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In vitro stereospecific hydration activities of the 3-vinyl group of chlorophyll derivatives by BchF and BchV enzymes involved in bacteriochlorophyll c biosynthesis of green sulfur bacteria

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Abstract

The photosynthetic green sulfur bacterium Chlorobaculum (Cba.) tepidum produces bacteriochlorophyll (BChl) c pigments bearing a chiral 1-hydroxyethyl group at the 3-position, which self-aggregate to construct main light-harvesting antenna complexes, chlorosomes. The secondary alcoholic hydroxy group is requisite for chlorosomal aggregation and biosynthesized by hydrating the 3-vinyl group of their precursors. Using recombinant proteins of Cba. tepidum BchF and BchV, we examined in vitro enzymatic hydration of some 3-vinyl-chlorophyll derivatives. Both the enzymes catalyzed stereoselective hydration of zinc 3-vinyl-8-ethyl-12-methyl-bacteriopheophorbide c or d to the zinc 31 R-bacteriopheophorbide c or d homolog, respectively, with a slight amount of the 31 S-epimric species. A similar R-stereoselectivity was observed in the BchF-hydration of zinc 3-vinyl-8-ethyl- and propyl-12-ethyl-bacteriopheophorbides c, while their BchV-hydration gave a relatively larger amount of the 31 S-epimers. The in vitro stereoselective hydration confirmed the in vivo production of the S-epimeric species by BchV. The enzymatic hydration for the above 8-propylated substrate proceeded more slowly than that for the 8-ethylated, and the 8-isobutylated substrate was no longer hydrated. Based on these results, biosynthetic pathways of BChl c homologs and epimers are proposed.

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Abbreviations

BChl:

Bacteriochlorophyll

BPheide:

Bacteriopheophorbide

BPheo:

Bacteriopheophytin

Cba. :

Chlorobaculum

Chl:

Chlorophyll

Chlide:

Chlorophyllide

PChlide:

Protochlorophyllide

Pheide:

Pheophorbide

R[E,E]:

(31 R)-8,12-diethyl

R[E,M]:

(31 R)-8-ethyl-12-methyl

R[P,E]:

(31 R)-8-propyl-12-ethyl

S[I,E]:

(31 S)-8-isobutyl-12-ethyl

S[P,E]:

(31 S)-8-propyl-12-ethyl

THF:

Tetrahydrofuran

3V:

3-Vinyl

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Acknowledgments

We thank Prof. Tadashi Mizoguchi of Ritsumeikan University for his assistance in HPLC analyses. This work was partially supported by a Grant-in-Aid for Scientific Research on Innovative Areas “Artificial Photosynthesis (AnApple)” (No. 24107002) (to HT) from the Japan Society for the Promotion of Science (JSPS).

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Authors and Affiliations

  1. Graduate School of Life Sciences, Ritsumeikan University, Kusatsu, Shiga, 525-8577, Japan

    Misato Teramura & Hitoshi Tamiaki

  2. Department of Medical Biochemistry, Kurume University School of Medicine, Kurume, Fukuoka, 830-0011, Japan

    Jiro Harada

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  1. Misato Teramura
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  2. Jiro Harada
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  3. Hitoshi Tamiaki
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Correspondence to Hitoshi Tamiaki.

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Teramura, M., Harada, J. & Tamiaki, H. In vitro stereospecific hydration activities of the 3-vinyl group of chlorophyll derivatives by BchF and BchV enzymes involved in bacteriochlorophyll c biosynthesis of green sulfur bacteria. Photosynth Res 130, 33–45 (2016). https://doi.org/10.1007/s11120-016-0220-7

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