The Oxygen Dilemma: A Severe Challenge for the Application of Monooxygenases?

Monooxygenases are promising catalysts because they in principle enable the organic chemist to perform highly selective oxyfunctionalisation reactions that are otherwise difficult to achieve. For this, monooxygenases require reducing equivalents, to allow reductive activation of molecular oxygen at...

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Bibliographic Details
Published in:Chembiochem : a European journal of chemical biology 2016-08, Vol.17 (15), p.1391-1398
Main Authors: Holtmann, Dirk, Hollmann, Frank
Format: Article
Language:English
Subjects:
biocatalysis
Catalysis
Chemistry, Organic - methods
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Minireviews
Mixed Function Oxygenases - metabolism
monooxygenases
Oxidation-Reduction
oxidoreductases
oxyfunctionalization
Oxygen
Oxygen - chemistry
uncoupling
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Summary:Monooxygenases are promising catalysts because they in principle enable the organic chemist to perform highly selective oxyfunctionalisation reactions that are otherwise difficult to achieve. For this, monooxygenases require reducing equivalents, to allow reductive activation of molecular oxygen at the enzymes' active sites. However, these reducing equivalents are often delivered to O2 either directly or via a reduced intermediate (uncoupling), yielding hazardous reactive oxygen species and wasting valuable reducing equivalents. The oxygen dilemma arises from monooxygenases' dependency on O2 and the undesired uncoupling reaction. With this contribution we hope to generate a general awareness of the oxygen dilemma and to discuss its nature and some promising solutions. A love–hate relationship? Monooxygenase‐catalysed reactions depend on the availability of oxygen. On the other hand, several side reactions between oxygen and the components of natural and artificial electron transfer pathways have a negative influence on the catalytic efficiency. This oxygen dilemma is discussed here.
ISSN:1439-4227
1439-7633
1439-7633
DOI:10.1002/cbic.201600176