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Department of Chemistry, Zakir Husain Delhi College, University of Delhi, JLN-Marg, New Delhi 110002, India
Department of Chemistry, School of Sciences, IGNOU, Maidan Garhi, New Delhi 110068, India
h i g h l i g h t s
g r a p h i c a l a b s t r a c t
TGA curves of (red) ligand (L), (voilet) [Ni(L1)(OAc)2(H2O)](H2O), (green) [Zn(L1)(OAc)2] complexes in
nitrogen atmosphere.
a r t i c l e
i n f o
Article history:
Received 26 March 2014
Received in revised form 31 May 2014
Accepted 16 June 2014
Available online 28 June 2014
Keywords:
Schiff base
Ni(II) and Zn(II) complexes
Spectroscopic studies
DFT calculations
Anticancer activity
a b s t r a c t
The paper presents the synthesis of Ni(II) and Zn(II) complexes of general composition M(L)X2 and
M(L)2X2 (M = Ni(II), Zn(II), X = Cl1, OAc1) with Schiff base obtained through the condensation of
2-aminobenzamide with thiophene-2-carbaldehyde. The characterization of newly formed complexes
was done by 1H NMR, UVVIS, TGA, IR, mass spectrophotometry and molar conductivity studies. The
thermal studies suggested that the complexes are more stable as compared to ligand. In DFT studies
the geometries of Schiffs base and metal complexes were fully optimized with respect to the energy
using the 6-31+g(d,p) basis set. On the basis of the spectral studies a distorted octahedral geometry
has been assigned for Ni(II) complexes and tetrahedral geometry for Zn(II) complexes. The effect of these
complexes on proliferation of human breast cancer cell line (MCF-7) and human hepatocellular liver
carcinoma cell line (HepG2) were studied and compared with those of free ligand.
2014 Elsevier B.V. All rights reserved.
Introduction
Benzamides derivatives show signicant antibacterial,
antifungal, analgesic, antihelmintic, anti-inammatory, antimalar Corresponding author. Tel.: +91 1122911267; fax: +91 1123215906.
E-mail address: schandra_00@yahoo.com (S. Chandra).
http://dx.doi.org/10.1016/j.saa.2014.06.112
1386-1425/ 2014 Elsevier B.V. All rights reserved.
ial, antitumor and antiallergic activities [17] and are still one of
the most common functional groups employed in the preparation
of an aromatic ligand. The ambidentate nature of amide group
leads to the formation of regioisomers when forming a metal complex, as it is possible to coordinate either through the nitrogen or
the oxygen atoms. The N and O chelating sites present in the amide
group is the indispensable building block of biologically vital poly-
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P. Tyagi et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 134 (2015) 200209
mers, for instance peptides and proteins play a noteworthy function in biochemistry and biology. Schiff bases are potential anticancer drugs and when administered as their metal complexes, the
anticancer activity of these complexes is enhanced in comparison
to the free ligand [8]. Similarly, the role of thiophene derivates in
medicinal chemistry is very well known for their therapeutic applications. Metal complexes containing amide functional groups conrm a wide spectrum of biological activities [914] and are also
used as drugs in medicinal elds. Very limited research has been
carried out on the synthesis of transition metal complexes with
oxygen and nitrogen donor Schiff base derivatives of 2-aminobenzamide. Recently, Seyed et al. have reported a novel one pot synthesis method for the synthesis of anthranilamide Schiff bases [16].
Mixed metal complexes of 2-aminobenzamide with Cu(II) in the
presence of some amino acids have been prepared, characterized
and tested for their antibacterial activities [17]. The ambidentate
nature of amide group and their resistance to hydrolysis
(which means ligand cleavage are less likely to occur) makes it a
preferred subject of study. Therefore, it is worthwhile to carry
out the synthesis and study the spectral properties of the Schiff
base derived from 2-aminobenzamide and thiophene-2-carbaldehyde. The goal of the study presented here is to synthesize the
Ni(II) and Zn(II) metal complexes of Schiff base produced from condensation of 2-aminobenzamide & thiophene-2-carbaldehyde and
to provide a baseline of structural data using various spectroscopic
techniques, their thermal behavior, DFT studies and anticancer
activity.
