Agarwal Rachna, Chauvet Adrien A P
Department of Biological Sciences, Purdue University, West Lafayette, Indiana 47907, USA and Molecular Biology Division, Bhabha Atomic Research Centre, Mumbai 400 085, India.
Ecole Polytechnique Fédérale de Lausanne (EPFL), Laboratoire de Spectroscopie Ultrarapide (LSU), ISIC, Faculté des Sciences de Base and Lausanne Centre for Ultrafast Science (LACUS), Station 6, 1015 Lausanne, Switzerland.
Phys Chem Chem Phys. 2017 Jan 25;19(4):3287-3296. doi: 10.1039/c6cp08077d.
The dynamics of hemes b and c within the cytochrome bf complex are investigated by means of ultrafast broad-band transient absorption spectroscopy. On the one hand, the data reveal that, subsequent to visible light excitation, part of the b hemes undergoes pulse-limited photo-oxidation, with the liberated electron supposedly being transferred to one of the adjacent aromatic amino acids. Photo-oxidation is followed by charge recombination in about 8.2 ps. Subsequent to charge recombination, heme b is promoted to a vibrationally excited ground state that relaxes in about 4.6 ps. On the other hand, heme c undergoes ultrafast ground state recovery in about 140 fs. Interestingly, the data also show that, in contrast to previous beliefs, Chl a is involved in the photochemistry of hemes. Indeed, subsequent to heme excitation, Chl a bleaches and recovers to its ground state in 90 fs and 650 fs, respectively. Chl a bleaching allegedly corresponds to the formation of a short lived Chl a anion. Beyond the previously suggested structural role, this study provides unique evidence that Chl a is directly involved in the photochemistry of the hemes.
