Record number :
1626777
Title of article :
Reaction-coordinate tracking in the excited-state deactivation of the photoactive yellow protein chromophore in solution
Author/Authors :
Agathe and Changenet-Barret، نويسنده , , Pascale and Lacombat، نويسنده , , Fabien and Plaza، نويسنده , , Pascal، نويسنده ,
Issue Information :
روزنامه با شماره پیاپی سال 2012
Pages :
10
From page :
171
To page :
180
Abstract :
The earliest steps of the photoactive yellow protein (PYP) photocycle are known to involve cis–trans photoisomerization of its chromophore, the deprotonated trans-p-coumaric acid. In aqueous solution PYP chromophore analogues bearing the same thioester function as in the protein however do not isomerize and restore the initial trans configuration via a short-lived charge-transfer intermediate. In order to gain further insight into the nature of this non-radiative process, we report the first study by femtosecond transient absorption spectroscopy of a ketone derivative of the trans-p-coumaric acid, pCK−, which has been used as a PYP chromophore model in recent theoretical studies. While the transient spectra of pCK− in basic aqueous solution are similar to those of the thioester derivatives, we identify in decanol an additional deactivation route. It involves the formation of photoproduct with a lifetime of a few seconds, which we attribute to the cis isomer. These results are discussed in terms of both static and dynamic solvent effects on the excited-state deactivation.
Keywords :
p-Coumaric acid , PYP , Photoisomerization , Transient absorption spectroscopy , Charge transfer state
Journal title :
Journal of Photochemistry and Photobiology:A:Chemistry
Serial Year :
2012
Link To Document :
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