Electric field effects on red chlorophylls, beta-carotenes and P700 in cyanobacterial Photosystem I complexes.

We have probed the absorption changes due to an externally applied electric field (Stark effect) of Photosystem I (PSI) core complexes from the cyanobacteria Synechocystis sp. PCC 6803, Synechococcus elongatus and Spirulina platensis. The results reveal that the so-called C719 chlorophylls in S. elongatus and S. platensis are characterized by very large polarizability differences between the ground and electronically excited states (with Tr(Deltaalpha) values up to about 1000 A(3) f(-2)) and by moderately high change in permanent dipole moments (with average Deltamu values between 2 and 3 D f(-1)). The C740 chlorophylls in S. platensis and, in particular, the C708 chlorophylls in all three species give rise to smaller Stark shifts, which are, however, still significantly larger than those found before for monomeric chlorophyll. The results confirm the hypothesis that these states originate from strongly coupled chlorophyll a molecules. The absorption and Stark spectra of the beta-carotene molecules are almost identical in all complexes and suggest similar or slightly higher values for Tr(Deltaalpha) and Deltamu than for those of beta-carotene in solution. Oxidation of P700 did not significantly change the Stark response of the carotenes and the red antenna states C719 and C740, but revealed in all PSI complexes changes around 700-705 and 690-693 nm, which we attribute to the change in permanent dipole moments of reduced P700 and the chlorophylls responsible for the strong absorption band at 690 nm with oxidized P700, respectively.