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Issue 22, 2014
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Neocarzinostatin-based hybrid biocatalysts for oxidation reactions

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Abstract

An anionic iron(III)-porphyrin–testosterone conjugate 1-Fe has been synthesized and fully characterized. It has been further associated with a neocarzinostatin variant, NCS-3.24, to generate a new artificial metalloenzyme following the so-called ‘Trojan Horse’ strategy. This new 1-Fe-NCS-3.24 biocatalyst showed an interesting catalytic activity as it was found able to catalyze the chemoselective and slightly enantioselective (ee = 13%) sulfoxidation of thioanisole by H2O2. Molecular modelling studies show that a synergy between the binding of the steroid moiety and that of the porphyrin macrocycle into the protein binding site can explain the experimental results, indicating a better affinity of 1-Fe for the NCS-3.24 variant than testosterone and testosterone-hemisuccinate themselves. They also show that the Fe-porphyrin complex is sandwiched between the two subdomains of the protein providing with good complementarities. However, the artificial cofactor entirely fills the cavity and its metal ion remains widely exposed to the solvent which explains the moderate enantioselectivity observed. Some possible improvements in the “Trojan Horse” strategy for obtaining better catalysts of selective oxidations are presented.

Graphical abstract: Neocarzinostatin-based hybrid biocatalysts for oxidation reactions

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Publication details

The article was received on 15 Jan 2014, accepted on 17 Mar 2014 and first published on 17 Mar 2014


Article type: Paper
DOI: 10.1039/C4DT00151F
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Citation: Dalton Trans., 2014,43, 8344-8354

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    Neocarzinostatin-based hybrid biocatalysts for oxidation reactions

    E. Sansiaume-Dagousset, A. Urvoas, K. Chelly, W. Ghattas, J. Maréchal, J. Mahy and R. Ricoux, Dalton Trans., 2014, 43, 8344
    DOI: 10.1039/C4DT00151F

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