MetaCyc Pathway: pinosylvin metabolism
Traceable author statement to experimental supportInferred from experiment

Enzyme View:

Pathway diagram: pinosylvin metabolism

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: BiosynthesisSecondary Metabolites BiosynthesisPhenylpropanoid Derivatives BiosynthesisStilbenes Biosynthesis
BiosynthesisSecondary Metabolites BiosynthesisPhytoalexins BiosynthesisStilbene Phytoalexins Biosynthesis
Metabolic Clusters

Some taxa known to possess this pathway include : Pinus densiflora, Pinus strobus, Pinus sylvestris, Psilotum nudum

Expected Taxonomic Range: Euphyllophyta

General Background

Pinosylvin (3,5-dihydroxystilbene) is found predominantly as a constituent in the heartwood of trees but is also formed in response to biotic stress in young tree seedlings, thus considered as a phytoalexin. Unlike other related hydroxystilbenes such as resveratrol ( resveratrol biosynthesis) pinosylvin lacks a hydroxyl group in ring B and originates by condensation of 3 malonyl-CoA and cinnamoyl-CoA instead of p-coumaroyl-CoA [PreisigMuller99].

Beside pinosylvin (PS), pinosylvin monomethylether (PSM) is another major stilbene that has been found in heartwood of trees being considered as constitutive protectant preventing the decay of wood by microorganisms [Hart81] [Kindl85]. Both compounds are rapidly induced upon biotic stress, e.g. caused by the fungus Botrytis cinerea the pathogen of the gray-mold rot [Schwekendiek92] or abiotic stress such as exposure to ozone [Chiron00] or UV [Gehlert90]. It has been demonstrated that pinosylvin and its monomethylether is much more effective to prevent the growth of most wood-rotting fungi than the also tested resveratrol [Seppanen04].

The enzyme, stilbene synthase (STS), catalyzing the formation of pinosylvin belongs to the plant specific polyketide synthases (PKS) and is closely related to the chalcone synthase(s) (CHS) [Lanz91] [Tropf94]. Stilbene synthases (STS) are homodimeric, plant-specific polyketide synthases occurring in widely unrelated plants. Stilbene synthases function as unimodular PKS's with a single active site and each subunit of the protein is able to synthesize the end products but with lower efficiency and product specificity [Tropf95] [Kodan02].

Stilbene synthases have been found to represent a small multigene family in plants where the several members are differentially expressed in response to exogenous stimuli. This applies even to the most primitive vascular plant, i.e. Psilotum nudum [Yamazaki01] which contain a family of four CHS/STS synthases. The most receptive element to stress seems to correspond to only one sort of stilbene synthase [Schwekendiek92] [PreisigMuller99] in pine seedlings indicating a functional ranking among the STS's responsible for pinosylvin formation in heartwood and upon stress.

About This Pathway

The stilbene synthase specific for the catalyzation of pinosylvin not only accepts cinnamoyl-CoA but also its dihydro-isomer phenylpropionyl-CoA (dihydrocinnamoyl-CoA) forming dihydropinosylvin. However, this kind of reaction does not require a different enzyme (dihydropinosylvin synthase) as previously thought [Fliegmann92] but merely reflects the broader substrate acceptance of the pinosylvin-forming stilbene synthases [Schanz92] where some members of this family express a higher affinity towards phenylpropionyl-CoA than others. The product specificity and enzyme activity of different STS's can be influenced by a single amino acid exchange in the protein sequence [Raiber95].

The other enzyme of the pathway, pinosylvin methyltransferase (PMT) has been purified and sequenced [Chiron98]. The PMT like the STS is induced in the sapwood, phloem, and needles of conifers as a response to wounding, fungal attack [Chiron00] or chemical stress such as ozone or sulphur dioxide [Rosemann91] with pinosylvin and pinosylvin monomethylester accumulating in those tissues. The experimental data so far indicate a transcriptional induction of ozone-induced stilbene biosynthesis where the sequence of polyketide synthesis (pinosylvin) and O-methylation (pinosylvin monomethylether) is triggered upon stress [Chiron00a]. As for the STS's the pinosylvin methyltransferase (PMS) represents a small multigene family in pine species where various members might be differentially regulated upon environmental signals [Chiron00].

Created 22-Nov-2005 by Foerster H, TAIR


Chiron00: Chiron H, Drouet A, Lieutier F, Payer HD, Ernst D, Sandermann H (2000). "Gene induction of stilbene biosynthesis in Scots pine in response to ozone treatment, wounding, and fungal infection." Plant Physiol 124(2);865-72. PMID: 11027734

Chiron00a: Chiron H, Drouet A, Claudot AC, Eckerskorn C, Trost M, Heller W, Ernst D, Sandermann H (2000). "Molecular cloning and functional expression of a stress-induced multifunctional O-methyltransferase with pinosylvin methyltransferase activity from Scots pine (Pinus sylvestris L.)." Plant Mol Biol 44(6);733-45. PMID: 11202436

Chiron98: Chiron H, Drouet A, Heller W, Sandermann H (1998). "DNA-Sequenz der Pinosylsvin-3-O-methyltransferase (PMT)." inventors. August 13, 1998. Deutsches Patentamt A-Nr 198 36 774.0.

