Persistent spectral hole-burning study on photosystem II reaction center reconstructed with dibromothymoquinone

We report the results of persistent spectral hole burning (PSHB) at 4 K in the isolated photosystem II reaction center complex (PSII RC) in the presence and absence of externally added dibromothymoquinone DBMIB (2,6-dibromo-3-methyl-5-isopropyl-p-benzoquinone). The purified PSII complex (D1–D2–cytochrome b559 reaction center complex) has six molecules of chlorophyll a and lacks intrinsic electron acceptor plastoquinone (designated QA and QB, respectively). DBMIB replaces the function of QA. The efficiency for the hole formation at a long wavelength (680 nm) was higher than that at a shorter wavelength (671 nm). Addition of DBMIB lowered the efficiency at shorter wavelengths (671–674 nm) with little effect at longer wavelengths (677–680 nm). Temperature excursion experiments at 4–30 K indicated the higher temperature stability of the hole at the longer wavelength suggesting that the extent of thermally induced backward reaction of hole formation, i.e., the structural relaxation behavior of the matrix around the pigments was smaller at the longer wavelength. The hole burned at 671 nm can be attributed to the pheophytin in D2 subunit, while the hole at 680 nm to the electron-acceptor pheophytin in D1 subunit. The possibility remains that the peripheral Chl 667 is responsible for the hole at 671 nm. The temperature dependence of Debye–Waller factor also suggested that the PSII RC complex has stronger electron–phonon interaction than usual amorphous polymer systems.