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Measurement of the extent of electron transfer to the bacteriopheophytin in the M-subunit in reaction centers of Rhodopseudomonas viridis
Authors:Elaine C Kellogg  Stephen Kolaczkowski  Michael R Wasielewski  David M Tiede
Institution:(1) Chemistry Division, Argonne National Laboratory, 60439 Argonne, IL, U.S.A.;(2) Present address: Department of Chemistry, University of Arizona, 85721 Tucson, AZ, U.S.A.;(3) Chemistry Division D-200, Argonne National Laboratory, 60439 Argonne, IL, U.S.A.
Abstract:We have measured the extent of flash-induced electron transfer from the bacteriochlorophyll dimer, P, to the bacteriopheophytin in the M-subunit, HM, in reaction centers of Rhodopseudomonas viridis. This has been done by measuring the transient states produced by excitation of reaction centers trapped in the PHL HM state at 90 K. Under these conditions the normal forward electron transfer to the bacteriopheophytin in the L-subunit, HL, is blocked and the yield of transient P+HM can be estimated with respect to the lifetime of P*. Under these conditions flash induced absorbance decreases of the bacteriochlorophyll dimer 990 nm band suggest that a transient P+ state is formed with a quantum yield of 0.09±0.06 compared to that formed during normal photochemistry. These transient measurements provide an upper limited on the yield of a transient P+ HM state. An estimate of 0.09 as the yield of the P+ HM state is consistent with all current observations. This estimate and the lifetime of P* suggest that the electron transfer rate from P* to HM, kM, is about 5 × 109 sec–1 (tauM = 200ps). These measurements suggest that the a branching ratio kL/kM is on the order of 200. The large value of the branching ratio is remarkable in view of the structural symmetry of the reaction center. This measurement should be useful for electron transfer calculations based upon the reaction center structure.
Keywords:electron transfer  photochemistry  photosynthesis  transient spectroscopy
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