Cited by 137Antioxidant Activity and Oxidative StressRedox biology and oxidative stressFree Radicals and Antioxidants

Linoleic Acid Hydroperoxide Reacts With Hypochlorous Acid, Generating Peroxyl Radical Intermediates and Singlet Molecular Oxygen

Open access
Miyamoto, Sayuri, Martinez, Glaucia R., Rettori, Daniel, Augusto, Ohara, Medeiros, Marisa H. G., Di Mascio, Paolo·2006·Proceedings of the National Academy of Sciences

Abstract

The reaction of hypochlorous acid (HOCl) with hydrogen peroxide is known to generate stoichiometric amounts of singlet molecular oxygen [O2 (1Deltag)]. This study shows that HOCl can also react with linoleic acid hydroperoxide (LAOOH), generating O2 (1Deltag) with a yield of 13 +/- 2% at physiological pH. Characteristic light emission at 1,270 nm, corresponding to O2 (1Deltag) monomolecular decay, was observed when HOCl was reacted with LAOOH or with liposomes containing phosphatidylcholine hydroperoxides, but not with cumene hydroperoxide or tert-butyl hydroperoxide. The generation of O2 (1Deltag) was confirmed by the acquisition of the spectrum of the light emitted in the near-infrared region showing a band with maximum intensity at 1,270 nm and by the observation of the enhancing effect of deuterium oxide and the quenching effect of sodium azide. Mechanistic studies using 18O-labeled linoleic acid hydroperoxide (LA18O18OH) showed that its reaction with HOCl yields 18O-labeled O2 (1Deltag) [18O2 (1Deltag)], demonstrating that the oxygen atoms in O2 (1Deltag) are derived from the hydroperoxide group. Direct analysis of radical intermediates in the reaction of LAOOH with HOCl by continuous-flow electron paramagnetic resonance spectroscopy showed a doublet signal with a g-value of 2.014 and a hyperfine coupling constant from the alpha-hydrogen of a(H) = 4.3 G, indicating the formation of peroxyl radicals. Taken together, our results clearly demonstrate that HOCl reacts with biologically relevant lipid hydroperoxides, generating O2 (1Deltag). In addition, the detection of 18O2 (1Deltag) and peroxyl radicals strongly supports the involvement of a Russell mechanism in the generation of O2 (1Deltag).

Integrity signals

Registry

Crossref · 10.1073/pnas.0508170103

Cites

69 of 69 references verified0 citation errors · 0 not checkable

Statistics

Recomputing p-values needs the paper’s full text.

Claims the paper makes

We couldn’t retrieve this paper’s full text, so its claims and self-check weren’t run. The registry and citation checks still apply.

Claims other papers make about this one

Each is checked against this paper’s own text: does it say what the citing paper says it does?

  • HOCl-dependent formation of singlet oxygen has been documented without mechanistic involvement of photons downstream of peroxide, superoxide, or chloramine chemistry involving the chemical formation of photo-excited states ('chemiexcitation').

    “HOCl-dependent formation of highly reactive photoexcited molecular oxygen [1O2 (singlet oxygen)] has been documented without mechanistic involvement of photons downstream of peroxide (including linoleic acid hydroperoxide), superoxide, or chloramine chemistry involving the chemical formation of photo-excited states (commonly referred to as ‘chemiexcitation’) (69–71).”

Cites

Flagged first, then by citations

Cited by

Sorted by citations

Authors
Miyamoto, S., Martinez, G. R., Rettori, D., Augusto, O., Medeiros, M. H. G., & Di Mascio, P.
Affiliations
  • Universidade de São Paulo (BR)
  • Departamento de Bioquímica, Instituto de Química, Universidade de São Paulo, CP26077, CEP 05513-970, São Paulo, Brazil
  • National Institutes of Health (US)
Venue
Proceedings of the National Academy of Sciences
Published
2005-12-30
Volume
103
Issue
2
Pages
293-298
ISSN
  • 0027-8424 (ISSN-L)
  • 1091-6490
OpenAlex
W2011222045
Cited by
137
References
69
Citations by year
2026: 1 · 2025: 2 · 2024: 7 · 2023: 9 · 2022: 2 · 2021: 7 · 2020: 9 · 2019: 13 · 2018: 3 · 2017: 12 · 2016: 8 · 2015: 8 · 2014: 10 · 2013: 8 · 2012: 7
FWCI
2.55
Type
journal article
Language
en
Open access
Locations
  • Proceedings of the National Academy of Sciences (publishedVersion)
  • Europe PMC (PubMed Central) (publishedVersion)
  • PubMed Central (publishedVersion)
  • PubMed (publishedVersion)
Topics
  • Health Sciences › Medicine › Biochemistry › Antioxidant Activity and Oxidative Stress
  • Life Sciences › Biochemistry, Genetics and Molecular Biology › Molecular Biology › Redox biology and oxidative stress
  • Physical Sciences › Chemistry › Organic Chemistry › Free Radicals and Antioxidants
Keywords
singlet oxygen, hypochlorous acid, linoleic acid hydroperoxide, lipid hydroperoxides, peroxy radicals, phosphatidylcholine hydroperoxide, liposomes, electron spin resonance
MeSH terms
Hydrogen Peroxide, Hydrogen-Ion Concentration, Hypochlorous Acid, Linoleic Acids, Lipid Peroxides, Liposomes, Peroxides, Phospholipids, Spectrum Analysis, Molecular Structure, Singlet Oxygen

About these checks

Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.

Statistics and arithmetic are recomputed, not judged.

Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.

What counts as a claim ›How we measure confidence ›How we check this ›

Are you an author, or do you see a problem with this page? Request a review