From Xenobiotic to Antibiotic, Formation of Protoanemonin from 4-Chlorocatechol by Enzymes of the 3-Oxoadipate Pathway

Blasco, Rafael; Wittich, Rolf-Michael; Megharaj, Mallavarapu; Timmis, Kenneth N.; Pieper, Dietmar H.

doi:10.1074/jbc.270.49.29229

Cited by 119 publications

(99 citation statements)

References 42 publications

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“…Most likely it is either 2-or 5-chloromuconolactone, since 3-chloromuconolactone (standard available) was not detected and 4-chloromuconolactone has been described as unstable [10,40].…”

Section: Identification Of Novel Monochlorocatechols Degradation Intementioning

confidence: 99%

New branches in the degradation pathway of monochlorocatechols by Aspergillus nidulans: A metabolomics analysis

Martins

Núñez

Gallart-Ayala

et al. 2014

Journal of Hazardous Materials

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Research Highlights: One of the few studies on mono-chlorophenols/chlorocatechols degradation by fungi  Aspergillus nidulans showed major dechlorination paths and conjugation reactions  3-Chlorodienelactone and catechol are key intermediates in unknown degradation paths  The new fungal degradation paths might avoid known bacterial dead-ends *Highlights New branches in the degradation pathway of monochlorocatechols by Aspergillus nidulans: a metabolomics analysisTiago M. Martins, a Oscar Núñez, b Hector Gallart-Ayala, b Maria Cristina Leitão, a Maria Teresa Galceran, b and Cristina Silva Pereira, a* Novelty Statement: The present contribution focus on monochlorocatechols degradation by fungi. Its significance is highlighted by several facts: monochlorocatechols are key degradation intermediates of numerous chlorinated aromatic hydrocarbons (i), which are critical environmental pollutants (ii) but fungi role in their environmental mitigation remains largely ignored (iii). We believe this is of high relevance for the readers of the Journal of Hazardous Materials, particularly in the topics of biological degradation and environmental fate of critical pollutants. Our original data made apparent that fungi strongly influence the toxic-derived metabolome, ensuring unique degradation paths which might complement and/or compete with bacteria activity. AbstractA collective view of the degradation of monochlorocatechols in fungi is yet to be attained, though these compounds are recognised as key degradation intermediates of numerous chlorinated aromatic hydrocarbons, including monochlorophenols. In the present contribution we have analysed the degradation pathways of monochlorophenols in Aspergillus nidulans using essentially metabolomics. Degradation intermediates herein identified included those commonly reported (e.g. 3-chloro-cis,cis-muconate) but also compounds never reported before in fungi revealing for 4-chlorocatechol and for 3-chlorocatechol unknown degradation paths yielding 3-chlorodienelactone and catechol, respectively. A different 3-chlorocatechol degradation path led to accumulation of 2-chloromuconates (a potential dead-end), notwithstanding preliminary evidence of chloromuconolactones and protoanemonin simultaneous formation. In addition, some transformation intermediates, of which sulfate conjugates of monochlorophenols/chlorocatechols were the most common, were also identified. This study provides critical information for understanding the role of fungi in the degradation of chlorinated aromatic hydrocarbons; furthering their utility in the development of innovative bioremediation strategies.

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“…Most likely it is either 2-or 5-chloromuconolactone, since 3-chloromuconolactone (standard available) was not detected and 4-chloromuconolactone has been described as unstable [10,40].…”

Section: Identification Of Novel Monochlorocatechols Degradation Intementioning

confidence: 99%

New branches in the degradation pathway of monochlorocatechols by Aspergillus nidulans: A metabolomics analysis

Martins

Núñez

Gallart-Ayala

et al. 2014

Journal of Hazardous Materials

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“…cis-Dienelactone was kindly provided by Walter Reineke (Bergische Universität-Gesamthochschule Wuppertal, Wuppertal, Germany) and Stefan Kaschabeck (TU Bergakademie Freiberg, Freiberg, Germany). Protoanemonin, 4-methylmuconolactone, 3-methylmuconolactone, (ϩ)-muconolactone, cis,cis-muconate, and 2-chloro-cis,cis-muconate were prepared as described previously (1,39,42,46).…”

Section: Methodsmentioning

confidence: 99%

“…More importantly, muconate and chloromuconate cycloisomerases differ not only in substrate specificity but also in the reaction performed. Chloromuconate cycloisomerases catalyze a dehalogenation of 3-chloromuconate to form cis-dienelactone (53), and muconate cycloisomerases catalyze the formation of protoanemonin (1) with 4-chloromuconolactone as a reaction intermediate (1,32). 2-Chloromuconate is dehalogenated only by chloromuconate cycloisomerases (59), while mu-conate cycloisomerases form 2-chloro-and 5-chloromuconolactone (60).…”

