Enzymatic epoxidation I. Alkene epoxidation by the ω-hydroxylation system of Pseudomonas oleovorans

May, Sheldon W.; Abbott, Bernard J.

doi:10.1016/0006-291x(72)90842-x

Cited by 72 publications

(43 citation statements)

References 14 publications

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“…A trace of 3-hydroxy-1-propene is, however, detected, indicating that propene is oxidized both at the double bond and at the methyl group. This is analogous to the findings of van der Linden (1963) and May & Abbott (1973) in the oxidation of 1-octene.…”

Section: Alkane-utilizerssupporting

confidence: 90%

“…These early concepts were later confirmed with the w-hydroxylation system of Pseudomonas oleovorans. Octane-grown cell suspension of the bacterium catalyzes the epoxidation of terminal olefins (C6-C12), allyl benzene and alkadienes, along with the hydroxylation of the methyl group (May & Abbott, 1972& 1973de Smet et al, 1981bde Smet et al, & 1983. Styrene oxide is, however, not produced (May et al 1975).…”

Section: Alkane-utilizersmentioning

confidence: 99%

“…Pseudomonas oleovorans, however, produces the /?-monoepoxide from 1,7-octadiene in ee=84% (May etaL, 1976),/?-1,2-epoxyoctane in ee=70% (de Smet etal., 1981 a) and R-1.2-epoxydecane in ee=60% (de Smet et a l., 1983). It has been shown that 1,7-octadiene is more reactive than 1 -octene and 1 -decene in the reactions catalyzed by the w-hydroxylation system (May & Abbott, 1973;May et al, 1975). It is suggested that the optical purity of the enzymatic product parallels the relative reactivity of the substrates.…”

Section: Alkane-utilizersmentioning

confidence: 99%

“…A major difference between alkane-and alkenegrown bacteria is the specificity toward gaseous hydrocarbons of the monooxygenases responsible for the initial oxygenation. Alkane monooxygenases from alkane-utilizers can epoxidize olefins as well as hydroxylating 1-and 2-alkenes along with alkanes (May & Abbott, 1973;Hou etal., 1983;van Ginkel etal., 1987c), whereas the alkene monooxygenases can only epoxidize and do not hydroxylate olefins (Habets-Criitzen et al, 1984).…”

Section: Alkene-utilizersmentioning

confidence: 99%

“…Identification of microbial epoxides was confirmed by treatment of reaction mixtures with 10-20|il of concentrated T^SC^, followed by gas chromatography, to establish presence or absence of epoxide peak after acid hydrolysis (May & Abbott, 1973). Complete hydrolysis of epoxide occurred at room temperature within 5-10 minutes after addition of the acid.…”

Section: C2-c4 Epoxidesmentioning

confidence: 99%

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Biocatalysts for production of chiral epoxides

Mahmoudian

Michael

1992

Appl Microbiol Biotechnol

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An extensive screen for microorganisms capable of growth on olefins was carried out. Over 100 bacterial strains (mesophilic, thermophilic) were isolated in pure culture with gaseous or liquid (internal & terminal) olefins as the sole source of carbon and energy. The organisms included Aero coccus, Aeromonas,Alcaligenes, Flavobacterium, Micrococcus, Moraxella, Nocardia, Pseudomonas, Staphylococcus, Streptomyces and Vibrio spp. and a variety of Gram-negative, Gram-positive and Gram-variable rods/coccobacilli not yet identified. Given the success of isolating many different genera of alkene-utilizing bacteria, it would suggest that the ability to utilize olefin hydrocarbons is more widespread in nature than previously recognized.Initial studies involved testing a collection of strains for i) growth rate on the substrate of isolation and ii) evidence of epoxide accumulation from lower gaseous olefins. All of the 18 ethene-and propene-utilizing bacteria tested, stereospecifically formed R-1,2-epoxypropane (ee=90-96%), R -l,2-epoxybutane (ee=90-98%) and trans-(2/?,37?)-epoxybutane (ee=64-88%), as analyzed by chiral complexation glc. A particularly promising strain of Micrococcus sp. M90C was selected to demonstrate: a) Induction of epoxidation activity in carbohydrate-grown cells. b) Optimization of a biotransformation process for production of epoxyethane. c) Involvement of a specific monooxygenase in the formation of chiral epoxides. d) Stereoselectivity of epoxyalkane degradation. e) Substrate specificity toward a range of olefins.Micrococcus sp. M90C stereospecifically formed S-(+)-phenyl glycidyl ether (ee=93%) and /?-(+)-phenyl methyl sulphoxide (ee>98%), as analyzed by chiral-shift NMR and HPLC. The ability to catalyze heteroatom oxygenation as well as epoxidation of a wide range of olefins in high optical and chemical yields, demonstrates its potential as a 'general-purpose' biocatalyst for the production of optically pure oxygenated compounds.Two other promising ethene-utilizing bacteria (M26, M93 A) each catalyzed the stereospecific formation of S-(+)-phenyl glycidyl ether (ee=93%). This has attracted considerable industrial interest and is currently under investigation at ICI for commercial production of optically active./1-blockers. In addition to Micrococcus sp. M90C, the substrate specificities of 6 other organisms were studied in order to probe the active site of the enzymes involved. The pattern of reactivity for the group of 4 ethene-(M26, M90C, M93A, M186) and 2 propene-(M142, M l 56) utilizers differed from that expected with peracids, suggesting a considerable degree of enzymatic control.The nature of the substrate, however, modulated enzymatic epoxidations in Staphylcoccus sp. M97B. CONTENTS

