Ring cleavage reactions in the metabolism of (-)-menthol and (-)-menthone by a Corynebacterium sp.

Williams, Dean T.; Trudgill, Peter

doi:10.1099/00221287-140-3-611

Cited by 11 publications

(7 citation statements)

References 17 publications

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“…A 10 mM solution of ε-caprolactone in 50 mM Tris-HCl (pH 9.0) was incubated at 60°C for 16 h. The solution was cooled, and the pH was adjusted to 7.0 by addition of HCl. This solution contained no residual lactone when assayed, and the mass spectrum (MS) of the product was identical to that reported previously (32).…”

Section: Methodssupporting

confidence: 56%

“…The organoleptically important lactones generally have ␥-or ␦-lactone structures (five-or six-membered ring structures), while a few are macrocyclic (29). Lactones are intermediates in microbial degradation pathways of alicyclic compounds (1,5,32) but have also been implicated in certain microbial aromatic degradation pathways (ortho cleavage pathways) (14,19). The degradation of lactones is accomplished by the activity of lactone hydrolase, which catalyzes the hydrolysis of lactones to the corresponding hydroxy acids (Fig.…”

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confidence: 99%

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Genetic and Biochemical Characterization of a Novel Monoterpene ɛ-Lactone Hydrolase from Rhodococcus erythropolis DCL14

Vlugt-Bergmans

Werf

2001

Appl Environ Microbiol

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A monoterpene -lactone hydrolase (MLH) from Rhodococcus erythropolis DCL14, catalyzing the ring opening of lactones which are formed during degradation of several monocyclic monoterpenes, including carvone and menthol, was purified to apparent homogeneity. It is a monomeric enzyme of 31 kDa that is active with (4R)-4-isopropenyl-7-methyl-2-oxo-oxepanone and (6R)-6-isopropenyl-3-methyl-2-oxo-oxepanone, lactones derived from (4R)-dihydrocarvone, and 7-isopropyl-4-methyl-2-oxo-oxepanone, the lactone derived from menthone. Both enantiomers of 4-, 5-, 6-, and 7-methyl-2-oxo-oxepanone were converted at equal rates, suggesting that the enzyme is not stereoselective. Maximal enzyme activity was measured at pH 9.5 and 30°C. Determination of the N-terminal amino acid sequence of purified MLH enabled cloning of the corresponding gene by a combination of PCR and colony screening. The gene, designated mlhB (monoterpene lactone hydrolysis), showed up to 43% similarity to members of the GDXG family of lipolytic enzymes. Sequencing of the adjacent regions revealed two other open reading frames, one encoding a protein with similarity to the short-chain dehydrogenase reductase family and the second encoding a protein with similarity to acyl coenzyme A dehydrogenases. Both enzymes are possibly also involved in the monoterpene degradation pathways of this microorganism.Lactones, internal cyclic monoesters, are ubiquitous in nature and have been identified in all major classes of foods, including fruits, vegetables, nuts, meat, milk products, and baked products, contributing to taste and flavor nuances (13). The organoleptically important lactones generally have ␥-or ␦-lactone structures (five-or six-membered ring structures), while a few are macrocyclic (29). Lactones are intermediates in microbial degradation pathways of alicyclic compounds (1, 5, 32) but have also been implicated in certain microbial aromatic degradation pathways (ortho cleavage pathways) (14,19). The degradation of lactones is accomplished by the activity of lactone hydrolase, which catalyzes the hydrolysis of lactones to the corresponding hydroxy acids (Fig. 1). Lactone hydrolases are commercially applied for the debittering of triterpenes present in citrus juices (15) and for the production of the vitamin D-pantothenate (T. Morikawa, K. Wada, S. Kita, K. Tuzaki, K. Sakamoto, M. Kataoka, S. Shimizu, and H. Yamada, Book Abstr. 6th Japanese-Swiss Meet. Bio/Technol., p. [34][35] 1998).The application of Baeyer-Villiger monooxygenases (BVMOs) seems an attractive option for the production of lactones (12, 31). BVMOs are enzymes catalyzing the insertion of one atom of oxygen next to an alicyclic keto group, thus forming lactones. However, BVMOs are relatively unstable enzymes that generally use the very expensive NADPH as the cofactor (31). Therefore, the application of whole cells of BMVO activity containing microorganisms is a prerequisite to ascertain in situ cofactor regeneration and to increase the stability of the enzyme. However, most microorganisms containing...

