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    Catalytic Promiscuity: Catecholase-like Activity and Hydrolytic DNA Cleavage Promoted by a Mixed-Valence FeIIIFeII Complex

    Neves, Ademir and Bortoluzzi, Adailton J. and Jovito, Rafael and Peralta, Rosely A. and de Souza, Bernardo and Szpoganicz, Bruno and Joussef, Antonio C. and Terenzi, Hernan and Severino, Patricia C. and Fischer, Franciele L. and Schenk, Gerhard and Riley, Mark J. and Smith, Sarah J. and Gahan, Lawrence R. (2010) Catalytic Promiscuity: Catecholase-like Activity and Hydrolytic DNA Cleavage Promoted by a Mixed-Valence FeIIIFeII Complex. Journal of the Brazilian Chemical Society, 21 (7). pp. 1201-1212. ISSN 0103-5053

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    Catalytic promiscuity has emerged as an important property of many enzymes since the relationship of this property to enzymatic evolution became clear. Simultaneously, the development of suitable biomimetic catalytic systems capable of mimicking the promiscuous catalytic properties of such enzymes represents a new challenge for bioinorganic chemists. In this paper we report on the X-ray structure, the solution studies and the promiscuous catalytic activity of the mixed-valence complex [(bpbpmp)FeIII(m-OAc)2FeII](ClO4), (1), containing the unsymmetrical dinucleating ligand 2-{[(2-hydroxybenzyl)(2-pyridylmethyl)aminomethyl]-4-methyl-6-[bis(2-pyridylmethyl) aminomethyl]}phenol (H2bpbpmp). Potentiometric and spectrophotometric titrations and kinetics studies showed that this coordination compound generates active species that promote hydrolytic cleavage of double strand DNA (dsDNA), with a rate enhancement of 1.9×108 over the non-catalyzed reaction, as well as promote oxidation of 3,5-di-tert-butylcatechol (3,5-dtbc), with kcat = 1.16 × 10‑2 s-1 and KM = 7.1×10-4 mol L-1. Thus, complex 1 shows both hydrolase and oxidoreductase activities and can be regarded as a man-made model for studying catalytic promiscuity.

    Item Type: Article
    Additional Information: Licensed under a Creative Commons License. ©2010 Sociedade Brasileira de Química. The definitive version of this article is available at NEVES, Ademir et al. Catalytic promiscuity: catecholase-like activity and hydrolytic DNA cleavage promoted by a mixed-valence FeIIIFeII complex. J. Braz. Chem. Soc. [online]. 2010, vol.21, n.7, pp. 1201-1212. ISSN 0103-5053.
    Keywords: mixed-valence FeIIIFeII complex; unsymmetrical ligand; catalytic promiscuity; diester and DNA cleavage; catecholase activity;
    Academic Unit: Faculty of Science and Engineering > Chemistry
    Item ID: 3675
    Identification Number:
    Depositing User: Gary Schenk
    Date Deposited: 23 May 2012 15:33
    Journal or Publication Title: Journal of the Brazilian Chemical Society
    Publisher: Sociedade Brasileira de Química
    Refereed: Yes
    Use Licence: This item is available under a Creative Commons Attribution Non Commercial Share Alike Licence (CC BY-NC-SA). Details of this licence are available here

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