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Hydroxyl Radical Generation and DNA Nuclease Activity: A Mechanistic Study Based on a Surface‐Immobilized Copper Thioether Clip‐Phen Derivative
Author(s) -
Romo Adolfo I. B.,
Abreu Dieric S.,
de F. Paulo Tércio,
Carepo Marta S. P.,
Sousa Eduardo H. S.,
Lemus Luis,
Aliaga Carolina,
Batista Alzir A.,
Nascimento Otaciro R.,
Abruña Héctor D.,
Diógenes Izaura C. N.
Publication year - 2016
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201601719
Subject(s) - chemistry , electron paramagnetic resonance , thioether , copper , photochemistry , electrochemistry , hydroxyl radical , ligand (biochemistry) , surface plasmon resonance , nuclease , amine gas treating , derivative (finance) , reactive oxygen species , radical , stereochemistry , dna , organic chemistry , nanoparticle , nanotechnology , materials science , biochemistry , physics , receptor , electrode , nuclear magnetic resonance , financial economics , economics
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 H 2 O 2 , thus pointing to a mechanism involving a Fenton‐like reaction that results in the production of OH . .