Abstract
PsaC is a tightly bound ferredoxin in the Photosystem I (PS I) reaction center which contains two [4Fe-4S] clusters named FA and FB. We recently proposed that the mixed-ligand FB cluster in C14DPsaC and the mixed-ligand FA cluster in C51DPsaC exist in a spin state of S=3/2, and that a spin state crossover to S=1/2 occurs when the PsaC mutants are rebound onto P700-FX cores. Since EPR signals from a highly rhombic S=3/2 spin state can be difficult to study, wild-type PsaC was reconstituted with iron and selenium to introduce an easily detected S=7/2 spin state similar to that shown for Clostridial ferredoxin. When the unbound [4Fe-4Se] PsaC was chemically reduced, a sharp derivative resonance was found at g=5.171 attributed to the excited ±3/2 doublet from an S=7/2 spin multiplet. An additional peak was found at g=5.616 attributed to the superimposed ±1/2 and ±3/2 doublets from a highly rhombic S=3/2 spin multiplet, and an axial set of resonances found around g=2.0 attributed, in part, to a classical S=1/2 spin state. When the [4Fe-4Se] PsaC was rebound onto P700-FX cores, the spin population derived from the S=7/2 and 3/2 spin states was negligible. Illumination of the rebuilt PS I complex at 15 K resulted in two rhombic sets of resonances, one with g values of 2.043, 1.941 and 1.854, diagnostic of FA, and the other with g values of 2.067, 1.941 and 1.878, diagnostic of FB. Chemical reduction with sodium dithionite at pH 10.5 or photoaccumulation by freezing during illumination resulted in a set of resonances with g values of 2.046, 1.938, 1.920 and 1.883, characteristic of a spin-coupled FA –/FB – pair. The spin state crossover in this iron chalcogenide cluster is the first known to be induced by protein-protein association and reinforces the hypothesis that an S=3/2 to 1/2 crossover occurs in the PS I-rebound mutants C14DPsaC and C51DPsaC.
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Received: 6 August 1996 / Accepted: 28 December 1996
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Jung, YS., Vassiliev, I. & Golbeck, J. Crossover of a high-spin (S=7/2, 3/2) to a low-spin (S=1/2) iron-selenium cluster in FA and FB of photosystem I on rebinding of PsaC onto P700-FX cores. JBIC 2, 209–217 (1997). https://doi.org/10.1007/s007750050126
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DOI: https://doi.org/10.1007/s007750050126