ENDOR studies of substituted chlorophyll cation radicals

被引:24
作者
Kass, H
Lubitz, W
Hartwig, G
Scheer, H
Noy, D
Scherz, A
机构
[1] Tech Univ Berlin, Max Volmer Inst Biophys Chem & Biochem, D-10623 Berlin, Germany
[2] Univ Munchen, Inst Bot, D-80638 Munchen, Germany
[3] Weizmann Inst Sci, Dept Biochem, IL-76100 Rehovot, Israel
关键词
photosynthesis; EPR; ENDOR; MO theory; pigment radical cations; electronic structure; spin destiny distribution; hyperfine couplings; substituted chlorophylls; Zn-(bacterio)chlorophyll;
D O I
10.1016/S1386-1425(98)00065-1
中图分类号
O433 [光谱学];
学科分类号
0703 ; 070302 ;
摘要
Cation radicals of substituted chlorophyll (Chl) a molecules were characterized by EPR and ENDOR spectroscopy. The effect of substitutions of the vinyl group at position 3 and the carbomethoxy group at 13(2) as well as the replacement of the central magnesium atom by zinc were investigated. All major hyperfine coupling constants could be determined and assigned to specific molecular positions. Comparison of the experimental results with data from related bacteriochlorophyll (BChl) a cation radicals shows that introduction of the same substitution in Chl a and BChl a causes a similar change of the electron spin density distribution in both radicals. Semi-empirical calculations of the RHF-INDO/SP type were performed on all systems and yielded the isotropic and the anisotropic part of the proton hyperfine coupling tensors. The experimental and theoretical results are in good agreement. The data obtained for the Chl a species investigated are discussed with regard to the structure of the primary donor cation radicals in plant photosystem I and II. (C) 1998 Elsevier Science B.V. All rights reserved.
引用
收藏
页码:1141 / 1156
页数:16
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