Fliegmann92: Fliegmann J, Schroder G, Schanz S, Britsch L, Schroder J (1992). "Molecular analysis of chalcone and dihydropinosylvin synthase from Scots pine (Pinus sylvestris), and differential regulation of these and related enzyme activities in stressed plants." Plant Mol Biol 18(3);489-503. PMID: 1536925

Gehlert90: Gehlert R, Schoppner A, Kindl H (1990). "Stilbene synthase from seedlings of Pinus sylvestris: Purification and induction in response to fungal infection." Molecular Plant-Microbe Interactions, 3(6), 444-449.

Hart81: Hart JH (1981). "Role of phytostilbenes in decay and disease resistance." Ann. Rev. Phytopathol., 19, 437-458.

Kindl85: Kindl H (1985). "Biosynthesis of stilbenes." In: Higuchi T (ed) Biosynthesis and biodegradation of wood components, Academic Press, Inc., Orlando, San Diego, New York, London, Toronto, Montreal, Sydney, Tokyo, 349-377.

Kodan02: Kodan A, Kuroda H, Sakai F (2002). "A stilbene synthase from Japanese red pine (Pinus densiflora): implications for phytoalexin accumulation and down-regulation of flavonoid biosynthesis." Proc Natl Acad Sci U S A 99(5);3335-9. PMID: 11880657

Lanz91: Lanz T, Tropf S, Marner FJ, Schroder J, Schroder G (1991). "The role of cysteines in polyketide synthases. Site-directed mutagenesis of resveratrol and chalcone synthases, two key enzymes in different plant-specific pathways." J Biol Chem 266(15);9971-6. PMID: 2033084

PreisigMuller99: Preisig-Muller R, Schwekendiek A, Brehm I, Reif HJ, Kindl H (1999). "Characterization of a pine multigene family containing elicitor-responsive stilbene synthase genes." Plant Mol Biol 39(2);221-9. PMID: 10080690

Raiber95: Raiber S, Schroder G, Schroder J (1995). "Molecular and enzymatic characterization of two stilbene synthases from Eastern white pine (Pinus strobus). A single Arg/His difference determines the activity and the pH dependence of the enzymes." FEBS Lett 361(2-3);299-302. PMID: 7698342

Rosemann91: Rosemann D, Heller W, Sandermann Jr H (1991). "Biochemical Plant Responses to Ozone II. Induction of Stilbene Biosynthesis in Scots Pine (Pinus sylvestris L.) Seedlings." Plant Physiol. 97, 1280-1286.

Schanz92: Schanz S, Schroder G, Schroder J (1992). "Stilbene synthase from Scots pine (Pinus sylvestris)." FEBS Lett 313(1);71-4. PMID: 1426272

Schwekendiek92: Schwekendiek A, Pfeffer G, Kindl H (1992). "Pine stilbene synthase cDNA, a tool for probing environmental stress." FEBS Lett 301(1);41-4. PMID: 1451785

Seppanen04: Seppanen SK, Syrjala L, von Weissenberg K, Teeri TH, Paajanen L, Pappinen A (2004). "Antifungal activity of stilbenes in in vitro bioassays and in transgenic Populus expressing a gene encoding pinosylvin synthase." Plant Cell Rep 22(8);584-93. PMID: 14714142

Tropf94: Tropf S, Lanz T, Rensing SA, Schroder J, Schroder G (1994). "Evidence that stilbene synthases have developed from chalcone synthases several times in the course of evolution." J Mol Evol 38(6);610-8. PMID: 8083886

Tropf95: Tropf S, Karcher B, Schroder G, Schroder J (1995). "Reaction mechanisms of homodimeric plant polyketide synthase (stilbenes and chalcone synthase). A single active site for the condensing reaction is sufficient for synthesis of stilbenes, chalcones, and 6'-deoxychalcones." J Biol Chem 270(14);7922-8. PMID: 7713888

Yamazaki01: Yamazaki Y, Suh DY, Sitthithaworn W, Ishiguro K, Kobayashi Y, Shibuya M, Ebizuka Y, Sankawa U (2001). "Diverse chalcone synthase superfamily enzymes from the most primitive vascular plant, Psilotum nudum." Planta 214(1);75-84. PMID: 11762173

Other References Related to Enzymes, Genes, Subpathways, and Substrates of this Pathway

Latendresse13: Latendresse M. (2013). "Computing Gibbs Free Energy of Compounds and Reactions in MetaCyc."

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

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Please cite the following article in publications resulting from the use of MetaCyc: Caspi et al, Nucleic Acids Research 42:D459-D471 2014
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