Kinetics and Mechanism of Bilirubin Oxidation by Benzoyl Peroxide in Dimethyl Sulfoxide

ABSTRACT The kinetics of the redox reaction of bilirubin by the action of benzoyl peroxide in dimethyl sulfoxide was analyzed. It is shown that the first reaction product is biliverdin, which oxidizes to purpurin and further to choletelin. The kinetic and activation parameters of the oxidation react...

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Published inInternational journal of chemical kinetics Vol. 47; no. 1; pp. 27 - 35
Main Authors SEREBRYAKOVA, MARIA K., SOLOMONOV, ALEXEY V., RUMYANTSEV, EVGENIY V., IVANOV, SERGEI P.
Format Journal Article
LanguageEnglish
French
German
Published Hoboken Blackwell Publishing Ltd 01.01.2015
Wiley Subscription Services, Inc
Subjects
Free radicals
Oxidation
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Summary:ABSTRACT The kinetics of the redox reaction of bilirubin by the action of benzoyl peroxide in dimethyl sulfoxide was analyzed. It is shown that the first reaction product is biliverdin, which oxidizes to purpurin and further to choletelin. The kinetic and activation parameters of the oxidation reactions were obtained. A kinetic model of the process was proposed. An assumed route of the reaction is related to the exchange interaction of CH protons of methylene and methine spacers with free radicals in the rate‐limiting step with the further destruction of the “ridge‐tile” pigment conformation. The mechanism steps are confirmed by quantum‐chemical calculations and HPLC. It is found that in organic solvents the end products of bilirubin oxidation are not monopyrrolic derivatives. The data obtained will be useful in constructing antioxidant action models of the pigment.
Bibliography:ark:/67375/WNG-78GWL30F-C
President of the Russian Federation - No. МК-287.2014.3 (2014-2015)
Jewish Agency for Israel and the Government of Israel - No. 1504994 (2014-2015)
Russian Foundation for Basic Research - No. 12-03-31309; No. 13-03-90743
ArticleID:KIN20889
Bursary of the President of the Russian Federation - No. SP-6898.2013.4 (2013-2015)
istex:6D713C8549FFB21216CDD91D33DF1D33BFFDC2DD
Contract grant sponsor: Russian Foundation for Basic Research.
Contract grant sponsor: President of the Russian Federation.
Contract grant number: МК‐287.2014.3 (2014–2015).
Contract grant sponsor: Jewish Agency for Israel and the Government of Israel.
Contract grant number: 12‐03‐31309, 13‐03‐90743.
Contract grant sponsor: Bursary of the President of the Russian Federation.
Contract grant number: SP‐6898.2013.4 (2013–2015).
Contract grant number: 1504994 (2014–2015).
ISSN:0538-8066
1097-4601
DOI:10.1002/kin.20889