Monoterpene interconversions: Metabolism of pulegone by a cell-free system from Mentha piperita

Battaile, J.; Burbott, Alice J.; Loomis, W.David

doi:10.1016/s0031-9422(00)88264-3

Cited by 49 publications

(6 citation statements)

References 9 publications

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“…7). Pulegone reductase, which catalyzes the NADPH-dependent reduction of the conjugated double bond of the terpenone, was first demonstrated in 1968 [3], and this operationally soluble enzyme has been revisited a number of times since [21,23]. Indirect evidence from these previous studies had suggested that pulegone reductase lacked stereoselectivity in the reduction to produce both (−)-menthone and (+)-isomenthone.…”

Section: (−)-Isopiperitenone Reductasementioning

confidence: 99%

(−)-Menthol biosynthesis and molecular genetics

Croteau

Davis

Ringer

et al. 2005

Naturwissenschaften

288

215

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(-)-Menthol is the most familiar of the monoterpenes as both a pure natural product and as the principal and characteristic constituent of the essential oil of peppermint (Mentha x piperita). In this paper, we review the biosynthesis and molecular genetics of (-)-menthol production in peppermint. In Mentha species, essential oil biosynthesis and storage is restricted to the peltate glandular trichomes (oil glands) on the aerial surfaces of the plant. A mechanical method for the isolation of metabolically functional oil glands, has provided a system for precursor feeding studies to elucidate pathway steps, as well as a highly enriched source of the relevant biosynthetic enzymes and of their corresponding transcripts with which cDNA libraries have been constructed to permit cloning and characterization of key structural genes. The biosynthesis of (-)-menthol from primary metabolism requires eight enzymatic steps, and involves the formation and subsequent cyclization of the universal monoterpene precursor geranyl diphosphate to the parent olefin (-)-(4S)-limonene as the first committed reaction of the sequence. Following hydroxylation at C3, a series of four redox transformations and an isomerization occur in a general "allylic oxidation-conjugate reduction" scheme that installs three chiral centers on the substituted cyclohexanoid ring to yield (-)-(1R, 3R, 4S)-menthol. The properties of each enzyme and gene of menthol biosynthesis are described, as are their probable evolutionary origins in primary metabolism. The organization of menthol biosynthesis is complex in involving four subcellular compartments, and regulation of the pathway appears to reside largely at the level of gene expression. Genetic engineering to up-regulate a flux-limiting step and down-regulate a side route reaction has led to improvement in the composition and yield of peppermint oil.

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Section: (−)-Isopiperitenone Reductasementioning

confidence: 99%

(−)-Menthol biosynthesis and molecular genetics

Croteau

Davis

Ringer

et al. 2005

Naturwissenschaften

288

215

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“…Since the biosynthetic pathway leading from limonene to menthone involves numerous steps dependent on either NAD + or NADPH (Fig. 1) (Battaile et al 1968;Kjonaas et al 1982;Croteau and Venkatachalam 1986;Karp et al 1990), the effect of exogenous cofactors on the incorporation of [8-3H]geranyl pyrophosphate into monoterpenes was determined. Addition of 1 mM each of NAD § and NADP + had essentially no effect on the level of incorporation or the distribution of products formed, indicating that oxidized pyridine nucleotides alone were not able to support the subsequent metabolic steps.…”

Section: Permeability Of Isolated Secretory Cells Towards Substrates mentioning

confidence: 99%

Morphology and monoterpene biosynthetic capabilities of secretory cell clusters isolated from glandular trichomes of peppermint (Mentha piperita L.)

