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Superoxide- and semiquinone-linked activation of molecular hydrogen in metal-catalyst-free solution.

金属触媒非存在下におけるスーパーオキシドおよびセミキノンを介した分子状水素の活性化機構

in vitro study in vitro positive

Abstract

This in vitro study examined the chemical basis by which molecular hydrogen (H2) modulates superoxide (O2•−) kinetics in metal-free, membrane-free aqueous conditions. Using xanthine oxidase/hypoxanthine and potassium superoxide systems alongside the O2•−-specific chemiluminescent probe MPEC, bell-shaped and U-shaped kinetic profiles were recorded as a function of H2 concentration. In the absence of ubiquinone (Q), a bell-shaped profile consistent with tunneling-assisted electron transfer from H2 to O2•− was observed. When Q was included, U-shaped profiles emerged, suggesting semiquinone radical (Q•−)-mediated electron buffering followed by ubiquinol (QH2) formation. ESR radical scavenging experiments and quantitative HPLC analyses corroborated transient semiquinone-driven redox cycling. These findings establish the chemical feasibility of H2 participating in Q redox cycling via a metal-free, tunneling-compatible pathway, with physiological relevance yet to be determined.

Mechanism

H2 undergoes tunneling-assisted electron transfer to superoxide; in the presence of ubiquinone, semiquinone radicals act as electron buffers, ultimately driving ubiquinol formation through a metal-free redox cycling pathway.

Bibliographic

Authors
Ishibashi T, Harunari E, Ishihara G, Niiyama T, Noda-Urata M, Komori N
Journal
Front Mol Biosci
Year
2025
PMID
41195421
DOI
10.3389/fmolb.2025.1680812
PMC
PMC12582930

Tags

Disease:虚血再灌流障害 Mechanism:抗酸化酵素 ヒドロキシルラジカル消去 炎症抑制 ミトコンドリア 酸化ストレス 活性酸素種

Delivery context

This is basic research at the cellular or molecular level. For human application, inhalation is the most promising delivery route, but inhalation carries explosion risk and concentration matters (empirical LFL of 10%; high-concentration devices are not recommended).

Safety notes

This is basic research at the cellular or molecular level. For human application, inhalation is the most promising delivery route, but inhalation carries explosion risk and concentration matters (empirical LFL of 10%; high-concentration devices are not recommended).

See also:

Other papers on the same disease / condition

Cite as: H2 Papers — PMID 41195421. https://h2-papers.org/en/papers/41195421
Source: PubMed PMID 41195421