Abstract
Geranylgeranyl reductase (GGR) encoded by the bchP gene catalyzes the reductions of three unsaturated C = C double bonds (C6 = C7, C10 = C11, and C14 = C15) in a geranylgeranyl (GG) group of the esterifying moiety in 17-propionate residue of bacteriochlorophyll (BChl) molecules. It was recently reported that GGR in Halorhodospira halochloris potentially catalyzes two hydrogenations, yielding BChl with a tetrahydrogeranylgeranyl (THGG) tail. Furthermore, its engineered GGR, in which N-terminal insertion peptides characteristic for H. halochloris were deleted, performed single hydrogenation, producing BChl with a dihydrogeranylgeranyl (DHGG) tail. In some of these enzymatic reactions, it remained unclear in which order the C = C double bond in a GG group was first reduced. In this study, we demonstrated that the (variant) GGR from H. halochloris catalyzed an initial reduction of the C6 = C7 double bond to yield a 6,7-DHGG tail. The intact GGR of H. halochloris catalyzed the further hydrogenation of the C14 = C15 double bonds to give a 6,7,14,15-THGG group, whereas deleting the characteristic peptide region from the GGR suppressed the C14 = C15 reduction. We also verified that in a model bacterium, Blastochloris viridis producing standard BChl-b, the reduction of a GG to phytyl group occurred via 10,11-DHGG and 6,7,10,11-THGG. The high-performance liquid chromatographic elution profiles of BChls-a/b employed in this study are essential for identifying the regioisomeric diterpenoid tails in the BChls of phototrophic bacteria distributed in nature and elucidating GGR enzymatic reactions.
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Abbreviations
- APCI:
-
Atmospheric pressure chemical ionization
- BChl:
-
Bacteriochlorophyll
- BChlide:
-
Bacteriochlorophyllide
- DHGG:
-
Dihydrogeranylgeranyl
- DHGG-OH:
-
Dihydrogeranylgeraniol
- GC:
-
Gas chromatography
- GG:
-
Geranylgeranyl
- GG-OH:
-
Geranylgeraniol
- GGR:
-
Geranylgeranyl reductase
- HPLC:
-
High-performance liquid chromatography
- LC–MS:
-
Liquid chromatography–mass spectrometry
- LH:
-
Light-harvesting
- MS:
-
Mass spectrometry
- PDA:
-
Photodiode array
- RC:
-
Reaction center
- THGG:
-
Tetrahydrogeranylgeranyl
- THGG-OH:
-
Tetrahydrogeranylgeraniol
- tR:
-
Retention time
- UV–VIS–NIR:
-
Ultraviolet–visible–near infrared
- rt:
-
Room temperature
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Acknowledgements
We would like to thank Prof. Kazuhito Inoue of Kanagawa University for his kind provision of a purple photosynthetic bacterium, B. viridis DSM 133. This work was partially supported by the Japan Society for the Promotion of Science (JSPS) KAKENHI Grant Numbers, 21J22995 (to M.H.), 19H02018 (to Y.T.), 18H03743 (to Y.T.), 22H02203 (to H.T.), and 17H06436 in the Scientific Research on Innovative Areas “Innovation for Light-Energy Conversion (I4LEC)” (to H.T.).
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Hirose, M., Tsukatani, Y., Harada, J. et al. Characterization of regioisomeric diterpenoid tails in bacteriochlorophylls produced by geranylgeranyl reductase from Halorhodospira halochloris and Blastochloris viridis. Photosynth Res 154, 1–12 (2022). https://doi.org/10.1007/s11120-022-00938-3
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DOI: https://doi.org/10.1007/s11120-022-00938-3