Chlorophylls

Chlorophylls are a group of cyclic tetrapyrrole pigments that are involved in the light reactions of photosynthesis. All chlorophylls are synthesized from 5-aminolaevulinic acid via multiple enzymatic reactions.

Keywords: photosynthesis; photosystems; light-harvesting complex; reaction center; tetrapyrrole

Figure 1. (a, b) Two different nomenclature systems used in porphyrin and Chl chemistry: (a) the IUPAC nomenclature; (b) Fischer's nomenclature. (c–e) Three oxidation states of the cyclic tetrapyrroles present in Chls and BChls: (c) porphyrin; (d) chlorin (17,18-dihydroporphyrin); (e) bacteriochlorin (7,8,17,18-tetrahydroporphyrin). (f–i) Structures of Chl a and its derivatives lacking the magnesium ion and/or phytol: (f) Chl a; (g) chlorophyllide a; (h) pheophytin a; (i) pheophorbide a.
Figure 2. Structure of various Chls (a) and BChls (b). (a) Chls a, b, c and d. Differences in side-chains of Chls b, c and d from Chl a are highlighted with yellow boxes. (b) BChls a, b, c, d, e, g and Zn-BChl a. Differences in side-chains, ring oxidation state, and the central metal ion of BChls b, c, d, e, g and Zn-BChl a are highlighted with yellow boxes. See Table 2 for R1 (C7) and R2 (C8) in Chls c, and R1 (C7), R2 (C8), R3 (C12) and R4 (C20) in BChls c, d and e.
Figure 3. Biosynthetic route of Chls and BChls. Early steps of the Chl biosynthesis from the ALA formation to protoporphyrin IX. These steps are common to haem biosynthesis.
Figure 4. Biosynthetic route of Chls and BChls. Mg branch. Late steps from protoporphyrin IX are specific for Chls and BChls. Modifications of the intermediates at various stages are highlighted with a yellow box.
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 References
    book Akhtar M (2003) "Coproporphyrinogen III and protoporphyrinogen IX oxidases". In: Kadish KM, Smith KM and Guilard R (eds) Porphyrin Handbook vol. 13, pp. 75–92. Oxford: Academic Press.
    Bibby TS, Nield J and Barber J (2001) Iron deficiency induces the formation of an antenna ring around trimeric photosystem I in cyanobacteria. Nature 412: 743–745.
    Boekema EJ, Hifney A, Yakushevska AE et al. (2001) A giant chlorophyll–protein complex induced by iron deficiency in cyanobacteria. Nature 412: 745–748.
    book Bollivar DW (2003) "Intermediate steps in chlorophyll biosynthesis: methylation and cyclization". In: Kadish KM, Smith KM and Guilard R (eds) Porphyrin Handbook vol. 13, pp. 49–70. Oxford: Academic Press
    Cornah JE, Matthew JT and Smith AG (2003) Green or red: what stops the traffic in the tetrapyrrole pathway? Trends in Plant Science 8: 224–230.
    Frigaard N-U, Gomez Maqueo Chew A, Li H, Maresca JA and Bryant DA (2003) Chlorobium tepidum: insights into the structure, physiology, and metabolism of a green sulfur bacterium derived from the complete genome sequence. Photosynthesis Research 78: 93–117.
    book Fujita Y and Bauer CE (2003) "The light-independent protochlorophyllide reductase: a nitrogenase-like enzyme catalyzing a key reaction for greening in the dark". In: Kadish KM, Smith KM and Guilard R (eds) Porphyrin Handbook vol. 13, pp. 109–156. Oxford: Academic Press
    Heyes DJ, Hunter CN, van Stokkum IHM et al. (2003) Ultrafast enzymatic reaction dynamics in protochlorophyllide oxidoreductase. Nature Structural Biology 10: 491–492.
