Hydroxyl Radical Generation and DNA Nuclease Activity: A Mechanistic Study Based on a Surface-Immobilized Copper Thioether Clip-Phen Derivative.

Autor: Romo AI; Departamento de Química Orgânica e Inorgânica, Universidade Federal do Ceará, Cx. Postal 6021, Fortaleza, CE, 60451-970, Brasil., Abreu DS; Departamento de Química Orgânica e Inorgânica, Universidade Federal do Ceará, Cx. Postal 6021, Fortaleza, CE, 60451-970, Brasil., de F Paulo T; Departamento de Química Orgânica e Inorgânica, Universidade Federal do Ceará, Cx. Postal 6021, Fortaleza, CE, 60451-970, Brasil., Carepo MS; Departamento de Química Orgânica e Inorgânica, Universidade Federal do Ceará, Cx. Postal 6021, Fortaleza, CE, 60451-970, Brasil., Sousa EH; Departamento de Química Orgânica e Inorgânica, Universidade Federal do Ceará, Cx. Postal 6021, Fortaleza, CE, 60451-970, Brasil., Lemus L; Facultad de Química y Biología, Universidad de Santiago de Chile, Alameda 3363, Estación Central, Santiago, Chile., Aliaga C; Facultad de Química y Biología, Universidad de Santiago de Chile, Alameda 3363, Estación Central, Santiago, Chile.; Centro para el Desarrollo de la Nanociencia y la Nanotecnología, CEDENNA, Santiago, Chile., Batista AA; Departamento de Química, Universidade Federal de São Carlos, CP 676, CEP, 13565-905, São Carlos, SP, Brazil., Nascimento OR; Departamento de Física e Informática, Instituto de Física de São Carlos, Universidade de São Paulo, CP 369, CEP, 13560-970, São Carlos, SP, Brazil., Abruña HD; Department of Chemistry and Chemical Biology, Cornell University, Ithaca, NY, 14853-1301, USA. hda1@cornell.ed., Diógenes IC; Departamento de Química Orgânica e Inorgânica, Universidade Federal do Ceará, Cx. Postal 6021, Fortaleza, CE, 60451-970, Brasil. Izaura@dqoi.ufc.br.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2016 Jul 11; Vol. 22 (29), pp. 10081-9. Date of Electronic Publication: 2016 Jun 16.
DOI: 10.1002/chem.201601719
Abstrakt: Coordination compounds of copper have been invoked as major actors in processes involving the reduction of molecular oxygen, mostly with the generation of radical species the assignment for which has, so far, not been fully addressed. In the present work, we have carried out studies in solution and on surfaces to gain insights into the nature of the radical oxygen species (ROS) generated by a copper(II) coordination compound containing a thioether clip-phen derivative, 1,3-bis(1,10-phenanthrolin-2-yloxy)-N-(4-(methylthio)benzylidene)propan-2-amine (2CP-Bz-SMe), enabling its adsorption/immobilization to gold surfaces. Whereas surface plasmon resonance (SPR) and electrochemistry of the adsorbed complex indicated the formation of a dimeric Cu(I) intermediate containing molecular oxygen as a bridging ligand, scanning electrochemical microscopy (SECM) and nuclease assays pointed to the generation of a ROS species. Electron paramagnetic resonance (EPR) data reinforced such conclusions, indicating that radical production was dependent on the amount of oxygen and H2 O2 , thus pointing to a mechanism involving a Fenton-like reaction that results in the production of OH(.) .
(© 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.)
Databáze: MEDLINE
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