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Catalytic Promiscuity: Catecholase-like Activity and Hydrolytic DNA Cleavage Promoted by a Mixed-Valence FeIIIFeII Complex
Neves, Ademir ; Bortoluzzi, Adailton J.; Jovito, Rafael; Peralta, Rosely A.; de Souza, Bernardo; Szpoganicz, Bruno; Joussef, Antonio C.; Terenzi, Hernan; Severino, Patricia C.; Fischer, Franciele L.; Schenk, Gerhard; Riley, Mark J.; Smith, Sarah J.; Gahan, Lawrence R.
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.
Keyword(s): Chemistry; mixed-valence FeIIIFeII complex; unsymmetrical ligand; catalytic promiscuity; diester and DNA cleavage; catecholase activity
Publication Date:
Type: Journal article
Peer-Reviewed: Yes
Institution: Maynooth University
Citation(s): 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
Publisher(s): Sociedade Brasileira de Química
File Format(s): application/pdf
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First Indexed: 2020-01-31 06:06:22 Last Updated: 2020-04-02 07:27:31