    Jordan P, Fromme P, Witt HT et al. (2001) Three-dimensional structure of cyanobacterial photosystem I at 2.5 Å resolution. Nature 411: 909–916.
    Porra RJ (1997) Recent progress in porphyrin and chlorophyll biosynthesis. Photochemistry and Photobiology 65: 492–516.
    book Rüdiger W (2003) "The last steps of chlorophyll synthesis". In: Kadish KM, Smith KM and Guilard R (eds) Porphyrin Handbook vol. 13, pp. 71–108. Oxford: Academic Press
    book Shoolingin-Jordan PM (2003) "The biosynthesis of coproporphyrinogen III". In: Kadish KM, Smith KM and Guilard R (eds) Porphyrin Handbook vol. 12, pp. 33–74. Oxford: Academic Press
    book Smith KM (2003) "Chlorosome chlorophylls (bacteriochlorophylls c, d, and e): synthesis, partial syntheses, and biosynthetic proposals". In: Kadish KM, Smith KM and Guilard R (eds) Porphyrin Handbook vol. 13, pp. 157–182. Oxford: Academic Press
    Vavilin DV and Vermaas WFJ (2002) Regulation of the tetrapyrrole biosynthetic pathway leading to heme and chlorophyll in plants and cyanobacteria. Physiologia Plantarum 115: 9–24.
    book Willows RD and Hansson M (2003) "Mechanism, structure, and regulation of magnesium chelatase". In: Kadish KM, Smith KM and Guilard R (eds) Porphyrin Handbook vol. 13, pp. 1–47. Oxford: Academic Press
    Xiong J, Inoue K and Bauer CE (1999) Tracking molecular evolution of photosynthesis by characterization of a major photosynthesis gene cluster from Heliobacillus mobilis. Proceedings of the National Academy of Sciences of the USA 97: 13561–13566.
    Zouni A, Witt H-T, Kern J et al. (2001) Crystal structure of photosystem II from Synechococcus elongates at 38 Å resolution. Nature 409: 739–743.
 Further Reading
    book Aro E-M and Andersson B (2001) Regulation of Photosynthesis. Dordrecht, The Netherlands: Kluwer Academic.
    book Blankenship RE (2002) Molecular Mechanisms of Photosynthesis. Oxford: Blackwell Science.
    book Blankenship RE, Madigan MT and Bauer CE (eds) (1995) Anoxygenic Photosynthetic Bacteria. Dordrecht: Kluwer Academic.
    book Bryant DA (ed.) (1994) The Molecular Biology of Cyanobacteria. Dordrecht, The Netherlands: Kluwer Academic.
    book Kadish KM, Smith KM and Guilard R (eds) (2003) "The Porphyrin Handbook", vol. 12, The Iron and Cobalt Pigments: Biosynthesis, Synthesis, and Degradation. Oxford: Academic Press.
    book Kadish KM, Smith KM and Guilard R (eds) (2003) "The Porphyrin Handbook", vol. 13, Chlorophylls and Bilins: Biosynthesis, Synthesis, and Degradation. Oxford: Academic Press.
    Merritt JE and Loening KL (1979) Nomenclature of tetrapyrroles. Pure and Applied Chemistry 51: 2251–2304.
    book Ort DR and Yocum CF (eds) (1996) Oxygenic Photosynthesis: The Light Reactions. Dordrecht, The Netherlands: Kluwer Academic.
    Schubert W-D, Klukas O, Saenger W et al. (1998) A common ancestor for oxygenic and anoxygenic photosynthetic systems: a comparison based on the structural model of photosystem I. Journal of Molecular Biology 280: 297–314.
    book Sheer H (ed.) (1991) Chlorophylls. Boca Raton, FL: CRC Press.
    Willows RD (2003) Biosynthesis of chlorophylls from protoporphyrin IX. Natural Products Reports 20: 327–341.
    Xiong J and Bauer CE (2002) Complex evolution of photosynthesis. Annual Review of Plant Biology 53: 503–521.
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Fujita, Yuichi(May 2005) Chlorophylls. In: eLS. John Wiley & Sons Ltd, Chichester. http://www.els.net [doi: 10.1038/npg.els.0003887]