Hindawi Publishing Corporation
Bioinorganic Chemistry and Applications
Volume 2010, Article ID 973742, 9 pages
doi:10.1155/2010/973742
Research Article
Synthesis, Characterization, DNA Binding, and
Photocleavage Activity of Oxorhenium (V) Complexes with
α-Diimine and Quinoxaline Ligands
Christiana A. Mitsopoulou and Constantinos Dagas
Laboratory of Inorganic Chemistry, Department of Chemistry, University of Athens, Panepistimiopolis, Zografou, Athens 157 71, Greece
Correspondence should be addressed to Christiana A. Mitsopoulou, cmitsop@chem.uoa.gr
Received 11 March 2010; Accepted 1 April 2010
Academic Editor: Spyros Perlepes
Copyright © 2010 C. A. Mitsopoulou and C. Dagas. This is an open access article distributed under the Creative Commons
Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is
properly cited.
The complex [ReOCl
3
pq] (1) (where pq = 2-(2
′
pyridyl)quinoxaline) has been synthesized and fully characterized by UV-Vis, FTIR,
1 and 2D NMR, and cyclic voltammetry (CV). The DNA-binding properties of the complex 1 as well as of the compounds
[ReOCl
3
bpy] (2), [ReOCl
3
phen] (3), and pq (4) were investigated by UV-spectrophotometric (melting curves), CV (cyclic
voltammetry), and viscosity measurements. Experimental data suggest that complex 1 intercalates into the DNA base pairs. Upon
irradiation, complex 1 was found to promote the cleavage of plasmid pBR 322 DNA from supercoiled form I to nicked form II.
The mechanism of the DNA cleavage by complex 1 was also investigated.
1. Introduction
For many years transition metal complexes have piqued
curiosity owing to their efficient DNA binding and cleavage
properties under physiological conditions [1–14]. It has been
demonstrated that inorganic complexes can be used in foot-
printing studies, as sequence specific DNA binding agents, as
diagnostic agents in medicinal applications, and for genomic
research. Among different modes of DNA cleavage, oxidative
cleavage of DNA upon irradiation with visible light is of main
interest due to the potential applications of such compounds
in photodynamic therapy of cancer [3, 15] and references
therein.
On the other hand, coordination chemistry of rhenium
has been extensively developed in recent years due, to a
large extent, to the fact that its complexes with diimine
ligands display long lifetimes and also short-lived rhenium
isotopes hold promise as β-emitters in radiotherapy [14,
16, 17]. The chemistry of oxorhenium complexes arouses
particular interest among these compounds not only for their
implication in various reactions of industrial and biological
importance, including olefin epoxidation and catalysis by
cytochrome P-450 [18, 19], but also for their lipophilic
character and the oxidation states of rhenium that is Re(I)
to Re (VI) [17].
In this context, the design, synthesis, and reactivity of
novel rhenium oxocomplexes have become the aim of several
laboratories, including ours. To the best of our knowledge,
studies on oxorhenium (V) complexes incorporating planar
aromatic ligands that could bind to DNA have not been
studied before. Nevertheless, quinoxaline (pq) has recently
received considerable attention [20, 21]. The structure of
the quinoxaline ligand is recognized from a great number of
natural compounds such as riboflavin and molybdopterines,
and can be used as antibacterial, antiviral, anticancer,
antihelmintic, and insecticidal agent [22]. In addition, it
adopts a planar conformation when chelates to a metal ion
[20, 23, 24]. This planar appendage provides a handle for
intercalative binding to DNA, positioning the complex for
enhanced reactivity toward DNA.
In this paper, we present the synthesis and character-
ization of the oxorhenium (V) complex, [ReOCl
3
pq] (1).
In order to elucidate the reactivity of this compound, we
have also synthesized the complexes [ReOCl
3
bpy] (2) and
[ReOCl
3
phen] (3) and studied their intercalating abilities.
The ligands (2
′
pyridyl)quinoxaline (4), 2,2
′
bipyridine (5),