Yields of singlet molecular oxygen from peroxyl radical termination

Niu, Qingfen; Mendenhall, G. D.

doi:10.1021/ja00027a024

Cited by 69 publications

(43 citation statements)

References 2 publications

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“…The termination of peroxyl radicals via the concerted process results in the production of lipid ketones and alcohols [35]. This is consistent with the HPLC data and previous GC-MS studies showing two of the major products to be HODE and OODE.…”

Section: Figure 6 Hplc Analysis Of the Products Of The Reaction Betwesupporting

confidence: 80%

Mechanism of reaction of myoglobin with the lipid hydroperoxide hydroperoxyoctadecadienoic acid

Reeder

Wilson

1998

Biochemical Journal

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The reaction between myoglobin and the lipid hydroperoxide 13(S)-hydroperoxy-9,11(cis,trans)-octadecadienoic acid (HPODE) was studied kinetically by spectrophotometric, polarographic and analytical methods. Metmyoglobin catalysed the decomposition of HPODE, resulting in peroxide, oxygen and conjugated diene depletion, together with the transient production of ferryl myoglobin. The reaction stoichiometry was 2:1:1 for peroxide to oxygen to conjugated diene, whereas the myoglobin remained generally intact. This stoichiometry and the rates of change of conjugated diene and ferryl myoglobin concentrations were not completely consistent with previously proposed mechanisms. We propose a novel mechanism in which HPODE reacts with both ferric myoglobin and ferryl myoglobin to form a redox cycle. Both peroxyl and alkoxyl radicals are produced, explaining the observed stoichiometry of peroxide, oxygen and conjugated diene depletion and the transient appearance of ferryl myoglobin. Computer simulation shows that this mechanism is fully capable of reproducing the observed time courses of all components.

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Section: Figure 6 Hplc Analysis Of the Products Of The Reaction Betwesupporting

confidence: 80%

Mechanism of reaction of myoglobin with the lipid hydroperoxide hydroperoxyoctadecadienoic acid

Reeder

Wilson

1998

Biochemical Journal

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“…[25] The structural influence on the singlet oxygen yield was confirmed by Mendenhall and Niu, who reported values of 0 (tertiary) and 4-13 % (primary, secondary). [26] Together with the observed kinetic isotope effect, [24] these findings provided strong experimental evidence for the Russell rearrangement [27] of the tetroxide, leading to termination [Reaction (2)]. Recently, Peeters et al proposed a mechanism to explain the formation of singlet oxygen, via a five-membered, cyclic transition state.…”

mentioning

confidence: 84%

Peculiarities of β‐Pinene Autoxidation

2011

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The thermal oxidation of the renewable olefin β-pinene with molecular oxygen was experimentally and computationally investigated. Peroxyl radicals abstract weakly bonded allylic hydrogen atoms from the substrate, yielding allylic hydroperoxides (i.e., myrtenyl and pinocarvyl hydroperoxide). In addition, peroxyl radicals add to the C=C bond of the substrate to form an epoxide. It was found that a relatively high peroxyl radical concentration, together with the high rate of peroxyl cross-reactions, make radical-radical reactions surprisingly important for this particular substrate. Approximately 60 % of these peroxyl cross-reactions lead to termination (radical destruction), keeping a radical chain length of approximately 4 at 10 % conversion. Numerical simulation of the reaction-based on the proposed reaction mechanism and known or predicted rate constants-demonstrate the importance of peroxyl cross-reactions for the formation of alkoxyl radicals, which are the precursor of alcohol and ketone products.

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“…Actually, hydrotrioxides generate singlet oxygen with high efficiency, 40,41 while disproportionation of peroxyls usually gives small yields of 1 O 2 . 46 At the same time, the formation of excited carbonyls in reactions (7) and (13) proceeds with comparable efficiencies, 9 2 % 9 2 '. Such ratios of quantum yields explain the absence of infrared CL in the first stage of the HT decomposition and the two regions in the kinetic curves of visible CL.…”

Section: Mechanism Of Decomposition Of Hydrotrioxidesmentioning

confidence: 94%

“…35,46 Since quenching of CL emitters by hydroperoxide is negligible, the only explanation for the CL attenuation is the exchange of radicals according to reactions (14) and (15). Residual CL arises from incomplete capture of RO Á and HOO Á radicals by hydroperoxide.…”

Section: Mechanism Of Decomposition Of Hydrotrioxidesmentioning

confidence: 99%

Formation of hydrotrioxides during ozonation of hydrocarbons on silica gel. Decomposition of hydrotrioxides

Avzyanova

Timerghazin

Khalizov

et al. 2000

J. Phys. Org. Chem.

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Hydrotrioxides (HT), ROOOH, from isopentane, 1,4-dimethylcyclohexane, 1,3-dimethylcyclohexane, decalin and triphenylmethane were synthesized for the first time by low-temperature ozonation of the corresponding hydrocarbons on a silica surface. Thermal decomposition of hydrotrioxides is accompanied by the formation of radicals and by infrared and visible chemiluminescence (CL). In solution the HTs form self-associates and react reversibly with the solvent (acetone) producing Bayer-Villiger type intermediates (unsymmetrical dialkyl trioxides). These reactions cause a complex character of the decomposition kinetics of HTs, as evidenced by monitoring the dependence of CL intensity on time. Activation parameters of thermal decomposition of HTs show a compensation effect (logA vs E A ) which describes well the available experimental and theoretical data for the homolysis of organic trioxides.

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Yields of singlet molecular oxygen from peroxyl radical termination

Cited by 69 publications

References 2 publications

Mechanism of reaction of myoglobin with the lipid hydroperoxide hydroperoxyoctadecadienoic acid

Mechanism of reaction of myoglobin with the lipid hydroperoxide hydroperoxyoctadecadienoic acid

Peculiarities of β‐Pinene Autoxidation

Formation of hydrotrioxides during ozonation of hydrocarbons on silica gel. Decomposition of hydrotrioxides

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