Absolute stereochemistry of the dihydroanthracene-cis- and trans-1,2-diols produced from anthracene by mammals and bacteria

Akhtar, M. Naseem; Boyd, Derek R.; Thompson, Norris; Koreeda, Masato; Gibson, David T.; Mahadevan, V.; Jerina, Donald M.

doi:10.1039/p19750002506

Cited by 65 publications

(48 citation statements)

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“…Biotransformation assays have shown previously that wildtype NDO-O 9816-4 converts anthracene to enantiomerically pure (ϩ)-(1R,2S)-cis-dihydroxy-1,2-dihyroanthracene (1,16). In previous studies, the Phe-352-Val mutant was tested for comparison, and over 96% of the product formed was also (ϩ)-(1R,2S)-cis-dihydroxy-1,2-dihyroanthracene.…”

Section: Structures Of Ndo-o 9816-4 Phe-352-val Mutantmentioning

confidence: 99%

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Structural Basis for Regioselectivity and Stereoselectivity of Product Formation by Naphthalene 1,2-Dioxygenase

Ferraro

Okerlund²,

Mowers

et al. 2006

J Bacteriol

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Rieske oxygenase (RO) systems have been shown to catalyze the first step in the metabolism of aromatic compounds by various prokaryotic organisms (7). ROs produce cis-dihydrodiols from a large variety of substrates and molecular oxygen (dioxygen). In addition, this enzyme system is also able to perform oxidation with a high degree of stereo-, regio-, and enantiospecificity (35). These factors have made ROs a desirable platform for use in biosynthesis of compounds and in bioremediation (reviewed in references 3, 30, and 40).RO systems use electrons from NAD(P)H to activate molecular oxygen, which is then used to oxidize the substrate. RO systems are composed of two or three components, including a reductase, a ferredoxin (not found in all systems), and an oxygenase (Fig. 1). The reductase component liberates electrons from NAD(P)H and transfers the electrons to the ferredoxin. The ferredoxin shuttles the electrons to the oxygenase, where they are used in catalysis. In systems where the ferredoxin is absent, the reductase transfers electrons directly to the oxygenase. The oxygenase component of these systems is responsible for catalysis. This component consists of an ␣ subunit, which contains both a Rieske binding domain and a catalytic domain. In some cases, a beta subunit is present, which is believed to primarily function as a stabilizer for the alpha subunits. Structural studies have been performed on a number of ROs; all have been shown to have either an ␣ 3 or ␣ 3 ␤ 3 quaternary structure (9). This arrangement positions a Rieske domain of one subunit within ϳ12 Å of a catalytic mononuclear iron of another, thus allowing electron transfer to take place.The production of cis-diols occurs at the catalytic mononuclear iron and is coordinated by two histidines and a single aspartic acid. The 2-his-1-carboxylate facial triad motif is found in many enzymes (34). This motif is conserved in all known Rieske oxygenases. While the mononuclear iron provides the platform for catalysis, it alone is not able to control substrate specificity and product regio-and stereoselectivity for the enzyme. Naphthalene 1,2-dioxygenase from Pseudomonas sp. strain NCIB 9816-4 (NDO-O 9816-4 ) has been studied as a model system for the dioxygenation of small molecules containing one to three aromatic rings (35). Previous structural studies have determined the molecular structure of the terminal oxygenase (5,19,20), including the positions of both molecular oxygen and the aromatic substrate bound to the enzyme. These studies have demonstrated that the mononuclear iron binds to molecular oxygen in a side-on fashion, while the aromatic substrate binds in the active site above the ironoxygen complex. Structural studies of other ROs have demonstrated that the substrate binds in the active site with the atoms that would be oxidized closest to the mononuclear iron (10,12,13,26). This led to the hypothesis that interactions between substrate and enzyme control substrate orientation, which determines both substrate selectivity and product regio-an...

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Section: Structures Of Ndo-o 9816-4 Phe-352-val Mutantmentioning

confidence: 99%

“…1NDO). and NBDO-O JS765 from anthracene (1,16,31), phenanthrene (31,32), and 3-nitrotoluene (25,38 (37), using the KpnI and Bsu36I restriction sites. The DNA fragments were ligated using Quick T4 DNA ligase (New England Biolabs, Ipswich, MA).…”

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confidence: 99%

Structural Basis for Regioselectivity and Stereoselectivity of Product Formation by Naphthalene 1,2-Dioxygenase

Ferraro

Okerlund²,

Mowers

et al. 2006

J Bacteriol

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“…The HMW PAH benz [a]anthracene is considered to be environmentally recalcitrant, is classified as a group 2A carcinogen by the International Agency for Research on Cancer, and is included in the U.S. Environmental Protection Agency's Priority Pollutant List. As such, there is much interest in understanding the environmental fate of benz[a]anthracene and the mechanisms by which it may be transformed.Few studies have documented the bacterial biotransformation of benz [a]anthracene even though many studies have documented the biotransformation of the structurally similar threering angular kata-annelated PAH phenanthrene (7-16) and, although less so, also the structurally similar three-ring linear kata-annelated PAH anthracene (7,13,(17)(18)(19). The benz [a]anthracene molecule itself is comprised of four aromatic rings that are bonded via both linear and angular kata annelation, and it may be thought of as a benzannelated derivative of either phenanthrene or anthracene.…”

