Synthesis and structural characterization of some divalent metal complexes: DNA binding and antitumor activity

Article abstract of DOI:10.1016/j.molliq.2017.07.009

New Complexes (1–4) of Cu(II), Ni(II) Zn(II) and Mn(II) with 3-Ethoxy-6-(phenyl azo)-7-hydroxy coumarin (HL) have been prepared and characterized by elemental analyses, IR, ¹H NMR, ¹³C NMR, mass spectroscopy and UV–Visible spectra as well as thermal measurements. IR spectra showed that the ligand (HL) acts as a monobasic bidentate and coordinating via the nitrogen atom of the azo group ([sbnd]N[dbnd]N[sbnd]) and oxygen atom of the deprotonated phenolic OH group. The molar conductance measurements proved that all the complexes are non-electrolytes. Also the important fragments in the ligand and Ni(II) complex were done using mass spectra and the main peaks were corresponding to the molecular weights. The molecular and electronic structures of the investigated compounds were also studied using quantum chemical calculations. The bonding parameters of the complexes have been calculated. Molecular docking was used to predict the binding between azo compound with the receptor of 3hb5-oxidoreductase receptor of breast cancer and of 2q7k-hormone of prostate cancer. The calf thymus DNA binding activity of the ligand and its metal complexes was studied by absorption spectra and viscosity measurement. The antitumor activity of the ligand and its metal complexes was tested against human cancer MCV-7 (breast cancer).

Full text of DOI:10.1016/j.molliq.2017.07.009

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Accepted Manuscript
Synthesis and structural characterization of some divalent metal
complexes: DNA binding and antitumor activity
A.A. El-Bindary, N. Hassan, M.A. El-Afify
PII:
DOI:
Reference:
S0167-7322(17)32177-3
doi: 10.1016/j.molliq.2017.07.009
MOLLIQ 7586
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Journal of Molecular Liquids
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Accepted date:
17 May 2017
2 July 2017
4 July 2017
Please cite this article as: A.A. El-Bindary, N. Hassan, M.A. El-Afify , Synthesis and
structural characterization of some divalent metal complexes: DNA binding and antitumor
activity, Journal of Molecular Liquids (2017), doi: 10.1016/j.molliq.2017.07.009
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Synthesis and structural characterization of some divalent metal complexes: DNA
binding and antitumor activity
A.A. El-Bindary1,*, N. Hassan2, M.A. El-Afify2
1Chemistry Department, Faculty of Science, University of Damietta, Damietta 34517,
Egypt
2Chemistry Department, Faculty of Science, University of Port Said, Egypt
*Corresponding author. E-mail: abindary@yahoo.com (A.A. El-Bindary).
Abstract
New Complexes (1-4) of Cu(II), Ni(II) Zn(II) and Mn(II) with 3-Ethoxy-6-(phenyl azo)-
7-hydroxy coumarin (HL) have been prepared and characterized by elemental analyses,
1
13
IR, H NMR, C NMR, mass spectroscopy and UV–Visible spectra as well as thermal
measurements. IR spectra showed that the ligand (HL) acts as a monobasic bidentate and
coordinating via the nitrogen atom of the azo group (-N=N-) and oxygen atom of the
deprotonated phenolic OH group. The molar conductance measurements proved that all
the complexes are non-electrolytes. Also the important fragments in the ligand and Ni(II)
complex were done using mass spectra and the main peaks were corresponding to the
molecular weights. The molecular and electronic structures of the investigated
compounds were also studied using quantum chemical calculations. The bonding
parameter of the complexes have been calculated. Molecular docking was used to predict
the binding between azo compound with the receptor of 3hb5-oxidoreductase receptor of
breast cancer and of 2q7k-hormone of prostate cancer. The calf thymus DNA binding
activity of the ligand and its metal complexes was studied by absorption spectra and
viscosity measurement. The antitumor activity of the ligand and its metal complexes was
tested against human cancer MCV-7 (breast cancer).
Keywords: Azo coumarin; Molecular structure; Molecular docking; CT-DNA binding;
Antitumor.

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1. INTRODUCTION
Coumarin (2H-1-benzopyran-2-one), the parent molecule of coumarin derivatives, is the
simplest compound of a large class of naturally occurring phenolic substances made of
fused benzene and a-pyrone rings [1]. Coumarins owe their class name to ‘Coumarou’,
the vernacular name of the tonka bean (Dipteryx odorata Willd, Fabaceae), from which
coumarin, it was isolated in 1820 (Bruneton, 1999). There are four main coumarin sub-
types: Coumarin and its derivatives are principal oral anticoagulants. Coumarin is water
insoluble; however 4-hydroxy substitution confers weakly acidic properties to the
molecule that makes it water soluble under slightly alkaline conditions.
Many products which contain a coumarin moiety exhibit excellent biological activity
such as molluscicides, anthelmintic, hypnotic, insecticidal, activity fluorescent
brighteners, antitumor [2], antibacterial [3], antifungal [4], anticoagulant [5], estrogenic,
vasodilator, sedative, analgesic and hypothermic activity and anti-inflammatory [6]. In
addition, these compounds are used as additives to food and cosmetics preparation as a
dye and preservatives [7]. As like coumarin, azo dye functional group containing
compound are have huge important is there commercially, it act as anti-microbial, and
food coloring agent [8]. We felt it of interest to study the chemical reactivity of these
heterocyclic coumarin moieties fuse with azo dyes to give a novel azo coumarin dye
obtained by the diazotization followed by coupling with aromatic hydro carbon. The
synthesized compound influencing biological behaviors of individual coumarin as well as
azo dye compound. Monohydroxy compounds containing coumarin nucleus have proved
to be of great importance, introduction of azo group to such hydroxy coumarins increases
its chelating tendency. The formation of diazotizing reagent starts with protonation of
nitrous acid under strongly acidic conditions and azo coupling is carried out at low
temperature in the presence of nucleophilic coupling components. They exist in the trans
form with a bond angle of 120˚ [9]. The complexes of azo compounds have reasonably
good technical properties, including light and weather fastness and resistance to solvents
and water. The biological importance of azo complexes is well known due to their use as
inflammatory [10], anticancer [11], antibacterial [12], and antifungal [13]. Azo

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complexes have received much attention due to their versatile use in many practical
applications such as coloring fiber [14].
A qualified plan for this study will be established on the basis of the properties of azo
coumarin and its metal complexes which have many different properties. The present
work is devoted to the preparation of new complexes of Cu(II), Ni(II) Zn(II) and Mn(II)
with 3-Ethoxy-6-(phenyl azo)-7-hydroxy coumarin. Their structures and thermal stability
are elucidated by means of partial elemental analysis, spectroscopic (IR, UV-visible and
1
H NMR) as well as magnetic measurements. Also, the thermal behavior of the
synthesized complexes was investigated using TGA and the corresponding kinetic
parameters are evaluated. The calf thymus DNA binding activity of the ligand and its
metal complexes were studied by absorption spectra and viscosity measurements. The
antitumor activity of the ligand and its metal complexes was tested against human cancer
MCF-7 (breast cancer).