Bstract
Secondary electron transfer in photosystem II
(PSII), which occurs when water oxidation is inhibited
involves,, Redox-active carotenoids (Car), as well as chloro -
phylls (Chl), and cytochrome
B 559 (Cyt B
), 559 and is believed
to play. A role in photoprotection. Car
may D2 be the initial
point of secondary electron transfer because it is the closest
cofactor. To both P
, 680The initial oxidant and to, Cyt
, B 559 the terminal secondary electron donor within PSII. In order to
characterize the. Role of Car
and D2 to determine the effects of
perturbing Car D2 on both the electron-transfer events and on
the identity. Of the redox-active cofactors it is, necessary to
vary the properties of Car
selectively D2 without affecting the
ten other. Car per PSII To, this end.Site-directed mutations
around the binding pocket of Car
, D2 (D2-G47W D2-G47F
and, D2-T50F) have been generated in
, Synechocystis sp. PCC
6803. Characterization by near-IR and EPR spectroscopy
provides the first experimental evidence that Car
D2 is one of the. Redox-active carotenoids in PSII. There is a specific
perturbation of the Car
-
.
near-IR spectrum in all three
mutated. PSII, samplesAllowing the assignment of the
spectral signature of Car D2
-
.
-
; Car D2?
exhibits a near-IR peak at
980 nm and is. The predominant secondary donor oxidized in
a charge separation at low temperature in ferricyanide-trea -
Ted wild-type, PSII. The yield of secondary donor radicals is
substantially decreased in PSII complexes isolated from each
mutant, In addition.The kinetics of radical formation are
altered in the mutated PSII samples. These results are con -
sistent with oxidation. Of Car
being D2 the initial step in sec -
ondary electron transfer. Furthermore normal light, levels
during mutant cell growth. Perturb the shape of the Chl
-
.
near-IR absorption peak and generate a dark-stable radical
observable in the, EPR spectraIndicating a higher suscep -
tibility to photodamage further linking the secondary elec -
tron-transfer pathway to photoprotection
.
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