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confidence: 99%

“…Few studies have documented the bacterial biotransformation of benz [a]anthracene even though many studies have documented the biotransformation of the structurally similar threering angular kata-annelated PAH phenanthrene (7-16) and, although less so, also the structurally similar three-ring linear kata-annelated PAH anthracene (7,13,(17)(18)(19). The benz [a]anthracene molecule itself is comprised of four aromatic rings that are bonded via both linear and angular kata annelation, and it may be thought of as a benzannelated derivative of either phenanthrene or anthracene.…”

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confidence: 99%

Benz[ a ]anthracene Biotransformation and Production of Ring Fission Products by Sphingobium sp. Strain KK22

Kunihiro

Ozeki

Nogi

et al. 2013

Appl Environ Microbiol

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A soil bacterium, designated strain KK22, was isolated from a phenanthrene enrichment culture of a bacterial consortium that grew on diesel fuel, and it was found to biotransform the persistent environmental pollutant and high-molecular-weight polycyclic aromatic hydrocarbon (PAH) benz[a]anthracene. Nearly complete sequencing of the 16S rRNA gene of strain KK22 and phylogenetic analysis revealed that this organism is a new member of the genus Sphingobium. An 8-day time course study that consisted of whole-culture extractions followed by high-performance liquid chromatography (HPLC) analyses with fluorescence detection showed that 80 to 90% biodegradation of 2.5 mg liter H igh-molecular-weight polycyclic aromatic hydrocarbons (HMW PAHs) are commonly occurring environmental pollutants that are generally considered to be more resistant to biodegradation than their lower-molecular-weight aromatic counterparts (1-4). Many are suspected carcinogens and display genotoxic and immunotoxic properties in addition to causing oxidative cell damage (5, 6). The HMW PAH benz [a]anthracene is considered to be environmentally recalcitrant, is classified as a group 2A carcinogen by the International Agency for Research on Cancer, and is included in the U.S. Environmental Protection Agency's Priority Pollutant List. As such, there is much interest in understanding the environmental fate of benz[a]anthracene and the mechanisms by which it may be transformed.Few studies have documented the bacterial biotransformation of benz [a]anthracene even though many studies have documented the biotransformation of the structurally similar threering angular kata-annelated PAH phenanthrene (7-16) and, although less so, also the structurally similar three-ring linear kata-annelated PAH anthracene (7,13,(17)(18)(19). The benz [a]anthracene molecule itself is comprised of four aromatic rings that are bonded via both linear and angular kata annelation, and it may be thought of as a benzannelated derivative of either phenanthrene or anthracene. Initial enzymatic oxidation of the aromatic ring system of benz [a]anthracene may occur at various locations on the molecule, including via the 1,2-or 3,4-carbon positions, an angular kata-type initial dioxygenation, via the 8,9-or 10,11-carbon positions, a linear kata-type initial dioxygenation, or via the K-region at the 5,6-carbon positions. If metabolites that represent the initial oxidation steps are not directly recovered in metabolism studies, identification of downstream metabolites may allow for predicting whether an angular kata-, linear kata-, or K region-type initial dioxygenation originally occurred. For example, 2-hydroxy-3-naphthoic acid may occur as a downstream metabolite of benz [a]anthracene biotransformation through an angular katatype initial dioxygenation event.To date, metabolites from the biotransformation of benz[a]anthracene by bacteria have been identified from only four organisms. In chronological order, they are (i) Sphingobium yanoikuyae mutant strain B8/36 (20-22), (ii) S. yanoiku...

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“…Species known to perform this pathway are from the genera Pseudomonas, Sphingobium, Nocardia, Rhodococcus, and Mycobacterium (4,7,8,10,21,22). Degradation from anthracene to 3-hydroxy-2-naphthoic acid proceeds through dioxygenation (1,10,22) and dehydration by which 1,2-dihydroxyanthracene is formed. This compound is cleaved by meta-ring cleavage and the cleavage product is further degraded to 2-hydroxy-3-naphthaldehyde and then to 2-hydroxy-3-naphthoic acid.…”

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confidence: 99%

Degradation of Anthracene by Mycobacterium sp. Strain LB501T Proceeds via a Novel Pathway, through o -Phthalic Acid

Herwijnen

Springael

Slot

et al. 2003

Appl Environ Microbiol

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Mycobacterium sp. strain LB501T utilizes anthracene as a sole carbon and energy source. We analyzed cultures of the wild-type strain and of UV-generated mutants impaired in anthracene utilization for metabolites to determine the anthracene degradation pathway. Identification of metabolites by comparison with authentic standards and transient accumulation of o-phthalic acid by the wild-type strain during growth on anthracene suggest a pathway through o-phthalic acid and protocatechuic acid. As the only productive degradation pathway known so far for anthracene proceeds through 2,3-dihydroxynaphthalene and the naphthalene degradation pathway to form salicylate, this indicates the existence of a novel anthracene catabolic pathway in Mycobacterium sp. LB501T.

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Absolute stereochemistry of the dihydroanthracene-cis- and trans-1,2-diols produced from anthracene by mammals and bacteria

Cited by 65 publications

References 0 publications

Structural Basis for Regioselectivity and Stereoselectivity of Product Formation by Naphthalene 1,2-Dioxygenase

Structural Basis for Regioselectivity and Stereoselectivity of Product Formation by Naphthalene 1,2-Dioxygenase

Benz[ a ]anthracene Biotransformation and Production of Ring Fission Products by Sphingobium sp. Strain KK22

Degradation of Anthracene by Mycobacterium sp. Strain LB501T Proceeds via a Novel Pathway, through o -Phthalic Acid

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