This view shows enzymes only for those organisms listed below, in the list of taxa known to possess the pathway. If an enzyme name is shown in bold, there is experimental evidence for this enzymatic activity.
|Superclasses:||Biosynthesis → Secondary Metabolites Biosynthesis → Phenylpropanoid Derivatives Biosynthesis → Flavonoids Biosynthesis → Anthocyanins Biosynthesis|
Expected Taxonomic Range: Magnoliophyta
Anthocyanins are produced in two distinguished sets of reactions, the first one (early-stage) leading to the first stable anthocyanidin, i.e. anthocyanidin-3-O-glucosides ( anthocyanin biosynthesis (cyanidin 3-O-glucoside)) and the second one (late-stage) comprising further modification of those compounds such as glycosylation, acylation and methylation (this pathway). These late-stage reactions are concerned with fine adjustment for a variety of floral color which is diverse and less understood than the steps involved in the early-stage reactions [Yamazaki99] [YonekuraSakakib00].
The decoration of pelargonidin (this pathway) is typical for a variety of plants such as Perilla frutescens, Glandularia x hybrida, Silene dioica [Yamazaki99] and Dahlia pinnata [Suzuki02b]. Many of the above mentioned plants are characterized by anthocyanins that are intermediately 5-O-glucosylated.
About This Pathway
All the modifications of the anthocyanidin-3-O-glucosides contribute to the stability of the anthocyanins and/or the refinement of the colors which appear in flowers and fruits. The 5-O-glucosylation of anthocyanidin-3-O-glucosides, catalyzed by the anthocyanin 5-O-glucosyltransferase (5-GT) does not significantly change the color of anthocyanins but is important for further modification of anthocyanin molecules [Yamazaki02] [Yamazaki99]. It has been discussed that these modifications increase the stability and color variation towards purple hues by inter- and intramolecular stacking of the anthocyanins with polyphenols [Brouillard94].
A significant contribution to intensification of color and color shift towards blue is accomplished by aromatic acylation with hydroxycinnamic acids of the anthocyanin molecules due to a bathochromic shift. The enzyme catalyzing this step, anthocyanin 3-O-glucoside-6"-O-acyltransferase has been characterized in Perilla frutescens [Fujiwara98] [YonekuraSakakib00]. The exact metabolic succession of aromatic acylation (C-ring 3-position, A-ring 5-position) of the anthocyanin glucosides (mono-, diglucoside) is not known and may depend on the species involved (compare salvianin biosynthesis and gentiodelphin biosynthesis).
The other type of acylation that commonly contributes to furnish anthocyanins and many other secondary metabolites, i.e. aliphatic acylation, such as malonylation is thought to enhance pigment solubility in water, protect the anthocyanins from enzymatic degradation and facilitates the uptake of anthocyanins into vacuoles [Heller94]. The malonylation of anthocyanins, for instance catalyzed by the anthocyanidin 3-O-glucoside-6"-O-malonyltransferase [Suzuki02b] generally occurs under strict regiocontrol during the late stage of their biosynthesis.
Other modifications of the anthocyanins involve further glycosylations catalyzed by anthocyanidin 3-O-glucoside-6"-O-rhamnosyltransferase [Kamsteeg80] and anthocyanidin 3-O-rutinoside-5-O-glucosyltransferase [Kamsteeg78]. Rhamnosylation appears to be a frequent step altering the structure of compounds and the nucleoside has been shown to be produced in plants, e.g. in red campion [Kamsteeg78a].
Fujiwara98: Fujiwara H, Tanaka Y, Fukui Y, Ashikari T, Yamaguchi M, Kusumi T (1998). "Purification and characterization of anthocyanin 3-aromatic acyltransferase from Perilla frutescens." Plant Science, 137, 87-94.
Heller94: Heller W, Forkmann G (1994). "Biosynthesis of flavonoids." In: Harborne JB (editor) The flavonoids. Advances in research since 1986. Chapman & Hall, London Glasgow New York Tokyo Melbourne Madras, 499-537.
