Catalytic promiscuity: catecholase-like activity and hydrolytic DNA cleavage promoted by a mixed-valence FeIII FeII complex

Journal of the Brazilian Chemical Society

Smith, Sarah J.¹  Peralta, Rosely A.¹  Schenk, Gerhard¹  University of Queensland, Australia¹  Bortoluzzi, Adailton J.¹  Jovito, Rafael¹  Souza, Bernardo de¹  Gahan, Lawrence R.¹  Riley, Mark J.¹  Universidade Federal de Santa Catarina, Florianópolis, Brazil¹  Joussef, Antônio C.¹  Severino, Patricia C.¹  Neves, Ademir¹  LABINC¹  Terenzi, Hernán¹  Szpoganicz, Bruno¹  Fischer, Franciele L.¹ 

关键词: mixed-valence FeIIIFeII complex;    unsymmetrical ligand;    catalytic promiscuity;    diester and DNA cleavage;    catecholase activity;   

DOI  :  10.1590/S0103-50532010000700007

学科分类：化学（综合）

来源: SciELO

【 摘 要 】

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(µ-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.

【 授权许可】

Unknown