Plant isoprenoids metabolism

Relatively little is known about plant sterols. (Most of the research effort in steroid metabolism has been expended in the investigation of steroid-related human diseases.) It appears, however, that the initial phase of plant sterol synthesis is very similar to that of cholesterol synthesis with the following exception. In plants and algae the cyclization of squalene-2,3-epoxide leads to the synthesis of cycloartenol (Figure 12.30) instead of lanosterol. Many subsequent reactions in plant sterol pathways involve SAM-mediated methylation reactions. There appear to be two separate isoprenoid biosynthetic pathways in plant cells the ER/cyto-plasm pathway and a separate chloroplast pathway. The roles of these pathways in plant isoprenoid metabolism are still unclear. 

FRASER, P.D., ELISABETE, M., PINTO, S., HOLLOWAY, D.E., BRAMLEY, P.M., Application of high-performance liquid chromatography with photodiode array detection to the metabolic profiling of plant isoprenoids, Plant J., 2000, 24, 551-558. 

Perhaps the most interesting arthropodan defensive compounds from the point of view of structural diversity are the alkaloids. While alkaloids had long been believed to arise only as a consequence of plant secondary metabolism, it has become apparent over the last few decades that arthropods are both prolific and innovative alkaloid chemists. The millipede Polyzonium rosalbum, once thought to secrete camphor (20), in fact gives off a camphoraceous/earthy aroma produced by the spirocyclic isoprenoid imine polyzonimine (21). 

Liu Y, Wang H, Ye H-C, Li G-F. (2005) Advances in the plant isoprenoid biosynthesis pathway and its metabolic engineering. J Integr Plant Biol 47 769-782. 

SCHEME 1.—The Biosynthesis and Metabolism of Dolichyl Phosphate and Other Plant Isoprenoids. 

Investigations of isoprenoid metabolism and biochemistry in plants have been hampered for several reasons. Some isoprenoids accumulate over long developmental time courses, which suggests that the enzymes responsible for their biosynthesis are either present in low abundance or have low activity levels. Sterols... 

Figure 10.5 Plant cell cultures have proven to be very useful for studying plant-pathogen interactions and isoprenoid metabolism. Tobacco cell cultures respond rapidly to the addition of fungal elicitors (0.5 pg cellulase/ml of culture) by browning (A) (analogous to a hypersensitive response) and the production of phytoalexins (B). Media was collected from elicited cell cultures at the indicated times, partitioned against an organic solvent, and concentrated aliquots run on a silica TLC plate. The plates were then sprayed with a suspension of Cladosporium cucumerinum spores and incubated in a humid environment for 5 days before viewing (B). The compound released from the elicitor-treated tobacco cells that inhibits spore germination is capsidiol, a sesquiterpene.

Ayabe S, Nagashima S, Furuno T, Takahashi T, Yuki TT, Hirota H (1991) Growth and isoprenoid metabolism of cultured Picrama quassioides cells. Plant Tissue Cult Lett 8 198-200... 

Bramley PM (1997) Isoprenoid metabolism. In Dey PM, Harbome JB (eds) Plant biochemistry. Academic Press, San Diego, USA, pp 417-437... 

Branched-chain amino acids as precursurs of plant isoprenoids L-Leucine and L-valine, when fed to germinating pea seeds (Pisum sativum) were incorporated into squalene and 6-amyrin [39]. Chemical degradation by ozonolysis of the radioactive squalene revealed an equal distribution of the radioactivity in the IPP-derived (4 portions per molecule) and the DMAPP-derived moieties (2 portions per molecule). However, an unbalanced distribution in favor of the DMAPP-derived moiety of monoterpenoids was found after feeding radioisotopically labeled L-leucine, L-valine, DL-alanine, acetate, and R,S-MVA to intact plants of Cinnamomum camphora and of Pelargonium roseum [40]. The relatively low incorporation of amino acids was explained by several hypotheses a) the radioactivity of amino acids is scattered into other metabolites rather than monoterpenoids b) there is a great pool of the amino acids which leads to dilution of radioactivity, and c) the low permeation of the amino acids into the biosynthetic site of monoterpenoids [40]. The DMAPP-derived moiety of monoterpenoids, biosynthesized from [U- C]leucine and [U- ]valine was labeled with more than 64% of the incorporated tracers, while this moiety when derived from [2- " C]MVA contained less than 32% of the tracers [40]. This lends support to the interpretation that both amino acids are incorporated not via MV A, but by an alternate route, e,g, a combination of the well known mammalian leucine degradation pathway and a reversal of the MVA shunt (see below). The distribution pattern in monoterpenoids after administration of [2- ]alanine was similar to that after incorporation of MVA, which indicates that alanine is first metabolized to acetyl-CoA, which then constructs preferentially the IPP-derived moiety of the monoterpenoids via MVA [40]. 

