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.

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.
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球形红假单胞菌反应中心主要供体阳离子自由基 P .865 的 15N 电子核双共振:二聚体模型的额外证据。

DOI:
10.1073/pnas.81.24.7792
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发表时间:
1984
影响因子:
11.1
通讯作者:
Feher,G
Feher,G
中科院分区:
综合性期刊1区
文献类型:
--
作者:
Lubitz,W;Isaacson,RA;Abresch,EC;Feher,G

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在球形红假单胞菌R-26的反应中心,用电子核双共振(Endor)和电子核三重共振(Triple)测量了细菌叶绿素a自由基阳离子BChla+和光诱导的初级供体自由基阳离子P+865的四个15N超精细耦合常数,包括符号。数据的比较表明,超精细耦合常数在两个基团中具有相同的符号,并且在P+.865中平均小2倍。这些结果进一步证明P+.865是细菌叶绿素二聚体,与O‘Malley和Babcock最近提出的P+.865的单体结构相矛盾。单个15N偶合的还原因子,以及来自质子Endor数据和分子轨道计算的证据,表明了一种二聚体结构,其中只有细菌-叶绿素大环的两个环(I和I或III和III)重叠。
Four 15N hyperfine coupling constants, including signs, have been 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, P+.865, in reaction centers of Rhodopseudomonas sphaeroides R-26. A comparison of the data shows that the hyperfine coupling constants have the same sign in both radicals and are, on the average, smaller by a factor of 2 in P+.865. These results provide additional evidence that P+.865 is a bacteriochlorophyll dimer and are in contradiction with the monomer structure of P+.865 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 two rings (either I and I or III and III) of the bacteriochlorophyll macrocycles overlap.
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