Photooxidation of Dipyrrinones: Reaction with Singlet Oxygen
and Characterization of Reaction Intermediates

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Photooxidation of Dipyrrinones: Reaction with Singlet Oxygen and Characterization of Reaction ...

Přehled o publikaci

J 2025

Photooxidation of Dipyrrinones: Reaction with Singlet Oxygen and Characterization of Reaction Intermediates

MADEA, Dominik; Júlia PEŇÁKOVÁ; Jaya MEHARA; Rikuo AKISAKA; Marek MARTÍNEK et. al.

Basic information

Original name

Photooxidation of Dipyrrinones: Reaction with Singlet Oxygen and Characterization of Reaction Intermediates

Authors

MADEA, Dominik; Júlia PEŇÁKOVÁ; Jaya MEHARA; Rikuo AKISAKA; Marek MARTÍNEK; Jana ROITHOVÁ and Petr KLÁN

Edition

Journal of Organic Chemistry, WASHINGTON, AMER CHEMICAL SOC, 2025, 0022-3263

Other information

Language

English

Type of outcome

Article in a journal

Country of publisher

United States of America

Confidentiality degree

is not subject to a state or trade secret

References:

URL

Organization

Přírodovědecká fakulta – Repository – Repository

DOI

http://dx.doi.org/10.1021/acs.joc.4c02954

UT WoS

001415261700001

EID Scopus

2-s2.0-85217244925

Keywords in English

DYE-SENSITIZED PHOTOOXYGENATION; REVERSIBLE-E PHOTOISOMERIZATION; ELECTRON-TRANSFER; PYRROLE PHOTOOXIDATION; AQUEOUS-SOLUTION; BILIRUBIN; OXIDATION; CHEMILUMINESCENCE; PRODUCTS; PROPENTDYOPENTS

Links

GA22-27598S, research and development project. LM2023069, research and development project. 857560, interní kód Repo.

Changed: 19/6/2025 00:50, RNDr. Daniel Jakubík

Abstract

V originále

Bilirubin (BR) is a water-insoluble product of heme catabolism in mammals. Elevated blood concentrations of BR, especially in the neonatal period, are treated with blue-green light phototherapy. The major mechanism of BR elimination during phototherapy is photoisomerization, while a minor, less studied mechanism of degradation is oxidation. In this work, we studied the oxidation of the bilirubin model tetramethyl-dipyrrinone (Z-13) by singlet oxygen in methanol using UV-vis and ESI-MS spectroscopy, resulting in propentdyopents as the main oxidation products. We also identified two additional intermediates that were formed during the reaction (hydroperoxide 21a and imine 17). The structure of the hydroperoxide was confirmed by helium-tagging IR spectroscopy. Such reaction intermediates formed during the oxidation of BR or bilirubin models have not been described so far. We believe that this work can be used as a first step in studying the complex oxidation mechanism of BR during phototherapy.

Files attached

https://is.muni.cz/publication/2483613/2483613.pdf

Cite

MADEA, Dominik; Júlia PEŇÁKOVÁ; Jaya MEHARA; Rikuo AKISAKA; Marek MARTÍNEK; Jana ROITHOVÁ and Petr KLÁN. Photooxidation of Dipyrrinones: Reaction with Singlet Oxygen and Characterization of Reaction Intermediates. Journal of Organic Chemistry. WASHINGTON: AMER CHEMICAL SOC, 2025, vol. 90, No 6, p. 2403-2420. ISSN 0022-3263. Available from: https://dx.doi.org/10.1021/acs.joc.4c02954.

@article{69556,
   author = {Madea, Dominik and Peňáková, Júlia and Mehara, Jaya and Akisaka, Rikuo and Martínek, Marek and Roithová, Jana and Klán, Petr},
   article_location = {WASHINGTON},
   article_number = {6},
   doi = {http://dx.doi.org/10.1021/acs.joc.4c02954},
   keywords = {DYE-SENSITIZED PHOTOOXYGENATION; REVERSIBLE-E PHOTOISOMERIZATION; ELECTRON-TRANSFER; PYRROLE PHOTOOXIDATION; AQUEOUS-SOLUTION; BILIRUBIN; OXIDATION; CHEMILUMINESCENCE; PRODUCTS; PROPENTDYOPENTS},
   language = {eng},
   issn = {0022-3263},
   journal = {Journal of Organic Chemistry},
   title = {Photooxidation of Dipyrrinones: Reaction with Singlet Oxygen and Characterization of Reaction Intermediates},
   url = {https://pubs.acs.org/doi/10.1021/acs.joc.4c02954},
   volume = {90},
   year = {2025}
}

TY  - JOUR
ID  - 69556
AU  - Madea, Dominik - Peňáková, Júlia - Mehara, Jaya - Akisaka, Rikuo - Martínek, Marek - Roithová, Jana - Klán, Petr
PY  - 2025
TI  - Photooxidation of Dipyrrinones: Reaction with Singlet Oxygen and Characterization of Reaction Intermediates
JF  - Journal of Organic Chemistry
VL  - 90
IS  - 6
SP  - 2403-2420
EP  - 2403-2420
PB  - AMER CHEMICAL SOC
SN  - 0022-3263
KW  - DYE-SENSITIZED PHOTOOXYGENATION
KW  - REVERSIBLE-E PHOTOISOMERIZATION
KW  - ELECTRON-TRANSFER
KW  - PYRROLE PHOTOOXIDATION
KW  - AQUEOUS-SOLUTION
KW  - BILIRUBIN
KW  - OXIDATION
KW  - CHEMILUMINESCENCE
KW  - PRODUCTS
KW  - PROPENTDYOPENTS
UR  - https://pubs.acs.org/doi/10.1021/acs.joc.4c02954
N2  - Bilirubin (BR) is a water-insoluble product of heme catabolism in mammals. Elevated blood concentrations of BR, especially in the neonatal period, are treated with blue-green light phototherapy. The major mechanism of BR elimination during phototherapy is photoisomerization, while a minor, less studied mechanism of degradation is oxidation. In this work, we studied the oxidation of the bilirubin model tetramethyl-dipyrrinone (Z-13) by singlet oxygen in methanol using UV-vis and ESI-MS spectroscopy, resulting in propentdyopents as the main oxidation products. We also identified two additional intermediates that were formed during the reaction (hydroperoxide 21a and imine 17). The structure of the hydroperoxide was confirmed by helium-tagging IR spectroscopy. Such reaction intermediates formed during the oxidation of BR or bilirubin models have not been described so far. We believe that this work can be used as a first step in studying the complex oxidation mechanism of BR during phototherapy.
ER  -

MADEA, Dominik; Júlia PEŇÁKOVÁ; Jaya MEHARA; Rikuo AKISAKA; Marek MARTÍNEK; Jana ROITHOVÁ and Petr KLÁN. Photooxidation of Dipyrrinones: Reaction with Singlet Oxygen and Characterization of Reaction Intermediates. \textit{Journal of Organic Chemistry}. WASHINGTON: AMER CHEMICAL SOC, 2025, vol.~90, No~6, p.~2403-2420. ISSN~0022-3263. Available from: https://dx.doi.org/10.1021/acs.joc.4c02954.