Abstract
The bacterial dioxygenation of mono- or polycyclic aromatic compounds is an intensely studied field. However, only in a few cases has the repeated dioxygenation of a substrate possessing more than a single aromatic ring been described. We previously characterized the aryl-hydroxylating dioxygenase BphA-B4h, an artificial hybrid of the dioxygenases of the biphenyl degraders Burkholderia xenovorans LB400 and Pseudomonas sp. strain B4-Magdeburg, which contains the active site of the latter enzyme, as an exceptionally powerful biocatalyst. We now show that this dioxygenase possesses a remarkable capacity for the double dioxygenation of various bicyclic aromatic compounds, provided that they are carbocyclic. Two groups of biphenyl analogues were examined: series A compounds containing one heterocyclic aromatic ring and series B compounds containing two homocyclic aromatic rings. Whereas all of the seven partially heterocyclic biphenyl analogues were solely dioxygenated in the homocyclic ring, four of the six carbocyclic bis-aryls were converted into ortho,meta-hydroxylated bis-dihydrodiols. Potential reasons for failure of heterocyclic dioxygenations are discussed. The obtained bis-dihydrodiols may, as we also show here, be enzymatically re-aromatized to yield the corresponding tetraphenols. This opens a way to a range of new polyphenolic products, a class of compounds known to exert multiple biological activities. Several of the obtained compounds are novel molecules.
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Acknowledgments
The authors wish to thank Enno Michaelis, Yasmin Wenzel, Anne Heidelmann and Sandra Berger for help with DHD preparations, Ulrike Beutling for LC-MS analyses, Christel Kakoschke for NMR measurements and Andrea Abrahamik, Anja Meier and Manfred Nimtz for ESI-HRMS analyses. We also gratefully acknowledge financial support from CONICYT-BMBF (2009-174, 2011-642, 01DN12108). MS also acknowledges support through CONICYT 21120887 PhD and GO fellowships (to VM), FONDECYT (1110992, 1151174), USM (131109, 131342 and 131562) and CN&BS grants.
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Overwin, H., González, M., Méndez, V. et al. An aryl dioxygenase shows remarkable double dioxygenation capacity for diverse bis-aryl compounds, provided they are carbocyclic. Appl Microbiol Biotechnol 100, 8053–8061 (2016). https://doi.org/10.1007/s00253-016-7570-0
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DOI: https://doi.org/10.1007/s00253-016-7570-0