Kamsteeg78: Kamsteeg J, van Brederode J, van Nigtevecht G (1978). "Identification, properties, and genetic control of UDP-glucose: cyanidin-3-rhamnosyl-(1 leads to 6)-glucoside-5-O-glucosyltransferase isolated from petals of the red campion (Silene dioica)." Biochem Genet 16(11-12);1059-71. PMID: 751641
Kamsteeg78a: Kamsteeg J, Van Brederode J, Van Nigtevecht G (1978). "The formation of UDP-L-rhamnose from UDP-D-glucose by an enzyme preparation of red campion (Silene dioica (L) Clairv) leaves." FEBS Lett 91(2);281-4. PMID: 680134
Kamsteeg80: Kamsteeg J, Van Brederode J, Van Nigtevecht G (1980). "Identification, properties and genetic control of UDP-L-rhamnose:anthocyanidin 3-O-glucoside, 6"-O-rhamnosyltransferase isolated from petals of the red campion (Silene dioica)." Z. Naturforsch., 35c, 249-257.
Suzuki02b: Suzuki H, Nakayama T, Yonekura-Sakakibara K, Fukui Y, Nakamura N, Yamaguchi MA, Tanaka Y, Kusumi T, Nishino T (2002). "cDNA cloning, heterologous expressions, and functional characterization of malonyl-coenzyme a:anthocyanidin 3-o-glucoside-6"-o-malonyltransferase from dahlia flowers." Plant Physiol 130(4);2142-51. PMID: 12481098
Yamazaki02: Yamazaki M, Yamagishi E, Gong Z, Fukuchi-Mizutani M, Fukui Y, Tanaka Y, Kusumi T, Yamaguchi M, Saito K (2002). "Two flavonoid glucosyltransferases from Petunia hybrida: molecular cloning, biochemical properties and developmentally regulated expression." Plant Mol Biol 48(4);401-11. PMID: 11905966
Yamazaki99: Yamazaki M, Gong Z, Fukuchi-Mizutani M, Fukui Y, Tanaka Y, Kusumi T, Saito K (1999). "Molecular cloning and biochemical characterization of a novel anthocyanin 5-O-glucosyltransferase by mRNA differential display for plant forms regarding anthocyanin." J Biol Chem 274(11);7405-11. PMID: 10066805
YonekuraSakakib00: Yonekura-Sakakibara K, Tanaka Y, Fukuchi-Mizutani M, Fujiwara H, Fukui Y, Ashikari T, Murakami Y, Yamaguchi M, Kusumi T (2000). "Molecular and biochemical characterization of a novel hydroxycinnamoyl-CoA: anthocyanin 3-O-glucoside-6"-O-acyltransferase from Perilla frutescens." Plant Cell Physiol 41(4);495-502. PMID: 10845463
Matsuba10: Matsuba Y, Sasaki N, Tera M, Okamura M, Abe Y, Okamoto E, Nakamura H, Funabashi H, Takatsu M, Saito M, Matsuoka H, Nagasawa K, Ozeki Y (2010). "A novel glucosylation reaction on anthocyanins catalyzed by acyl-glucose-dependent glucosyltransferase in the petals of carnation and delphinium." Plant Cell 22(10);3374-89. PMID: 20971893
Rubio06: Rubio S, Larson TR, Gonzalez-Guzman M, Alejandro S, Graham IA, Serrano R, Rodriguez PL (2006). "An Arabidopsis mutant impaired in coenzyme A biosynthesis is sugar dependent for seedling establishment." Plant Physiol 140(3);830-43. PMID: 16415216
Suzuki04a: Suzuki H, Nakayama T, Yamaguchi M, Nishino T (2004). "cDNA cloning and characterization of two Dendranthema × morifoliumanthocyanin malonyltransferases with different functional activities." Plant Science 166:89-96.
Teusch87: Teusch M, Forkmann G, Seyffert W (1987). "Genetic control of hydroxycinnamoyl-coenzymes A:anthocyanidin 3-glycoside-hydroxycinnamoyltransferase from petals of Matthiola incana." Phytochemistry 26(4):991-994.
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