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Section: Alkane-utilizerssupporting

confidence: 90%

Section: Alkane-utilizersmentioning

confidence: 99%

Section: Alkane-utilizersmentioning

confidence: 99%

Section: Alkene-utilizersmentioning

confidence: 99%

Section: C2-c4 Epoxidesmentioning

confidence: 99%

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Biocatalysts for production of chiral epoxides

Mahmoudian

Michael

1992

Appl Microbiol Biotechnol

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Epoxidation of 1,7-octadiene byPseudomonas oleovorans in a membrane bioreactor

Doig

Boam

Livingston

et al. 1999

Biotechnol. Bioeng.

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Bioconversion of hydrophobic compounds in a continuous closed-gas-loop bioreactor: Feasibility assessment and epoxide production

Steinig

Livingston²,

Stuckey³

2000

Biotechnol. Bioeng.

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Microorganisms can be used as catalysts to produce organic compounds in a highly chemo‐, regio‐ and enantioselective manner, and whole cells do not require the costly addition of cofactors for redox reactions. However, bioconversions are slow compared to alternative chemical reactions, and the biocatalyst works at its best in an aqueous medium, while the transformations of interest frequently involve compounds with a low‐aqueous solubility and that are toxic to microorganisms. This results in low‐volumetric productivity in classical bioreactors. The Continuous Closed‐Gas‐Loop Bioreactor is described here—a reactor system with high productivity, but without the problems associated with two‐phase systems, such as an emulsified product stream and phase toxicity. Its working principle is to recirculate a gas phase through a bioreaction compartment and a saturator/absorber module where the product accumulates as a clear organic solution. A wide range of bioconversions should be possible in this set‐up, and proof of concept was established for the epoxidation of 1,7‐octadiene to (R)‐1,2‐epoxyoct‐7‐ene by a native strain of Pseudomonas oleovorans. This reaction represents a group of terminal alkene epoxidations where the bioconversion substrate does not support growth of the microorganism. Practical results at a 5l‐scale are presented for this bioconversion for both batch and continuous operation with respect to the aqueous phase, showing continuous stable epoxidation at productivities >14 μmol min−1 L−1 (U L−1). The results confirm that the metabolism does not allow a simple optimization strategy, because growth and biotransformation substrates compete for the same enzyme sites, and conversely growth on a substrate using this very enzyme system is necessary for longterm bioconversion. Integrated removal of the CO2 formed via the liquid overflow was estimated from theory and verified in experimental work. © 2000 John Wiley & Sons, Inc. Biotechnol Bioeng 70: 553–563, 2000.

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Enzymatic epoxidation I. Alkene epoxidation by the ω-hydroxylation system of Pseudomonas oleovorans

Cited by 72 publications

References 14 publications

Biocatalysts for production of chiral epoxides

Biocatalysts for production of chiral epoxides

Epoxidation of 1,7-octadiene byPseudomonas oleovorans in a membrane bioreactor

Bioconversion of hydrophobic compounds in a continuous closed-gas-loop bioreactor: Feasibility assessment and epoxide production

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