15N electron nuclear double resonance of the primary donor cation radical P+.865 in reaction centers of Rhodopseudomonas sphaeroides: additional evidence for the dimer model.

Abstract
Four 15N hyperfine coupling constants, including signs, were measured by electron nuclear double resonance (ENDOR) and electron nuclear nuclear triple resonance (TRIPLE) for the bacteriochlorophyll a radical cation, BChla+, in vitro and for the light-induced primary donor radical cation, .**GRAPHIC**. in reaction centers of R. sphaeroides R-26. A comparison of the data shows that the hyperfine coupling constants have the same sign in both radicals and are .apprx. 2 times smaller in .**GRAPHIC**. These results provide additional evidence that .**GRAPHIC**. is a bacteriochlorophyll dimer and are in contradiction with the monomer structure of .**GRAPHIC**. recently proposed by O''Malley and Babcock. The reduction factors of the individual 15N couplings, together with the evidence from proton ENDOR data and molecular orbital calculations, indicate a dimer structure in which only 2 rings (either I and I or III and III) of the bacteriochlorophyll macrocycles overlap.

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