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Hydroxylation of naphthalene by aromatic peroxygenase from Agrocybe aegerita proceeds via oxygen transfer from H2O2 and intermediary epoxidation

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Abstract

Agrocybe aegerita peroxidase/peroxygenase (AaP) is an extracellular fungal biocatalyst that selectively hydroxylates the aromatic ring of naphthalene. Under alkaline conditions, the reaction proceeds via the formation of an intermediary product with a molecular mass of 144 and a characteristic UV absorption spectrum (A max 210, 267, and 303 nm). The compound was semistable at pH 9 but spontaneously hydrolyzed under acidic conditions (pH <7) into 1-naphthol as major product and traces of 2-naphthol. Based on these findings and literature data, we propose naphthalene 1,2-oxide as the primary product of AaP-catalyzed oxygenation of naphthalene. Using 18O-labeled hydrogen peroxide, the origin of the oxygen atom transferred to naphthalene was proved to be the peroxide that acts both as oxidant (primary electron acceptor) and oxygen source.

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Acknowledgement

The authors would like to thank the following institutions and organizations for financial support: European Union (integrated project BIORENEW), the German Ministry of Education and Research (BMBF, project 0313433D), and the German Environmental Foundation (DBU, project 13225-32).

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Authors and Affiliations

  1. Unit of Environmental Biotechnology, International Graduate School of Zittau, Zittau, Germany

    Martin Kluge, René Ullrich, Christoph Dolge & Martin Hofrichter

  2. University of Applied Sciences Lausitz, Senftenberg, Germany

    Katrin Scheibner

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  1. Martin Kluge
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  2. René Ullrich
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  3. Christoph Dolge
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  4. Katrin Scheibner
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  5. Martin Hofrichter
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Correspondence to Martin Kluge.

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Kluge, M., Ullrich, R., Dolge, C. et al. Hydroxylation of naphthalene by aromatic peroxygenase from Agrocybe aegerita proceeds via oxygen transfer from H2O2 and intermediary epoxidation. Appl Microbiol Biotechnol 81, 1071–1076 (2009). https://doi.org/10.1007/s00253-008-1704-y

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  • DOI: https://doi.org/10.1007/s00253-008-1704-y

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