Simulation for the primary electronic donor of photosystem IIin vitro

Histidine coordinated to Chi a is a distinct characteristic of Chl ain vivo. By using histidine analogue of 1-methylimidazole (C₄H₆N₂2) and measuring the UV/vis absorption, CD and MCD spectra of the interaction between C₄H₆N₂ and Chl a in CCI₄, we have obtained that: (i) In pure CCl₄ solvent, Chl a molecule is in five-coordinate state, and two Chl a molecules form an asymmetric compact-dimer with strong coupling interaction. We propose that the two Chl a molecules are connected by two unequally coordinated Mg-O bonds (the two oxygen atoms come from the C=O of C13¹ keto and C17 ester, respectively); (ii) when the molar ratio of C₄H₆N₂/Chl a is 0.5 or 1 (corresponding to 2Chl a · 1C₄H₆N₂ and 2Chl a · 2C₄H₆N₂, respectively), significant changes have been observed in the absorption, CD and MCD spectra, which indicate that the Chl a remains in dimer form, but the coupling interaction between them reduces greatly. We postulate that C₄H₆N₂ replaces the ligation of C=O of C17 ester and C13¹ keto to Mg atoms sequentially. The two Chl a molecules linked by two weakly interacted Mg…O bonds form a relaxed-dimer. The structure of the model is essentially similar to that of the primary electronic donor, P₆₈₀, of photosystem II in high plants and algae.