Conformational Control of the Photodynamics of a Bilirubin Dipyrrinone Subunit: Femtosecond Spectroscopy Combined with Nonadiabatic Simulations

Investor logo
Investor logo


This publication doesn't include Faculty of Medicine. It includes Faculty of Science. Official publication website can be found on

JANOŠ Jiří MADEA Dominik MAHVIDI Sadegh MUJAWAR Taufiqueahmed Pirsah ŠVENDA Jakub SUCHAN Jiří SLAVÍČEK Petr KLÁN Petr

Year of publication 2020
Type Article in Periodical
Magazine / Source Journal of Physical Chemistry
MU Faculty or unit

Faculty of Science

Keywords Quantum yield; Photoisomerization; Cyclization; Molecular structure; Excited states
Description The photochemistry of bilirubin has been extensively studied due to its importance in the phototherapy of hyperbilirubinemia. In the present work, we investigated the ultrafast photodynamics of a bilirubin dipyrrinone subunit, vinylneoxanthobilirubic acid methyl ester. The photoisomerization and photocyclization reactions of its (E) and (Z) isomers were studied using femtosecond transient absorption spectroscopy and by multireference electronic structure theory, where the nonadiabatic dynamics was modeled with a Landau–Zener surface hopping technique. The following picture has emerged from the combined theoretical and experimental approach. Upon excitation, dipyrrinone undergoes a very fast vibrational relaxation, followed by an internal conversion on a picosecond time scale. The internal conversion leads either to photoisomerization or regeneration of the starting material. Further relaxation dynamics on the order of tens of picoseconds was observed in the ground state. The nonadiabatic simulations revealed a strong conformational control of the photodynamics. The ultrafast formation of a cyclic photochemical product from a less-populated conformer of the studied subunit was predicted by our calculations. We discuss the relevance of the present finding for the photochemistry of native bilirubin. The work has also pointed to the limits of semiclassical nonadiabatic simulations for simulating longer photochemical processes, probably due to the zero-point leakage issue.
Related projects:

You are running an old browser version. We recommend updating your browser to its latest version.

More info