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Design and catalytic studies of structural and functional models of the catechol oxidase enzyme

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Abstract

The catechol oxidase activity of three copper/bicompartmental salen derivatives has been studied. One mononuclear, [CuL] (1), one homometallic, [Cu2L(NO3)2] (2), and one heterometallic, [CuMnL(NO3)2] (3) complexes were obtained using the ligand H2L = N,N′-bis(3-methoxysalicylidene)-1,3-propanediamine through different synthetic methods (electrochemical, chemical and solid state reaction). The structural data indicate that the metal ion disposition models the active site of type-3 copper enzymes, such as catechol oxidase. In this way, their ability to act as functional models of the enzyme has been spectrophotometrically determined by monitorization of the oxidation of 3,5-di-tert-butylcatechol (3,5-DTBC) to 3,5-di-tert-butyl-o-benzoquinone (3,5-DTBQ). All the complexes show significant catalytic activity with ratio constants (kobs) lying in the range (223–294) × 10–4 min−1. A thorough kinetic study was carried out for complexes 2 and 3, since they show structural similarities with the catechol oxidase enzyme. The greatest catalytic activity was found for the homonuclear dicopper compound (2) with a turnover value (kcat) of (3.89 ± 0.05) × 106 h−1, which it is the higher reported to date, comparable to the enzyme itself (8.25 × 106 h−1).

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Acknowledgements

The authors gratefully acknowledge the Spanish Ministry of Economy and Competitiveness (MINECO/FEDER) for financial support (Project CTQ2015-63858-P) and Comunidad de Madrid (Project S2017/BMD-3770-CM). One of us (Aarón Terán) acknowledge Comunidad de Madrid (Project S2017/BMD-3770-CM) for a predoctoral Grant.

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  1. Departamento de Química Inorgánica, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, 28040, Madrid, Spain

    Aarón Terán, Aida Jaafar, Ana E. Sánchez-Peláez, M. Carmen Torralba & Ángel Gutiérrez

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  1. Aarón Terán
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Correspondence to Aarón Terán.

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Dedicated to Professor José Antonio Campo Santillana, in memoriam.

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Terán, A., Jaafar, A., Sánchez-Peláez, A.E. et al. Design and catalytic studies of structural and functional models of the catechol oxidase enzyme. J Biol Inorg Chem 25, 671–683 (2020). https://doi.org/10.1007/s00775-020-01791-2

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