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confidence: 99%

A Gene Cluster Involved in Degradation of Substituted Salicylates viaorthoCleavage inPseudomonassp. Strain MT1 Encodes Enzymes Specifically Adapted for Transformation of 4-Methylcatechol and 3-Methylmuconate

et al. 2007

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Pseudomonas sp. strain MT1 has recently been reported to degrade 4-and 5-chlorosalicylate by a pathway assumed to consist of a patchwork of reactions comprising enzymes of the 3-oxoadipate pathway. Genes encoding the initial steps in the degradation of salicylate and substituted derivatives were now localized and sequenced. One of the gene clusters characterized (sal) showed a novel gene arrangement, with salA, encoding a salicylate 1-hydroxylase, being clustered with salCD genes, encoding muconate cycloisomerase and catechol 1,2-dioxygenase, respectively, and was expressed during growth on salicylate and chlorosalicylate. A second gene cluster (cat), exhibiting the typical catRBCA arrangement of genes of the catechol branch of the 3-oxoadipate pathway in Pseudomonas strains, was expressed during growth on salicylate. Despite their high sequence similarities with isoenzymes encoded by the cat gene cluster, the catechol 1,2-dioxygenase and muconate cycloisomerase encoded by the sal cluster showed unusual kinetic properties. Enzymes were adapted for turnover of 4-chlorocatechol and 3-chloromuconate; however, 4-methylcatechol and 3-methylmuconate were identified as the preferred substrates. Investigation of the substrate spectrum identified 4-and 5-methylsalicylate as growth substrates, which were effectively converted by enzymes of the sal cluster into 4-methylmuconolactone, followed by isomerization to 3-methylmuconolactone. The function of the sal gene cluster is therefore to channel both chlorosubstituted and methylsubstituted salicylates into a catechol ortho cleavage pathway, followed by dismantling of the formed substituted muconolactones through specific pathways.

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“…Sin embargo, algunos compuestos xenobióticos no son fácilmente biodegradables. Es más, se ha demostrado que el metabolismo de algunos compuestos xenobióticos por bacterias normalmente presentes en el suelo puede producir compuestos más tóxicos que los originales (Blasco et al, 1995). Resultados como este justifican la construcción racional, por ingeniería genética, de nuevas cepas con rutas híbridas que eviten la formación de intermediarios tóxicos, que podrían ser dotadas de sistemas de autocontención para evitar su posible expansión (Munthali et al, 1996).…”

Section: Conceptos Fundamentalesunclassified

Acerca de la biotecnología ambiental

Blasco¹,

Rodríguez²

2014

Arbor

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RESUMEN: La Biotecnología ambiental trata de corregir los desequilibrios causados en el medio ambiente por actividades industriales que alteran los ecosistemas naturales mediante contaminación química o biológica y que también afectan a los grandes ciclos biogeoquímicos en la biosfera, mayoritariamente catalizados por seres vivos, entre los que los microrganismos juegan un papel esencial. Las desviaciones en los balances de compuestos carbonados, nitrogenados y azufrados atmosféricos pueden causar fenómenos de gran complejidad como el calentamiento global, la destrucción de la capa de ozono, la contaminación ambiental o la lluvia ácida. Por otra parte, las interacciones de los microorganismos entre sí y con el medio, desconocidas en su mayor parte, tiene importantes repercusiones en la generación y persistencia de especies químicas que, depositadas en las cadenas tróficas, son altamente tóxicas para los organismos vivos. Para atajar estos problemas es necesario avanzar en el conocimiento a nivel molecular de la ecología microbiana y del funcionamiento de los ciclos biogeoquímicos, aunque no es menos necesario desarrollar tecnologías para la eliminación de contaminantes industriales in situ y ex situ, evitar su producción y utilización incontroladas así como corregir las actuaciones desequilibrantes, actuales o futuras, de la biogeoquímica planetaria.

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From Xenobiotic to Antibiotic, Formation of Protoanemonin from 4-Chlorocatechol by Enzymes of the 3-Oxoadipate Pathway

Cited by 119 publications

References 42 publications

New branches in the degradation pathway of monochlorocatechols by Aspergillus nidulans: A metabolomics analysis

New branches in the degradation pathway of monochlorocatechols by Aspergillus nidulans: A metabolomics analysis

A Gene Cluster Involved in Degradation of Substituted Salicylates viaorthoCleavage inPseudomonassp. Strain MT1 Encodes Enzymes Specifically Adapted for Transformation of 4-Methylcatechol and 3-Methylmuconate

Acerca de la biotecnología ambiental

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