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Which side of the π-macrocycle plane of (bacterio)chlorophylls is favored for binding of the fifth ligand?

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Abstract

Reported crystallographic data and calculated molecular models indicated that chlorophyll (Chl) a and bacteriochlorophyll (BChl) a tend to bind the fifth ligand on the side of the macrocycle where the C132-(R)-methoxycarbonyl moiety protrudes (denoting the ‘back’ side). The crystal structures of 34 photosynthetic proteins possessing (B)Chl cofactors revealed that most of Chl a and BChl a (and b) are coordinated by any peptidyl residue (e.g., histydyl-imidazolyl group), peptidyl backbone or water from the ‘back’ side. Almost all the cofactors that bind a water molecule as the fifth ligand in these proteins have a ‘back’ configuration. Theoretical model calculations for methyl chlorophyllide a (MeChlid a) and methyl bacteriochlorophyllide a (MeBChlid a) bound to an imidazole molecule indicated that the ‘back’ side is energetically favored for the ligand binding. These results are consistent with the fact that ethyl chlorophyllide a (EtChlid a) dihydrate crystal consists of the ‘back’ complex. The modeling also showed that both removal and stereochemical inverse of the C132-methoxycarbonyl group affect the relative stability between the ‘back’ and ‘face’ complexes. The effect of the C132-moiety on the choice of the macrocycle side for the ligand binding is discussed in relation to the function of P700.

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Author notes

  1. Toru Oba

    Present address: Institute for Molecular Science, Okazaki, Aichi, 444-8535, Japan

Authors and Affiliations

  1. Department of Applied Chemistry, Faculty of Engineering, Utsunomiya University, Utsunomiya, Tochigi, 321-8585, Japan

    Toru Oba

  2. Department of Bioscience and Biotechnology, Faculty of Science and Engineering, Ritsumeikan University, Kusatsu, Shiga, 525-8577, Japan

    Hitoshi Tamiaki

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  1. Toru Oba
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  2. Hitoshi Tamiaki
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Correspondence to Hitoshi Tamiaki.

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Oba, T., Tamiaki, H. Which side of the π-macrocycle plane of (bacterio)chlorophylls is favored for binding of the fifth ligand?. Photosynthesis Research 74, 1–10 (2002). https://doi.org/10.1023/A:1020816128794

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