Photochemistry of (Z)-isovinylneoxanthobilirubic acid methyl ester, a bilirubin dipyrrinone subunit: femtosecond transient absorption and stimulated Raman emission spectroscopy

0568051 - FZÚ 2023 RIV US eng J - Journal Article
Madea, D. - Mujawar, T. - Dvořák, A. - Pospíšilová, K. - Muchová, L. - Čubáková, Petra - Kloz, M. - Švenda, J. - Vítek, L. - Klán, P.
Photochemistry of (Z)-isovinylneoxanthobilirubic acid methyl ester, a bilirubin dipyrrinone subunit: femtosecond transient absorption and stimulated Raman emission spectroscopy.
Journal of Organic Chemistry. Roč. 87, č. 5 (2022), s. 3089-3103. ISSN 0022-3263. E-ISSN 1520-6904
R&D Projects: GA ČR(CZ) GM21-09692M
Institutional support: RVO:68378271
Keywords : multivariate cure resolution * singlet oxygen * propentdyopents 5-(2-oxo-2h-pyrrol-5-ylmethylene)pyrrol-2(5H)-ones * sensitized photooxygenation
OECD category: Particles and field physics
Impact factor: 3.6, year: 2022
Method of publishing: Limited access
https://doi.org/10.1021/acs.joc.1c02870

Bilirubin (BR) is an essential metabolite formed by the catabolism of heme. Phototherapy with blue-green light can be applied to reduce high concentrations of BR in blood and is used especially in the neonatal period. In this work, we studied the photochemistry of (Z)-isovinylneoxanthobilirubic acid methyl ester, a dipyrrinone subunit of BR, by steady-state absorption, femtosecond transient absorption, and stimulated Raman spectroscopies. Both the (Z)- and (E)-configurational isomers of isovinylneoxanthobilirubic acid undergo wavelength-dependent and reversible photoisomerization. The isomerization from the excited singlet state is ultrafast (the lifetimes of (Z)- and (E)- isomers were found to be ∼0.9 and 0.1 ps, respectively), and its efficiencies increase with increased photon energy. In addition, we studied sensitized photooxidation of the dipyrrinone subunit by singlet oxygen that leads to the formation of propentdyopents.
Permanent Link: https://hdl.handle.net/11104/0339401