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Peer-reviewedCC BY-NC-ND 4.0Journal of Clinical Biochemistry and Nutrition

Molecular characterization of the hypochlorite peroxyl radical (OClOO•), a reactive agent in acidic chlorite solutions and a potentially new disinfectant

  • Ayuta Kishimoto1
  • Yuta Okada2
  • Kenta Sugiyama2
  • Kazutomo Yamazaki3
  • Azham Zulkharnain3
  • Hiroumi Tamoi4
  • Masatoshi Kidowaki4
  • Hisataka Goda5
  • Toshikazu Yoshikawa6
  • Masahiro Kohno1,6
  • Koji Fukui1,2
6 affiliations
  1. 1Molecular Cell Biology Laboratory, Department of Functional Control Systems, Graduate School of Engineering and Science, Shibaura Institute of Technology, Fukasaku 307, Minuma-ku, Saitama 337-8570, Japan
  2. 2Molecular Cell Biology Laboratory, Graduate School of Systems Engineering and Science, Shibaura Institute of Technology, Fukasaku 307, Minuma-ku, Saitama 337-8570, Japan
  3. 3Molecular Microbiology Laboratory, Department of Bioscience and Engineering, College of Systems Engineering and Science, Shibaura Institute of Technology, Fukasaku 307, Minuma-ku, Saitama 337-8570, Japan
  4. 4Functional Organic Chemistry Laboratory, Course of Chemistry and Biotechnology, Program of Chemistry and Materials, College of Engineering, Shibaura Institute of Technology, Toyosu 3-7-5, Koto-ku, Tokyo 135-8548, Japan
  5. 5Sankei Co. Ltd., Shiromi 2-2-53, Chuo-ku, Osaka 540-0001, Japan
  6. 6Louis Pasteur Center for Medical Research, Tanaka Monzen-cho 103-5, Sakyo-ku, Kyoto 606-8225, Japan
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Abstract

The COVID-19 pandemic led to a global increase in the use of disinfectants such as sodium hypochlorite (NaOCl) and sodium chlorite (NaClO2). NaClO2 is generally recognized as safe (GRAS) and exhibits strong bactericidal activity when converted to acidified sodium chlorite (ASC) immediately before use. Although ASC is effective against various pathogens, including coronaviruses, the chemical species responsible for its bactericidal activity and the underlying disinfection mechanisms remain unclear. In this study, the reactions of NaOCl and NaClO2 under acidic conditions were investigated using UV-visible spectrophotometry (UV-vis), ion chromatography (IC), electron spin resonance (ESR), and mass spectrometry (MS). ESR analysis detected an unknown chlorine-containing peroxyl radical species (X-OO•), whose spectroscopic characteristics were consistent with a radical containing chlorine and oxygen atoms based on its hyperfine coupling constants and g values. MS analysis further provided evidence consistent with the presence of an OClO-containing dimetric species. Because NaClO2 is generally produced through reactions involving chlorine dioxide and sodium hydroxide (NaOH), such a dimetric species may be present as a relatively stable species in solution. Based on the combined experimental findings, we propose that the detected X-OO• species is a novel hypochlorite peroxyl radical (OClOO•) generated through reactions between NaClO2 and NaOCl under acidic conditions. Furthermore, bacterial inactivation was enhanced under conditions that promoted radical formation. Collectively, these findings suggest that OClOO• may contribute substantially to the bactericidal activity of ASC and provide new insights into the chemical basis of chlorine-based disinfectants.

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Cite

BibTeXRIS
BibTeX
@article{kishimoto2026molecular,
  title = {{Molecular characterization of the hypochlorite peroxyl radical (OClOO•), a reactive agent in acidic chlorite solutions and a potentially new disinfectant}},
  author = {Ayuta Kishimoto and Yuta Okada and Kenta Sugiyama and Kazutomo Yamazaki and Azham Zulkharnain and Hiroumi Tamoi and Masatoshi Kidowaki and Hisataka Goda and Toshikazu Yoshikawa and Masahiro Kohno and Koji Fukui},
  journal = {Journal of Clinical Biochemistry and Nutrition},
  year = {2026},
  month = sep,
  doi = {10.3164/jcbn.26-137},
  url = {https://doi.org/10.3164/jcbn.26-137},
  note = {CC BY-NC-ND 4.0},
}
RIS
TY  - JOUR
TI  - Molecular characterization of the hypochlorite peroxyl radical (OClOO•), a reactive agent in acidic chlorite solutions and a potentially new disinfectant
AU  - Ayuta Kishimoto
AU  - Yuta Okada
AU  - Kenta Sugiyama
AU  - Kazutomo Yamazaki
AU  - Azham Zulkharnain
AU  - Hiroumi Tamoi
AU  - Masatoshi Kidowaki
AU  - Hisataka Goda
AU  - Toshikazu Yoshikawa
AU  - Masahiro Kohno
AU  - Koji Fukui
PY  - 2026
DA  - 2026/09/30
JO  - Journal of Clinical Biochemistry and Nutrition
DO  - 10.3164/jcbn.26-137
UR  - https://doi.org/10.3164/jcbn.26-137
AB  - The COVID-19 pandemic led to a global increase in the use of disinfectants such as sodium hypochlorite (NaOCl) and sodium chlorite (NaClO2). NaClO2 is generally recognized as safe (GRAS) and exhibits strong bactericidal activity when converted to acidified sodium chlorite (ASC) immediately before use. Although ASC is effective against various pathogens, including coronaviruses, the chemical species responsible for its bactericidal activity and the underlying disinfection mechanisms remain unclear. In this study, the reactions of NaOCl and NaClO2 under acidic conditions were investigated using UV-visible spectrophotometry (UV-vis), ion chromatography (IC), electron spin resonance (ESR), and mass spectrometry (MS). ESR analysis detected an unknown chlorine-containing peroxyl radical species (X-OO•), whose spectroscopic characteristics were consistent with a radical containing chlorine and oxygen atoms based on its hyperfine coupling constants and g values. MS analysis further provided evidence consistent with the presence of an OClO-containing dimetric species. Because NaClO2 is generally produced through reactions involving chlorine dioxide and sodium hydroxide (NaOH), such a dimetric species may be present as a relatively stable species in solution. Based on the combined experimental findings, we propose that the detected X-OO• species is a novel hypochlorite peroxyl radical (OClOO•) generated through reactions between NaClO2 and NaOCl under acidic conditions. Furthermore, bacterial inactivation was enhanced under conditions that promoted radical formation. Collectively, these findings suggest that OClOO• may contribute substantially to the bactericidal activity of ASC and provide new insights into the chemical basis of chlorine-based disinfectants.
SN  - 0912-0009
SN  - 1880-5086
ER  -