Plastoquinone biosynthesis

With carotenoid biosynthesis, plastoquinone is involved as an electron acceptor, which we encounter further in photosynthetic electron transport [2]. An important precursor in the synthesis of plastoquinone, which also serves as a cofactor for the PDS enzyme, is homogentisic acid, which is formed from 4-hydroxyphenyl-pyruvate by 4-hydroxyphenylpyruvate dioxygenase (HPPD)... 

The shikimate pathway is the major route in the biosynthesis of ubiquinone, menaquinone, phyloquinone, plastoquinone, and various colored naphthoquinones. The early steps of this process are common with the steps involved in the biosynthesis of phenols, flavonoids, and aromatic amino acids. Shikimic acid is formed in several steps from precursors of carbohydrate metabolism. The key intermediate in quinone biosynthesis via the shikimate pathway is the chorismate. In the case of ubiquinones, the chorismate is converted to para-hydoxybenzoate and then, depending on the organism, the process continues with prenylation, decarboxylation, three hydroxy-lations, and three methylation steps. - ... 

The third pathway involved in the quinones biosynthesis is the isoprenoid route. This pathway is primarily important for the formation of prenyl side chains of prenylquinones (ubiquinone, menaquinone, plastoquinones, etc.). The side chains of ubiquinones and prenylated naphthoquinones derive from polyprenyl diphosphates. 

The biosynthesis of monoterpenes, the major components of peppermint essential oils, can be divided into four stages (Fig. 9.4). Stage 1 includes the formation of isopentenyl diphosphate (IPP) and dimethylallyl alcohol (DMAPP). In plants, two separate pathways are utilized for the synthesis of these universal C5 intermediates, with the cytosolic mevalonate pathway being responsible for the formation of sterols and certain sesquiterpenes, and the plastidial mevalonate-independent pathway being involved in the biosynthesis of isoprene, monoterpenes, certain sesquiterpenes, diterpenes, tetraterpenes, as well as the side chains of chlorophyll and plastoquinone.16 In peppermint oil gland secretory cells, however, the mevalonate pathway is blocked and the biosynthesis of monoterpenoid essential... 

SCHWENDER, J., SEEMANN, M LICHTENTHALER, H.K., ROHMER, M., Biosynthesis of isoprenoids (carotenoids, sterols, prenyl side-chains of chlorophylls and plastoquinone) via a novel pyruvate/glyceraldehyde 3-phosphate non-mevalonate pathway in the green alga Scenedesmus obliquus, Biochem. J., 1996, 316, 73-80. 

The molecular target site of triketone herbicides is the enzyme -hydroxyphenylpyruvate dioxygenase (HPPD). Inhibition of this enzyme disrupts the biosynthesis of carotenoids and causes a bleaching (loss of chlorophyll) effect on the foliage similar to that observed with inhibitors ofphytoene desaturase (e.g. norflurazon). However, the mechanism of action of HPPD inhibitors is different. Inhibtion of HPPD stops the synthesis of homogen tisate (HGA), which is a key precursor of the 8 different tocochromanols (tocopherols and tocotrienols) and prenyl quinones. In the absence of prenylquinone plastoquinone, phytoene desaturase activity is interrupted. The bleaching of the green tissues ensues as if these compounds inhibited phytoene desaturase. 

The enzyme p-hydroxyphenylpyruvate dioxygenase is involved in the conversion of p-hydroxyphenylpyruvate into homogentisate, a key step in plastoquinone biosynthesis. Inhibition of this enzyme has an indirect effect on carotenoid biosynthesis as plastoquinone is a co-factor of the enzyme phytoene desaturase. The new maize herbicide isoxaflutole and the triketone herbicides such as sulcotrione (Figure 2.7), inhibit p-hydroxyphenylpyruvate dioxygenase and this leads to the onset of bleaching in susceptible weeds and ultimately plant death.4... 

In addition to its role as an intermediate in cholesterol biosynthesis, isopentenyl pyrophosphate is the activated precursor of a huge array of biomolecules with diverse biological roles (Fig. 21-48). They include vitamins A, E, and K plant pigments such as carotene and the phytol chain of chlorophyll natural rubber many essential oils (such as the fragrant principles of lemon oil, eucalyptus, and musk) insect juvenile hormone, which controls metamorphosis dolichols, which serve as lipid-soluble carriers in complex polysaccharide synthesis and ubiquinone and plastoquinone, electron carriers in mitochondria and chloroplasts. Collectively, these molecules are called isoprenoids. More than... 

Figure 25-4 Pathways of biosynthesis of ubiquinones, plastoquinones, tocopherols, and vitamin K.

