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Ultrafast light-induced response of photoactive yellow protein chromophore analogues

Espagne, Agathe and Paik, Daniel H. and Changenet-Barret, Pascale and Plaza, Pascal and Martin, Monique M. and Zewail, Ahmed H. (2007) Ultrafast light-induced response of photoactive yellow protein chromophore analogues. Photochemical and Photobiological Sciences, 2007 (6). pp. 780-787. ISSN 1474-905X.

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The fluorescence decays of several analogues of the photoactive yellow protein (PYP) chromophore in aqueous solution have been measured by femtosecond fluorescence up-conversion and the corresponding time-resolved fluorescence spectra have been reconstructed. The native chromophore of PYP is a thioester derivative of p-coumaric acid in its trans deprotonated form. Fluorescence kinetics are reported for a thioester phenyl analogue and for two analogues where the thioester group has been changed to amide and carboxylate groups. The kinetics are compared to those we previously reported for the analogues bearing ketone and ester groups. The fluorescence decays of the full series are found to lie in the 1–10 ps range depending on the electron-acceptor character of the substituent, in good agreement with the excited-state relaxation kinetics extracted from transient absorption measurements. Steady-state photolysis is also examined and found to depend strongly on the nature of the substituent. While it has been shown that the ultrafast light-induced response of the chromophore in PYP is controlled by the properties of the protein nanospace, the present results demonstrate that, in solution, the relaxation dynamics and pathway of the chromophore is controlled by its electron donor–acceptor structure: structures of stronger electron donor–acceptor character lead to faster decays and less photoisomerisation.

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Additional Information:This journal is © The Royal Society of Chemistry and Owner Societies 2007. Received 22nd January 2007, Accepted 29th March 2007. First published on the web 18th April 2007. The authors thank Jean-Bernard Baudin and Ludovic Jullien for providing pCMH, pCEH and pCTH which were synthesized in their group. MMM thanks Albert M. Brouwer for helpful suggestions. This collaborative work was done within the framework of a Blaise Pascal Chair AHZ was awarded at the Department of Chemistry of the Ecole Normale Supérieure (ENS) in Paris. Financial support from the ENS Foundation is acknowledged. AE is grateful to Caltech for a Graduate Fellowship during her stay in Pasadena. Electronic supplementary information (ESI) available: Steady-state absorption and fluorescence spectra of PYP chromophore analogues (Fig. S1). See DOI: 10.1039/b700927e
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Ecole Normale Supérieure (ENS)UNSPECIFIED
Issue or Number:6
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Official Citation:Ultrafast light-induced response of photoactive yellow protein chromophore analogues Agathe Espagne, Daniel H. Paik, Pascale Changenet-Barret, Pascal Plaza, Monique M. Martin and Ahmed H. Zewail Photochem. Photobiol. Sci., 2007,6, 780-787 DOI: 10.1039/B700927E
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:8798
Deposited By: Archive Administrator
Deposited On:18 Sep 2007
Last Modified:02 Oct 2019 23:54

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