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Section: Methodssupporting

confidence: 56%

mentioning

confidence: 99%

Genetic and Biochemical Characterization of a Novel Monoterpene ɛ-Lactone Hydrolase from Rhodococcus erythropolis DCL14

Vlugt-Bergmans

Werf

2001

Appl Environ Microbiol

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“…However, the lactone hydrolase present in R. erythropolis DCL14 might be essential for complete mineralization of other monoterpenes used as carbon and energy sources by this strain, such as dihydrocarvone and menthol. These monoterpenes do require lactone hydrolase activity for complete mineralization (44,53). Apparently, limonene acts as a fortuitous inducer for other monoterpene degradation pathways present in R. erythropolis DCL14.…”

Section: Discussionmentioning

confidence: 99%

Rhodococcus erythropolis DCL14 Contains a Novel Degradation Pathway for Limonene

Werf¹,

Swarts

Bont³

1999

Appl Environ Microbiol

147

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Strain DCL14, which is able to grow on limonene as a sole source of carbon and energy, was isolated from a freshwater sediment sample. This organism was identified as a strain of Rhodococcus erythropolis by chemotaxonomic and genetic studies. R. erythropolis DCL14 also assimilated the terpenes limonene-1,2-epoxide, limonene-1,2-diol, carveol, carvone, and (؊)-menthol, while perillyl alcohol was not utilized as a carbon and energy source. Induction tests with cells grown on limonene revealed that the oxygen consumption rates with limonene-1,2-epoxide, limonene-1,2-diol, 1-hydroxy-2-oxolimonene, and carveol were high. Limonene-induced cells of R. erythropolis DCL14 contained the following four novel enzymatic activities involved in the limonene degradation pathway of this microorganism: a flavin adenine dinucleotide-and NADH-dependent limonene 1,2-monooxygenase activity, a cofactor-independent limonene-1,2-epoxide hydrolase activity, a dichlorophenolindophenol-dependent limonene-1,2-diol dehydrogenase activity, and an NADPH-dependent 1-hydroxy-2-oxolimonene 1,2-monooxygenase activity. Product accumulation studies showed that (1S,2S,4R) [(1R,2R,4S)-limonene-1,2-diol, (1R,4S)-1-hydroxy-2-oxolimonene, and (3S)-3-isopropenyl-6-oxoheptanoate] were found in the (4S)-limonene degradation pathway, while accumulation of (1R,2S,4S)-limonene-1,2-diol from (4S)-limonene was also observed. These results show that R. erythropolis DCL14 metabolizes both enantiomers of limonene via a novel degradation pathway that starts with epoxidation at the 1,2 double bond forming limonene-1,2-epoxide. This epoxide is subsequently converted to limonene-1,2-diol, 1-hydroxy-2-oxolimonene, and 7-hydroxy-4-isopropenyl-7-methyl-2-oxo-oxepanone. This lactone spontaneously rearranges to form 3-isopropenyl-6-oxoheptanoate. In the presence of coenzyme A and ATP this acid is converted further, and this finding, together with the high levels of isocitrate lyase activity in extracts of limonene-grown cells, suggests that further degradation takes place via the ␤-oxidation pathway. -limonene-1,2-diol, (1S,4R)-1-hydroxy-2-oxolimonene, and (3R)-3-isopropenyl-6-oxoheptanoate were intermediates in the (4R)limonene degradation pathway. The opposite enantiomers

