overview of studies regarding PPD penetration through skin (analogues) and studies on the amino acids that are targeted by PPD. To complete this review, the auto-oxidation and N-acetylation steps involved in PPD metabolism are described. In summary, under normal hair dyeing exposure conditions, <1% of the applied PPD dose penetrates the skin. The majority (>80%) of PPD that penetrates will be converted into the detoxification products monoacetyl-PPD and diacetyl-PPD by the N-acetyltransferase enzymes. The small amount of PPD that does not become N-acetylated is susceptible to auto-oxidation reactions, yielding protein-reactive PPD derivatives. These derivatives may bind to specific amino acids, and some of the formed adducts might be the complexes responsible for sensitization. However, true in vivo evidence is lacking, and further research to unravel the definite mechanism of sensitization is needed.

Use of nitro blue tetrazolium in the reaction of adrenaline autooxidation for the determination of superoxide dismutase activity

Addition of nitro blue tetrazolium (NBT) into the reaction of adrenaline autooxidation allows to identify directly superoxide anion formation (02.-) in this superoxide-generating system. The kinetics of formation of adrenochrome and 02.- were compared under the same conditions. Three possible approaches to the use the adrenaline autooxidation reaction for determining the activity of superoxide dismutase (SOD) and revealing the antioxidant properties of various compounds are discussed. Two of these approaches have been described previously: the spectrophotometric method of the registration of adrenochrome, the final product of adrenaline autoxidation, at 347 nm (Sirota, 1999) and the polarographic method, based on determination of oxygen consumption for 02.- formation (Sirota, 2011). Here, a novel approach to this problem is presented; it consists in the spectrophotometric determination of 02.- using NBT. The application of this approach enables one to lower the pH of carbonate buffer from 10.5 to 9.7 and to decrease (4-fold) the amount of added adrenaline, i.e., to generate milder and more effective conditions for revealing and studying the antioxidant properties of examined materials.

The Hydroperoxide Lyase Branch of the Oxylipin Pathway and Green Leaf Volatiles in Plant/Insect Interaction

The lipoxygenase (LOX) catalysed peroxidation of polyunsaturated fatty acids (PUFA) is a key starting point in defence mechanisms common to plant, animal and at least some microorganisms. In human, the peroxidation of arachidonic acid finally leads to the biosynthesis of important defence effectors such as leukotrienes and lipoxins. In plant, the most common substrates of lipoxygenases are represented by linoleic (C18:2) and linolenic (C18:3) acids. Differently from auto-oxidation reactions which produce a huge number of hydroperoxide derivatives, the oxidation reaction catalysed by LOXs is positional and stereo-specific. Indeed, only 9- or 13-hydroperoxides (with a prevalence of the S steroisomers) are produced from these substrates. PUFA hydroperoxides are per se signal molecules or can be used as substrates for a number of enzymatic reactions carried out by other enzymes of the LOX pathway. At the end, an array of volatile and non volatile compounds, collectively known as phyto-oxylipins are produced upon specific stress signals, by the contribution of a multitude of enzymes localised in different subcellular compartments. Thanks to the excellent work of several groups of scientists around the world, our knowledge on the contribution of the oxylipin pathway on plant defence mechanisms dramatically increased in recent years. In the present contribution, we’ll focus our attention on the hydroperoxide lyase branch of the plant oxylipins pathway, responsible for the synthesis of volatile aldehydes, alcohols and other related compounds which are important constituents of fruit aromas and the green leaf volatiles.

Selective Cytotoxicity of a Grape Seed Proanthocyanidin Extract to Human Oral Carcinoma HSC-2 Cells

Grape seed extract (GSE), a nutraceutical rich in polyphenol proanthocyanidins, was evaluated for its toxicity to human oral cells. Using the neutral red cytotoxicity assay, human squamous carcinoma (HSC-2) cells were shown to be more sensitive to GSE than were gingival fibroblasts. Polyphenols undergo auto-oxidation reactions in cell culture medium, to generate reactive oxygen species, in particular, hydrogen peroxide. Using the FOX assay to quantify hydrogen peroxide, GSE, when added to cell culture medium, generated hydrogen peroxide, albeit at relatively low levels. No hydrogen peroxide was detected in the presence of catalase, which catalyzes the decomposition of hydrogen peroxide, and minor levels were detected in the presence of superoxide dismutase, which stabilizes polyphenols. Superoxide free radical, detected with nitroblue tetrazolium, was identified in GSE-amended medium. Focusing on carcinoma HSC-2 cells, the 24-hr toxicity of GSE was unaffected by the hydrogen peroxide scavengers, catalase and pyruvate, indicating that hydrogen peroxide played no role in toxicity. For HSC-2 cells cotreated with GSE and D,L-buthionine-[S,R]-sulfoximine, a depleter of intracellular glutathione, no potentiation of toxicity occurred. Over the 24 hr toxicity range, GSE did not affect the level of intracellular glutathione; however, some depletion occurred, but only at elevated GSE concentrations. GSE toxicity, apparently, was independent of oxidative stress. The 24-hr cytotoxicity of GSE to HSC-2 cells was potentiated in the presence of SOD, indicating that the proanthocyanidins per se, rather than their auto-oxidation products, accounted for toxicity. To confirm the instability of GSE in cell culture medium with a concomitant lowering of potency, studies compared medium freshly-amended with GSE to “spent” medium, i.e., GSE-amended medium left in the incubator for 24 hr prior to usage. The potency of GSE to HSC-2 cells was significantly lowered following incubated in “spent” medium for 24 hours.

Use of nitro blue tetrazolium in the reaction of adrenaline autooxidation for the determination of superoxide dismutase activity

Use of nitro blue tetrazolium in the reaction of adrenaline autooxidation for the determination of superoxide dismutase activity

Spin Trapping Studies of Amine-Stabilized Trialkylborane Free Radical Initiator Systems: Kinetics and Mechanism

The free radical initiation chemistry of highly reactive trialkylboranes (R3B, R = n-butyl), stabilized by complexation to amines (A–R3B), has been investigated using spin trapping methods and electron paramagnetic resonance spectroscopy. Protonation of A–R3B leads to release of R3B and its subsequent autooxidation in the presence of molecular oxygen. This reaction provides highly reactive alkyl and alkoxy radicals for initiation of α–olefin polymerization. Kinetic traces of the R3B autooxidation reaction were obtained by monitoring the relative concentrations of trapped radical species as a function of time for several different initial conditions (acid concentrations). Analysis of a representative kinetic run is discussed in terms of several proposed mechanisms from the literature.

A novel approach to study the reaction of adrenaline autooxidation: A possibility for polarographic determination of superoxide dismutase activity and antioxidant properties of various preparations

The reaction of adrenaline autooxidation in an alkaline carbonate buffer followed by formation of superoxide radicals and the product of its oxidation, adrenochrome, which models the quinone pathway of adrenaline metabolism in the body, is accompanied by oxygen consumption. A study of this process by the polarographic method enabled one to apply this reaction to determine the activity of superoxide dismutase and antioxidant properties of biological and chemical compounds; it is based on evaluation of a latent period and the rate of oxygen consumption, which are measured in the presence of examined compounds. It was suggested that known neuroand cardiotoxicity of the quinone products of adrenaline oxidation may be associated not only to their intrinsic properties and reactive oxygen species formed but also local hypoxia of those regions of the cell and tissue where the quinone oxidation of adrenaline occurs.