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55Mn ENDOR of the S2-State Multiline EPR Signal of Photosystem II: Implications on the Structure of the Tetranuclear Mn Cluster

Peloquin, Jeffrey M., Campbell, Kristy A., Randall, David W., Evanchik, Marc A., Pecoraro, Vincent L., Armstrong, William H., Britt, R. David·2000·Journal of the American Chemical Society

Abstract

We have performed continuous-wave electron paramagnetic resonance (CW-EPR) and electron spin echo electron nuclear double resonance (ESE-ENDOR) experiments on the multiline form of the S 2 -state of untreated, MeOH-treated, and ammonia-treated spinach photosystem II (PS II) centers. Through simultaneously constrained simulations of the CW-EPR and ESE-ENDOR data, we conclude that four effective 55 Mn hyperfine tensors ( A X, A Y, A Z ) are required to properly simulate the experimental data [untreated and MeOH-treated PS II centers (MHz): −232, −232, −270; 200, 200, 250; −311, −311, −270; 180, 180, 240; ammonia-treated PS II centers (MHz): 208, 208, 158; −150, −150, −112; 222, 222, 172; −295, −315, −390]. We further show that these effective hyperfine tensors are best supported by a trimer/monomer arrangement of three Mn(IV) ions and one Mn(III) ion. In this topology, Mn A, Mn B, and Mn C form a strongly exchange coupled core ( J AB and J BC < −100 cm -1 ) while Mn D is weakly exchange coupled ( J CD ) to one end of the trinuclear core. For untreated and MeOH-treated PS II centers, the Mn(III) ion is either Mn A or Mn C, with a zero-field-splitting of D = −1.25 to −2.25 cm - 1 . For ammonia-treated PS II centers, the Mn(III) ion is Mn D, with a zero-field-splitting of D = +0.75 to +1.75 cm - 1 . The binding of the ammonia ligand results in a shift of the Mn(III) ion from the trinuclear core to the monomer Mn ion. This structural model can also account for the higher spin of the g = 4.1 signal and the magnetic properties of the S 0 -state.

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Metadata

Authors
Peloquin, J. M., Campbell, K. A., Randall, D. W., Evanchik, M. A., Pecoraro, V. L., Armstrong, W. H., & Britt, R. D.
Venue
Journal of the American Chemical Society
Published
2000-10-21
Volume
122
Issue
44
Pages
10926-10942
ISSN
  • 0002-7863 (ISSN-L)
  • 1520-5126
OpenAlex
W1995414833
Cited by
377
References
11
FWCI
4.96
Type
journal article
Language
en
Open access
closed

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