Inhibitors of carotenoid synthesis also lead to chlorophyll destruction by destabilizing the photosynthetic apparatus. Total carotenoid content decreased with increased (-)-usnic concentration (Fig. 1.4). Carotenoid biosynthesis can be interrupted by inhibiting the enzyme phytoene desaturase that converts phytoene to carotenes or by inhibiting the enzyme HPPD responsible for plastoquinone (required for phytoene desaturase activity) synthesis.14 Usnic acid possesses some of the structural features of the triketone HPPD inhibitors, such as sulcotrione (Fig. 1.1C).8 (-)-Usnic acid had a strong inhibitory activity on HPPD, with an apparent IC50 of 70 nM, surpassing the activity obtained with the commercial herbicide sulcotrione (Fig. 1.5). 

Lichtenthaler, H.K. (2007) Biosynthesis, accumulation and emission of carotenoids, alpha-tocopherol, plastoquinone, and isoprene in leaves under high photosynthetic irradiance. Photosynth. Res., 92,163-79. 

Terpenoids, which are also known as isoprenoids, constitute the most abundant and structurally diverse group of plant secondary metabolites, consisting of more than 40,000 different chemical structures. The isoprenoid biosynthetic pathway generates both primary and secondary metabolites that are of great importance to plant growth and survival. Among the primary metabolites produced by this pathway are phytohormones, such as gibberellic acid (GA), abscisic acid (ABA), and cytokinins the carotenoids, such as chlorophylls and plastoquinones involved in photosynthesis the ubiquinones required for respiration and the sterols that influence membrane stmcture (see also Steroid and Triterpene Biosynthesis) (Fig. 1). Monoterpenoids (CIO), sesquiterpenoids (Cl5), diterpenoids (C20), and... 

Quinones.—Four menaquinone (139) homologues from Sarcina lutea have been identified as dihydromenaquinones-6, -7, -8, and -9. A novel quinone from bulbs and leaves of Iris is thought to be related to plastoquinone-9 (140) but to have a modified ring methylation pattern.No chemical data were reported. The distribution of ubiquinone (141) homologues in a number of Gram-negative bacteria has been surveyed.The biosynthesis of menaquinones and related quinones has been reviewed. The molecular structure and electronic properties of ubiquinone have been studied by semi-empirical molecular orbital theory. 

A good example of compartmentation, although not yet completely understood, is the apparent segregation of isoprenoid biosynthesis in plants (123). [2- 14C]-Mevalonate was easily incorporated in squalene, phytosterols, P-amyrin and ubiquinone but not in the plastid constituents P-carotene, chlorophyll phytyl group or plastoquinone. The opposite result was obtained with 14C02. 

A number of other herbicides interfere with photosynthesis in specific ways. Amitrole inhibits biosynthesis of chlorophyll and carotenoids. The affected plants present a bleached appearance before they die because of the loss of their characteristic pigments. Another herbicide, atrazine, inhibits the oxidation of water to hydrogen ion and oxygen. Still other herbicides interfere with electron transfer in the two photosystems. In photosystem II, diuron inhibits electron transfer to plastoquinone, whereas bigyridylium herbicides accept electrons by competing with the electron acceptors in photosystem I. The inhibitors active in photosystem I include diquat and paraquat. The latter substance attained some notoriety when it was used to interfere with an... 

Triketones with Heterocyclic Substituents. Triketones represent a well-studied, but still developing, family of herbicides. Some with pyiidyl substituents are among the most active. Much of the research in this area has been reviewed. The triketones are inhibitors of the plant enzyme 4-hydroxyphenylpymvate dioxygenase (HPPD), which plays a key role in the biosynthesis of plastoquinone and tocopherol. Compound 11.6, which is known as nicotinoyl syncarpic acid, is shown as a typical structure of this type. Its potent herbiddal activity led to synthetic work that has yielded many related stmctures in an effort to improve selectivity in the herbicidal action. 

Undecaprenol (bactoprenol) from Salmonella contains eleven isoprene units, and two irons and nine cis double bonds In the form of undecaprenyl phosphate, it acts as a carrier of carbohydrate residues in the biosynthesis of bacterial antigenic polysaccharides synthesis of Murein (see) also depends on undecaprenyl phosphate. In eukaryotes the Dolichol phosphates (see) function in the transfer of carbohydrate residues in the synthesis of glycoproteins and glycoli-pids. Probably the long lipid chains of these P serve to anchor them in membranes, while the phosphate group acts as a carrier by protruding into the cytoplasm. It is not known whether all P. function as carbohydrate carriers. The structural relationship between solanesol and plastoquinone-9 and ubiquinone-9, and the joint occurrence of these compounds suggest a precursor role for P. Biosynthesis of P. proceeds from mevalonic acid and the conformation of all double bonds is predetermined in early precursors. 

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