PULSED EPR STUDY OF SPIN-COUPLED RADICAL PAIRS IN PHOTOSYNTHETIC REACTION CENTERS - MEASUREMENT OF THE DISTANCE BETWEEN P-700(CENTER-DOT-DOT-) IN PHOTOSYSTEM-I AND BETWEEN P-865(CENTER-DOT+) AND Q(A)(CENTER-DOT-) IN BACTERIAL REACTION CENTERS() AND A(1)(CENTER)
R. Bittl et Sg. Zech, PULSED EPR STUDY OF SPIN-COUPLED RADICAL PAIRS IN PHOTOSYNTHETIC REACTION CENTERS - MEASUREMENT OF THE DISTANCE BETWEEN P-700(CENTER-DOT-DOT-) IN PHOTOSYSTEM-I AND BETWEEN P-865(CENTER-DOT+) AND Q(A)(CENTER-DOT-) IN BACTERIAL REACTION CENTERS() AND A(1)(CENTER), JOURNAL OF PHYSICAL CHEMISTRY B, 101(8), 1997, pp. 1429-1436
The spin-polarized radical pairs P(865)(.+)Q(A)(.-) in protonated and
deuterated Zn-substituted reaction centers from two different mutants
of the photosynthetic bacteria Rhodobacter sphaeroides and P(700)(.+)A
(1)(.-) in plant photosystem I from Synechococcus elongatus are invest
igated by pulsed EPR spectroscopy. Spin-polarized radical pairs give r
ise to a characteristic out-of-phase electron spin echo. This echo sho
ws a deep envelope modulation with a frequency governed by the spin-sp
in interaction. The known distance dependence of the magnetic dipolar
interaction allows the determination of the distance between the cofac
tors carrying the unpaired electron spins. For the bacterial reaction
centers this distance is known for the electronic ground state from cr
ystal structures and is compared here with the distance of the radical
pair spins, i.e. the charge-separated state. In photosystem I the loc
ation of the acceptor A(1) is not known yet. A distance of 25.4 +/- 0.
3 Angstrom between P-700(.+) and A(1)(.-) is obtained here and gives n
ew structural information on photosystem I.