Sub-Picosecond Mid-Infrared Spectroscopy of the Pfr Reaction of Phytochrome Agp1 from Agrobacterium tumefaciens
Christian Schumann 1, Ruth Groß 1, Matthias M.N. Wolf 1, Norbert Michael 2, Tilman Lamparter 3 and Rolf Diller 1*
1 Universität Kaiserslautern
2 Freie Universität Berlin
3 Universität Karlsruhe
* To whom correspondence should be addressed. E-mail: diller{at}physik.uni-kl.de.
Submitted on August 9, 2007
Revised on September 6, 2007
Accepted on 3 December 2007
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Abstract |
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Phytochromes are light-sensing pigments found in plants and bacteria. For the first time, the Pfr photoreaction of a phytochrome has been subject to ultrafast infrared vibrational spectroscopy. Three time constants of 0.3 ps, 1.3 ps and 4.0 ps were derived from the kinetics of structurally specific marker bands of the biliverdin chromophore of Agp1-BV from Agrobacterium tumefaciens after excitation at 765 nm. VIS-pump-VIS-probe experiments yield time constants of 0.44 ps and 3.3 ps for the underlying electronic state dynamics. A reaction scheme is proposed including two kinetic steps on the S1 excited state surface and the cooling of a vibrationally hot Pfr ground state. It is concluded that the upper limit of the E-Z isomerization of the C15 = C16 methine bridge is given by the intermediate time constant of 1.3 ps. The reaction scheme is reminiscent of that of the corresponding Pr reaction of Agp1-BV (Schumann et al., 2007. ChemPhysChem 8:1657-1663).
Key Words:
Pfr, infrared, photoreaction, phytochrome, spectroscopy, ultrafast
