Geranyl diphosphate synthase

Evidence for de novo synthesis of pheromone components was obtained by showing that labeled acetate and mevalonate were incorporated into ipsdienol by male Ips pini [103,104]. Similarly, labeled acetate and other labeled intermediates were shown to be incorporated into frontalin in a number of Dendroctonus species [105]. Possible precursors to frontalin include 6-methyl-6-hep-ten-2-one, which was incorporated into frontalin by D. ruffipennis [106]. The precursor 6-methyl-6-hepten-2-one also was shown to be converted to bre-vicomin in the bark beetle, Dendroctonus ponderosae [107]. In addition, the expression patterns of HMG-CoA reductase and HMG-CoA synthase are tightly correlated with frontalin production in Dendroctonus jeffreyi [108, 109]. A geranyl diphosphate synthase cDNA from I. pini was also isolated, functionally expressed, and modeled [110]. These data indicate that the de novo isoprenoid biosynthetic pathway is present in bark beetles. A variety of other monoterpene alcohols such as myrcenol, pityol, and sulcitol are probably synthesized through similar pathways [111]... 

Figure 9.4 Monoterpene biosynthesis in peppermint oil gland secretory cells. The enzymes involved in this pathway are (1) 1-deoxy-D-xylulose 5-phosphate synthase, (2) 2-C-methyl-D-erythritol 4-phosphate reductoisomerase, (3) 2-C-methyl-D-erythritol 4-phosphate cytidyltransferase, (4) 4-(cytidine 5 -diphospho)-2-C-methyl-D-erythritol kinase, (5) 2-C-methyl-D-erythritol 2,4-cyclodiphosphate synthase, (6) isopentenyl diphosphate isomerase, (7) geranyl diphosphate synthase, (8)...

BURKE C.C., WILDUNG, M.R., CROTEAU, R., Geranyl diphosphate synthase cloning, expression, and characterizatin of this prenyltransferase as a heterodimer, Proc. Natl. Acad. Sci. USA, 1999, 96,13062-13067. 

Turner GW, Croteau R (2004) Organization of monoterpene biosynthesis in Mentha. Immunocytochemical localizations of geranyl diphosphate synthase, Umonene-6-hydroxylase, isopiperitenol dehydrogenase, and pulegone reductase. Plant Physiol 136 4215 227... 

This enzyme [EC 2.5.1.1] (also referred to as prenyl-transferase and geranyl-diphosphate synthase) catalyzes the reaction of dimethylallyl diphosphate and isopen-tenyl diphosphate to produce geranyl diphosphate and pyrophosphate (or, diphosphate). The enzyme will not accept larger prenyl diphosphates as substrates. 

BORNYL PYROPHOSPHATE SYNTHASE Geranyl diphosphate synthase,... 

Young A., Tittiger C., Welch W. and Blomquist G. J. (2001) Monoterpenoid pheromone biosynthesis fishing for the elusive geranyl diphosphate synthase in bark beetles. Presented at Annu. Meet. Int. Soc. Chem. Ecol., 18th, Lake Tahoe. 

Clastre, M., Bantignies, B., Feron, G., Soler, E. and Ambid, G. (1993) Purification and characterization of geranyl diphosphate synthase from Vitis vinifera L. cv Muscat de Frontignan cell cultures. Plant Physiol., 102, 205-11. 

Geranyl diphosphate synthase (GPPS E.C 2.5.1.1) catalyzes the condensation of isopentenyl diphosphate with dimethylallyl diphosphate to give a CIO compound, geranyl diphosphate, which is the universal precursor of all monoterpenoids. Fig. (6) [314]. 

Fig. 1.5 Reactions catalyzed by short chain isoprenyl diphosphate synthases in plants. All use the same precursors, IPP and DMAPP, but the enzymes may reside in different subcelLular compartments. The reactions catalyzed by geranyl diphosphate synthase and geranylgeranyl diphosphate synthase are thought to occur in the plastid, and the reaction catalyzed by farnesyl diphosphate in the cytosol.

Fig. 1.6 Phylogenetic tree of gymnosperm and angiosperm isoprenyl diphosphate synthase sequences. The isolated Picea ahies sequences are marked other isoprcnyl diphosphate synthases sequences are listed according to the major reaction product of the recombinant protein. Abbreviations GPP synthase, geranyl diphosphate synthase FPP synthase, famesyl diphosphate synthase and GGPP synthase, geranyl geranyl diphosphate synthase large su, large subunit of protein small su, small subunit of protein.

THOLL, D., CROTEAU, R., GERSHENZON, J., Partial purification and characterization of the short-chain prenyltransferases, geranyl diphosphate synthase and famesyl diphosphate synthase, from Abies grandis (Grand fir).. Arch. Biochem. Biophys., 2001,386, 233-242. 

THOLL, D., KISH, C.M., ORLOVA, 1., SHERMAN, D., GERSHENZON, J., PICHERSKY, E., DUDAREVA, N., Formation of monoterpenes in Antirrhinum majus and Clarkia breweri flowers involves heterodimeric geranyl diphosphate synthases., Plant Cell, 2004,16, 977-992. 

BOUVIER, F., SUIRE, C., D HARLINGUE, A., BACKHAUS, R.A., CAMARA, B., Molecular cloning of geranyl diphosphate synthase and compartmentation of monoterpene synthesis in plant cells., Plant J, 2000,24, 241-252. 

Upon the synthesis of IPP (C5) and its isomer DMAPP (C5) by either MVA or DXP pathways, the next step is chain elongation. The carbonium ion is a potent alkylating agent that can react with IPP (three molecules of IPP converted into one molecule of geranyl diphosphate (GPP) by condensation reaction catalyzed by enzyme geranyl diphosphate synthase), to yield geranyl diphosphate (GPP). Famesyl pyrophosphate synthase (EPS) is the prenyltransferase that catalyzes l -4 condensation reactions of IPP with the allylic diphosphates, dimethylallyl diphosphate (DMAPP), to produce famesyl pyrophosphate (FPP). 

Fig. 99.1 Proposed biosynthetic pathway of artemisinin in Artemisia annua L. plant. SQS Squalene synthase, ADS amorpha-4,11-diene synthase, FPP Famesyl diphosphate, FPS Famesyl pyrophosphate synthase, GPP Geranyl diphosphate, GPPS Geranyle diphosphate synthase, GS germaciene A synthase, DMAPP Dimethylallyl diphosphate, IPP isopeniraiyl diphosphate, CPS P-caryophyllene synthase, DBR2 double bond reductase 2, ECS epi-cedrol synthase, FPP fanesyl diphosphate, PS (E)-P-famesene synthase (Drawn based on informatitm published by Abdin et al., [18] and Zhang et al., 2005)...

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