Abstract
Chlorophylls (Chls) are pigments involved in light capture and light reactions in photosynthesis. Chl a, Chl b, Chl d, and Chl f are characterized by unique absorbance maxima in the blue (Soret) and red (Qy) regions with Chl b, Chl d, and Chl f each possessing a single formyl group at a unique position. Relative to Chl a the Qy absorbance maximum of Chl b is blue-shifted while Chl d and Chl f are red-shifted with the shifts attributable to the relative positions of the formyl substitutions. Reduction of a formyl group of Chl b to form 7-hydroxymethyl Chl a, or oxidation of the vinyl group of Chl a into a formyl group to form Chl d was achieved using sodium borohydride (NaBH4) or β-mercaptoethanol (BME/O2), respectively. During the consecutive reactions of Chl b and Chl f using a three-step procedure (1. NaBH4, 2. BME/O2, and 3. NaBH4) two new 7-hydroxymethyl Chl a species were prepared possessing the 3-formyl or 3-hydroxymethyl groups and three new 2-hydroxymethyl Chl a species possessing the 3-vinyl, 3-formyl, or 3-hydroxymethyl groups, respectively. Identification of the spectral properties of 2-hydroxymethyl Chl a may be biologically significant for deducing the latter stages of Chl f biosynthesis if the mechanism parallels Chl b biosynthesis. The spectral features and chromatographic properties of these modified Chls are important for identifying potential intermediates in the biosynthesis of Chls such as Chl f and Chl d and for identification of any new Chls in nature.
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Abbreviations
- BME:
-
β-Mercaptoethanol
- CAO:
-
Chlorophyll a oxygenase
- CBR:
-
Chlorophyll b reductase
- Chl:
-
Chlorophyll
- Chlide:
-
Chlorophyllide
- HCAR:
-
Hydroxymethyl-chlorophyll a reductase
- MALDI-MS:
-
Matrix-assisted laser desorption/ionization mass spectrometry
- NaBH4 :
-
Sodium borohydride
- RP-HPLC:
-
Reversed-phase high-performance liquid chromatography
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Acknowledgements
We would like to thank Dr. Ben Crossett for access to the mass spectrometry facility at the Charles Perkins Centre, The University of Sydney. We also thank Dr. Ann Kwan for assisting with the NMR experiments.
Funding
The research is supported by The Australian Research Council Centre of Excellence for Translational Photosynthesis (CE20140100015).
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Sawicki, A., Willows, R.D. & Chen, M. Spectral signatures of five hydroxymethyl chlorophyll a derivatives chemically derived from chlorophyll b or chlorophyll f. Photosynth Res 140, 115–127 (2019). https://doi.org/10.1007/s11120-018-00611-8
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DOI: https://doi.org/10.1007/s11120-018-00611-8