Ultrafast deactivation of bilirubin: dark intermediates and two-photon isomerization
Please use this identifier to cite or link to this item:
http://hdl.handle.net/10347/17070
Files in this item
Metadata
Title: | Ultrafast deactivation of bilirubin: dark intermediates and two-photon isomerization |
Author: | Carreira Blanco, Carlos Singer, Patrick Diller, Rolf Pérez Lustres, José Luis |
Affiliation: | Universidade de Santiago de Compostela. Centro de Investigación en Química Biolóxica e Materiais Moleculares Universidade de Santiago de Compostela. Departamento de Química Física |
Date of Issue: | 2016 |
Publisher: | Royal Society of Chemistry |
Citation: | Carreira-Blanco, C., Singer, P., Diller, R., & Luis Pérez Lustres, J. (2016). Ultrafast deactivation of bilirubin: dark intermediates and two-photon isomerization. Physical Chemistry Chemical Physics, 18(10), 7148-7155. doi: 10.1039/c5cp06971h |
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 Z–E 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 Z–E isomerization could also be triggered by two-photon excitation. Implications for the photochemistry of protein-bound open tetrapyrroles are discussed |
Publisher version: | https://doi.org/10.1039/C5CP06971H |
URI: | http://hdl.handle.net/10347/17070 |
DOI: | 10.1039/C5CP06971H |
ISSN: | 1463-9076 |
E-ISSN: | 1463-9084 |
Rights: | This article is licensed under a Creative Commons Attribution 3.0 Unported Licence |
Collections
-
- CIQUS-Artigos [391]
- QB-Artigos [20]
- QF-Artigos [107]