| Publikationstyp: | Beitrag in wissenschaftlicher Zeitschrift |
| Art der Begutachtung: | Peer review (Publikation) |
| Titel: | Stereochemistry of LinB-catalyzed biotransformation of δ-HBCD to 1R,2R,5S,6R,9R,10S-pentabromocyclododecanol |
| Autor/-in: | Heeb, Norbert V. Zindel, Daniel Graf, Heidi Azara, Valeria Bernd Schweizer, W. Geueke, Birgit Kohler, Hans-Peter E. Lienemann, Peter |
| DOI: | 10.1016/j.chemosphere.2012.10.019 |
| Erschienen in: | Chemosphere |
| Band(Heft): | 90 |
| Heft: | 6 |
| Seite(n): | 1911 |
| Seiten bis: | 1919 |
| Erscheinungsdatum: | 2013 |
| Verlag / Hrsg. Institution: | Elsevier |
| ISSN: | 0045-6535 1879-1298 |
| Sprache: | Englisch |
| Schlagwörter: | Catalysis; Brominated hydrocarbons; Nucleotidyltransferases; Soil Pollutants; Sphingomonadaceae; Stereoisomerism; Biotransformation |
| Fachgebiet (DDC): | 572: Biochemie |
| Zusammenfassung: | The haloalkane dehalogenase LinB from Sphingobium indicum B90A converts β-hexachlorocyclohexane (β-HCH), the most persistent HCH stereoisomer, to mono- and dihydroxylated metabolites. Recently, we reported that LinB also transforms α-, β- and γ-hexabromocyclododecanes (HBCDs), which are structurally related to HCHs. Here, we show that LinB catalyzes the hydroxylation of δ-HBCD to two pentabromocyclododecanols (PBCDOHs) and two tetrabromocyclododecadiols (TBCDDOHs). The stereochemistry of this enzymatic transformation was deduced from XRD crystal structure data of the substrate δ-HBCD and α(2)-PBCDOH, one of the biotransformation products. Five stereocenters of δ-HBCD are unchanged but the one at C6 is converted to an alcohol with inversion from S- to R-configuration in a nucleophilic, S(N)2-like substitution reaction. Only α(2)-PBCDOH with the 1R,2R,5S,6R,9R,10S-configuration is obtained but not its enantiomer. With only two of the 64 PBCDOHs formed, these transformations indeed are regio- and stereoselective. A conformational analysis revealed that the triple-turn motive, which is predominant in δ-HBCD and in several other HBCD stereoisomers, is also found in the product. This shows that LinB preferentially converted reactive bromine atoms but not those in the conserved triple-turn motive. The widespread contamination with HCHs triggered the bacterial evolution of dehalogenases which acquired the ability to convert these pollutants and their metabolites. We here demonstrate that LinB of S. indicum also transforms HBCDs regio- and stereoselectively following a similar mechanism. |
| URI: | https://digitalcollection.zhaw.ch/handle/11475/12903 |
| Volltext Version: | Publizierte Version |
| Lizenz (gemäss Verlagsvertrag): | Lizenz gemäss Verlagsvertrag |
| Departement: | Life Sciences und Facility Management |
| Organisationseinheit: | Institut für Chemie und Biotechnologie (ICBT) |
| Enthalten in den Sammlungen: | Publikationen Life Sciences und Facility Management |
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Heeb, N. V., Zindel, D., Graf, H., Azara, V., Bernd Schweizer, W., Geueke, B., Kohler, H.-P. E., & Lienemann, P. (2013). Stereochemistry of LinB-catalyzed biotransformation of δ-HBCD to 1R,2R,5S,6R,9R,10S-pentabromocyclododecanol. Chemosphere, 90(6), 1911–1919. https://doi.org/10.1016/j.chemosphere.2012.10.019
Heeb, N.V. et al. (2013) ‘Stereochemistry of LinB-catalyzed biotransformation of δ-HBCD to 1R,2R,5S,6R,9R,10S-pentabromocyclododecanol’, Chemosphere, 90(6), pp. 1911–1919. Available at: https://doi.org/10.1016/j.chemosphere.2012.10.019.
N. V. Heeb et al., “Stereochemistry of LinB-catalyzed biotransformation of δ-HBCD to 1R,2R,5S,6R,9R,10S-pentabromocyclododecanol,” Chemosphere, vol. 90, no. 6, pp. 1911–1919, 2013, doi: 10.1016/j.chemosphere.2012.10.019.
HEEB, Norbert V., Daniel ZINDEL, Heidi GRAF, Valeria AZARA, W. BERND SCHWEIZER, Birgit GEUEKE, Hans-Peter E. KOHLER und Peter LIENEMANN, 2013. Stereochemistry of LinB-catalyzed biotransformation of δ-HBCD to 1R,2R,5S,6R,9R,10S-pentabromocyclododecanol. Chemosphere. 2013. Bd. 90, Nr. 6, S. 1911–1919. DOI 10.1016/j.chemosphere.2012.10.019
Heeb, Norbert V., Daniel Zindel, Heidi Graf, Valeria Azara, W. Bernd Schweizer, Birgit Geueke, Hans-Peter E. Kohler, and Peter Lienemann. 2013. “Stereochemistry of LinB-Catalyzed Biotransformation of δ-HBCD to 1R,2R,5S,6R,9R,10S-Pentabromocyclododecanol.” Chemosphere 90 (6): 1911–19. https://doi.org/10.1016/j.chemosphere.2012.10.019.
Heeb, Norbert V., et al. “Stereochemistry of LinB-Catalyzed Biotransformation of δ-HBCD to 1R,2R,5S,6R,9R,10S-Pentabromocyclododecanol.” Chemosphere, vol. 90, no. 6, 2013, pp. 1911–19, https://doi.org/10.1016/j.chemosphere.2012.10.019.
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