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.
Catalytic Promiscuity: Catecholase-like Activity and Hydrolytic DNA Cleavage
Promoted by a Mixed-Valence FeIIIFeII Complex.
Journal of the Brazilian Chemical Society, 21 (7).
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
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.
||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. http://dx.doi.org/10.1590/S0103-50532010000700007.
||mixed-valence FeIIIFeII complex; unsymmetrical ligand; catalytic promiscuity; diester and DNA cleavage; catecholase activity;
||Faculty of Science and Engineering > Chemistry
||23 May 2012 15:33
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||Journal of the Brazilian Chemical Society
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