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Issue 10, 2016
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Ultrafast deactivation of bilirubin: dark intermediates and two-photon isomerization

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Abstract

Bilirubin is a neurotoxic product responsible for neonatal jaundice, which is generally treated by phototherapy. The photoreaction involves ultrafast internal conversion via an elusive intermediate and ZE isomerization with minor yield (less than 3% in solution). The structure of the intermediate remains unclear. Here, the combination of UV-vis and mid-IR ultrafast transient absorption spectroscopy reports a comprehensive picture of the mechanism and provides essential structural information about the intermediate species. Thus, spectral dynamics during the earliest ps unveils a wavepacket travelling from the Franck–Condon region to the crossing point with a dark state. The latter shows a tighter molecular skeleton than the ground state and decays with 15 ps time constant. Remarkably, the relative contribution of a non-decaying component increases linearly with pump energy, suggesting that ZE isomerization could also be triggered by two-photon excitation. Implications for the photochemistry of protein-bound open tetrapyrroles are discussed.

Graphical abstract: Ultrafast deactivation of bilirubin: dark intermediates and two-photon isomerization

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Supplementary files

Article information


Submitted
13 Nov 2015
Accepted
21 Jan 2016
First published
27 Jan 2016

This article is Open Access

Phys. Chem. Chem. Phys., 2016,18, 7148-7155
Article type
Paper
Author version available

Ultrafast deactivation of bilirubin: dark intermediates and two-photon isomerization

C. Carreira-Blanco, P. Singer, R. Diller and J. Luis Pérez Lustres, Phys. Chem. Chem. Phys., 2016, 18, 7148
DOI: 10.1039/C5CP06971H

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