Red spectral forms of chlorophylls in green plant PSI -: a site-selective and high-pressure spectroscopy study

One of the special spectroscopic characteristics of photosystem I (PSI) complexes is that they possess absorption and emission bands at lower energy than those of the reaction center. In this paper, the red pigment pools of PSI-200, PSI-core, and LHCI complex from Arabidopsis thaliana have been characterized at low temperatures by means of spectrally selective (hole-buming and fluorescence line-narrowing) and high-pressure spectroscopic techniques. It was shown that the green plant PSI-200 complex has at least three red pigment pools, from which two are located in the PSI-core and one, in the peripheral light-harvesting complex I (LHCI). All of the red pigment pools are characterized by strong electron-phonon coupling. A Huang-Rhys factor of 2.9 found for the red pigments of LHCI is the largest found for any photosynthetic antenna system. This contrasts with the bulk pigments in the main Q, absorption band of chlorophyll a pigments for which the Huang-Rhys factors of less than unity are observed. This electron-phonon coupling difference of the red and bulk pigments is well reflected by the spectral dependence of the hole-burning efficiency, which is significantly reduced in the red absorption region. As a result of extremely low hole-burning efficiency in the red absorption band of LHCI, the hole-burning spectra of the PSI-200 complex mainly originate from the red pigments of the PSI-core complex. At the same time, the source of the red emission in PSI-200 is the red pigments of LHCL in agreement with previous studies. The hole-burning spectra of PSI-core complexes from green plant and cyanobacteria are similar, both in red and bulk absorption regions. High-pressure spectroscopy data reveal dramatically larger pressure-induced linear shift rates for the redmost absorption and emission bands relative to those of bulk absorption bands. This is interpreted as due mostly to increased conformational mixing between the locally excited and charge transfer configurations of the red pigment aggregates. On the basis of analysis of available experimental data, we suggest that pigment dimers are probably responsible for the redmost states. Consequently, the excited red states can be interpreted as excimer states.