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“…As far as we know, previously only one other bacterium, Corynebacterium sp. RWM1, was reported to be able to grow on 2-oxygenated limonene derivatives (Williams & Trudgill, 1994), but the metabolic pathway of these compounds in this micro-organism was not reported.…”

Section: Discussionmentioning

confidence: 99%

Metabolism of carveol and dihydrocarveol in Rhodococcus erythropolis DCL14

Werf

Boot

2000

Microbiology

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Rhodococcus erythropolis DCL14 assimilates all stereoisomers of carveol and dihydrocarveol as sole source of carbon and energy. Induction experiments with carveol-or dihydrocarveol-grown cells showed high oxygen consumption rates with these two compounds and with carvone and dihydrocarvone. (Dihydro)carveol-grown cells of R. erythropolis DCL14 contained the following enzymic activities involved in the carveol and dihydrocarveol degradation pathways of this micro-organism : (dihydro)carveol dehydrogenase (both NAD M -and dichlorophenolindophenol-dependent activities), an unknown cofactor-dependent carvone reductase, (iso-)dihydrocarvone isomerase activity, NADPH-dependent dihydrocarvone monooxygenase (Baeyer-Villiger monooxygenase), ε-lactone hydrolase and an NAD M -dependent 6-hydroxy-3- isopropenylheptanoate dehydrogenase. Product accumulation studies identified (4R)-carvone, (1R,4R)-dihydrocarvone, (4R,7R)-4-isopropenyl-7-methyl-2-oxo-oxepanone, (3R)-6-hydroxy-3-isopropenylheptanoate, (3R)-3-isopropenyl-6-oxoheptanoate, (3S,6R)-6-isopropenyl-3-methyl-2-oxooxepanone and (5R)-6-hydroxy-5-isopropenyl-2-methylhexanoate as intermediates in the (4R)-carveol degradation pathway. The opposite stereoisomers of these compounds were identified in the (4S)-carveol degradation pathway. With dihydrocarveol, the same intermediates are involved except that carvone was absent. These results show that R. erythropolis DCL14 metabolizes all four diastereomers of carveol via oxidation to carvone, which is subsequently stereospecifically reduced to (1R)-(iso-) dihydrocarvone. At this point also dihydrocarveol enters the pathway, and this compound is directly oxidized to (iso-)dihydrocarvone. Cell extracts contained both (1R)-(iso-)dihydrocarvone 1,2-monooxygenase and (1S)-(iso)-dihydrocarvone 2,3-monooxygenase activity, resulting in a branch point of the degradation pathway ; (1R)-(iso-)dihydrocarvone was converted to 4-isopropenyl-7-methyl-2-oxo-oxepanone, while (1S)-(iso)-dihydrocarvone, which in vivo is isomerized to (1R)-(iso-)dihydrocarvone, was converted to 6-isopropenyl-3-methyl-2-oxo-oxepanone. 4-Isopropenyl-7-methyl-2-oxooxepanone is hydrolysed to 6-hydroxy-3-isopropenylheptanoate, which is subsequently oxidized to 3-isopropenyl-6-oxoheptanoate, thereby linking the (dihydro)carveol degradation pathways to the limonene degradation pathway of this micro-organism. 6-Isopropenyl-3-methyl-2-oxo-oxepanone is, in vitro, hydrolysed to 6-hydroxy-5-isopropenyl-2-methylhexanoate, which is thought to be a dead-end metabolite.

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Ring cleavage reactions in the metabolism of (-)-menthol and (-)-menthone by a Corynebacterium sp.

Cited by 11 publications

References 17 publications

Genetic and Biochemical Characterization of a Novel Monoterpene ɛ-Lactone Hydrolase from Rhodococcus erythropolis DCL14

Genetic and Biochemical Characterization of a Novel Monoterpene ɛ-Lactone Hydrolase from Rhodococcus erythropolis DCL14

Rhodococcus erythropolis DCL14 Contains a Novel Degradation Pathway for Limonene

Metabolism of carveol and dihydrocarveol in Rhodococcus erythropolis DCL14

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