McCaskill

Gershenzon

Croteau

1992

Planta

157

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Secretory cells were isolated from the monoterpene-producing glandular trichomes (peltate form) of peppermint as clusters of eight cells each. These isolated structures were shown to be non-specifically permeable to low-molecular-weight, water-soluble cofactors and substrates. Short incubation periods with the polar dye Lucifer yellow iodoacetamide (Mr=660) resulted in a uniform staining of the cytoplasm, with exclusion of the dye from the vacuole. The molecular-weight exclusion limit for this permeability was shown to be less than approx. 1800, based on exclusion of fluorescein-conjugated dextran (Mr ∼ 1800). Intact secretory cell clusters very efficiently incorporated [(3)H]geranyl pyrophosphate into monoterpenes. The addition of exogenous cofactors and redox substrates affected the distribution of monoterpenes synthesized from [(3)H]geranyl pyrophosphate, demonstrating that the cell clusters were permeable to these compounds and that the levels of endogenous cofactors and redox substrates were depleted in the isolated cells. When provided with the appropriate cofactors, such as NADPH, NAD(+), ATP, ADP and coenzyme A, the isolated secretory cell clusters incorporated [(14)C]sucrose into monoterpenes, indicating that these structures are capable of the de-novo biosynthesis of monoterpenes from a primary carbon source, and that they maintain a high degree of metabolic competence in spite of their permeable nature.

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“…This procedure resulted in removal of more than 99% of the glandular trichomes as determined microscopically and is notable for the use of XAD-4 polystyrene resin (at 1 g/g leaf tissue) as an adsorbent of endogenous terpenoids, reducing these materials to negligible levels in the extracts (7,8,12). Following homogenization and filtration of the extracts, sequential centrifugation at 3,000g, 1 …”

Section: Enzyme Extractsmentioning

confidence: 99%

Biochemical Characterization of a Spearmint Mutant That Resembles Peppermint in Monoterpene Content

Croteau¹,

Karp²,

Wagschal³

et al. 1991

Plant Physiol.

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A radiation-induced mutant of Scotch spearmint (Mentha x graclis) was shown to produce an essential oil containing principally C3-oxygenated p-menthane monoterpenes that are typical of peppermint, instead of the CS-oxygenated monoterpene family characteristic of spearmint. In vitro measurement of all of the enzymes responsible for the production of both the C3-oxygenated and CS-oxygenated families of monoterpenes from the common precursor (-)-limonene indicated that a virtually identical complement of enzymes was present in wild type and mutant, with the exception of the microsomal, cytochrome P-450-dependent (-)-limonene hydroxylase; the C6-hydroxylase producing (-)-trans-carveol in the wild type had been replaced by a C3-hydroxylase producing (--trans-isopiperitenol in the mutant. Additionally, the mutant, but not the wild type, could carry out the cytochrome P-450-dependent epoxidation of the ai-unsaturated bond of the ketones formed via C3-hydroxylation. Although present in the wild type, the enzymes of the C3-pathway that convert trans-isopiperitenol to menthol isomers are synthetically inactive because of the absence of the key C3-oxygenated intermediate generated by hydroxylation of limonene. These results, which clarify the origins of the C3-and CS-oxygenation patterns, also allow correction of a number of earlier biogenetic proposals for the formation of monoterpenes in Mentha.The monoterpene constituents of the essential oils of peppermint (Mentha piperita L.) and spearmint (native = Mentha spicata L.; Scotch = Mentha x gracilis [28]) are distinguished by the position of oxygenation on the p-menthane ring3 (18,25). Peppermint produces almost exclusively monoterpenes bearing an oxygen function at C3, such as menthone and menthol, whereas spearmint species produce almost exclusively monoterpenes bearing an oxygen function at C6, typi-

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Monoterpene interconversions: Metabolism of pulegone by a cell-free system from Mentha piperita

Cited by 49 publications

References 9 publications

(−)-Menthol biosynthesis and molecular genetics

(−)-Menthol biosynthesis and molecular genetics

Morphology and monoterpene biosynthetic capabilities of secretory cell clusters isolated from glandular trichomes of peppermint (Mentha piperita L.)

Biochemical Characterization of a Spearmint Mutant That Resembles Peppermint in Monoterpene Content

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