Chappell J, Proulx J, Wolf F, Cuellar RE, Saunders C. Is HMG-CoA reductase a rate limiting step for isoprenoid metabolism Plant Physiol, 1991 96 (supplement) 127... 

Rodriguez-Concepcion, M. and Boronat, A., Elncidation of the methylerythritol phosphate pathway for isoprenoid biosynthesis in hacteria and plastids a metabolic milestone achieved throngh genomics. Plant Physiol. 130, 1079, 2002. Rodriguez-Concepcion, M., Early steps in isoprenoid biosynthesis multilevel regulation of the supply of common precursors in plant cells, Phytochem. Rev. 5, 1, 2006. Eisenreich, W., Rohdich, F., and Bacher, A., Deoxyxylulose phosphate pathway to terpenoids, Trends Plant Sci. 6, 78, 2001. 

Poly(3HB) synthesis in various subcellular compartments could be used to study how plants adjust their metabolism and gene expression to accommodate the production of a new sink, and how carbon flux through one pathway can affect carbon flux through another. For example, one could study how modifying the flux of carbon to starch or lipid biosynthesis in the plastid affects the flux of carbon to acetyl-CoA and poly(3HB). Alternatively, one could study how plants adjust the activity of genes and proteins involved in isoprenoid and flavonoid biosynthesis to the creation of the poly(3HB) biosynthetic pathway in the cytoplasm, since these three pathways compete for the same building block, i. e., acetyl-CoA. 

Fraser PD, Enfissi EMA, Halket JM, Truesdale MR, Yu D, Gerrish C, Bramley PM. 2007. Manipulation of phytoene levels in tomato fruit effects on isoprenoids, plastids, and intermediary metabolism. Plant Cell 19 3194-3211. 

Heldt HW and Heldt F. 2005. A large diversity of isoprenoids has multiple functions in plant metabolism. In Plant Biochemistry, 3rd ed. San Diego, CA Elsevier Academic Press, pp. 413 134. 

Isoprene metabolism in plants is very complex. Plants can synthesize many types of aromatic substances and volatile oils from isoprenoids. Examples include menthol (1= 2 ), camphor (1 = 2), and citronellal (1 = 2). These Cio compounds are also called monoterpenes. Similarly, compounds consisting of three isoprene units (1 = 3) are termed sesquiterpenes, and the steroids (1 = 6) are called triterpenes. 

Heintze, A., Goerlach, J., Leuschner, C., Hoppe, R, Hagelstein, R, Schulze-Siebert, D. and Schultz, G. (1990) Rlastidic isoprenoid synthesis during chloroplast development change from metabolic autonomy to division-of-labor stage. Plant Physiol., 93,1121-7. 

Enfissi EMA, Eraser PD, Lois LM, Boronat A, Schuch W, Bramley PM. Metabolic engineering of the mevalonate and non-mevalonate isopentenyl diphosphate-forming pathways for the production of health-promoting isoprenoids in tomato. Plant Biotechnol. J. 2003 3 17-27. 

Figure 1 The retrobiosynthetic principle. Labeling patterns of central metabolic intermediates (shown in yellow boxes) are reconstructed from the labeling patterns of sink metabolites, such as protein-derived amino acids, storage metabolites (starch and lipids), cellulose, isoprenoids, or RNA-derived nucleosides. The reconstruction is symbolized by retro arrows following the principles of retrosynthesis in synthetic organic chemistry. The figure is based on known biosynthetic pathways of amino acids, starch, cellulose, nucleosides, and isoprenoids in plants. The profiles of the central metabolites can then be used for predictions of the labeling patterns of secondary metabolites. In comparison with the observed labeling patterns of the target compounds, hypothetical pathways can be falsified on this basis.

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