Experimental
Materials and methods
All the chemicals were used of Anala R grade and received from
SigmaAldrich and Fluka. Metal salts were purchased from E.
Merck and used as received. MTT (3-(4,5-dimethylthiazole-2-yl)2,5-diphenyl tetrazolium bromide) and 0.25% trypsin and 0.02%
EDTA mixture was purchased from Himedia (India). Fetal bovine
serum (FBS) was purchased from Biowest (USA).
Synthesis of ligand
The Schiff base L (Fig. 1) was prepared by reuxing in ethanol
(2530 mL) an equimolar mixture of 2-aminobenzamide and thiophene-2-carbaldehyde for 34 h. On cooling the reaction mixture
overnight, white product was precipitated out. It was ltered off,
washed with cold ethanol and dried under vacuum over P4O10.
Synthesis of metal complexes
Hot ethanolic solution (15 mL) of metal salt (acetate or chloride) (1 mmol) were mixed with a hot ethanolic solution (20 mL)
of the ligand L (1 mmol or 2 mmol). The reaction mixture was
reuxed for 824 h at 8085 C. On keeping the resulting mixture
overnight at 0 C, the product was separated out, which was l-
Table 1
Physical and analytical data of the metal complexes (C1AC8) and ligand (L).
Comp.
no.
Color
White
C1
Light
green
C2
Green
C3
Shiny
green
C4
Light
green
C5
White
C6
White
C7
White
C8
White
M = Ni(II), Zn(II).
Molecular formula
Molecular
mass
m/z
Yield
(%)
Ma
C12H10N2OS
230
[Ni(L)(OAc)2(H2O)](H2O)
231
82
188
74
12.08
(12.16)
6.23
443
4.04
(4.38)
4.45
442
62.32
(62.59)
43.25
13.10
98
>280
(4.55)
4.01
(4.11)
3.77
(6.32)
8.76
(8.79)
6.71
(13.25)
9.15
(9.21)
14.01
194
>280
96
>280
218
>280
11
>280
197
>280
14
>280
208
>280
C16H20N2NiO7S
[Ni(L)2](OAc)2
C28H26N4NiO6S2
[Ni(L)(Cl)(H2O)2]ClH2O
636
637
62
412
413
68
(43.37)
52.54
(52.77)
34.77
C12H16Cl2N2NiO4S
[Ni(L)2](Cl)22H2O
624
625
56
(34.82)
46.12
(3.90)
3.74
(6.77)
8.90
(14.18)
9.26
412
413
76
642
643
72
364
365
68
612
613
64
(46.03)
46.33
(46.45)
52.01
(52.22)
39.13
(39.32)
46.54
(46.88)
(3.86)
3.78
(3.90)
4.03
(4.07)
2.69
(2.75)
3.25
(3.61)
(8.95)
6.62
(6.77)
8.56
(8.70)
7.23
(7.64)
9.02
(9.11)
(9.37)
15.71
(15.80)
10.13
(10.15)
17.72
(17.84)
10.56
(10.63)
C24H24Cl2N4NiO4S2
[Zn(L)(OAc)2]
C16H16N2O5SZn
[Zn(L)2](OAc)2
C28H26N4O6S2Zn
[Zn(L)(Cl)2]
C12H10Cl2N2OSZn
[Zn(L)2](Cl)2H2O
C24H22Cl2N4O3S2Zn
Molar conductance
(O1 cm2 mol1)
Melting Pt.
(C)
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P. Tyagi et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 134 (2015) 200209
tered off, washed with cold ethanol & ether and dried under vacuum over P4O10.
Analysis
The carbon and hydrogen were analyzed on Carlo-Erba 1106
elemental analyzer. The nitrogen content of the complexes was
determined using Kjeldahls method. Molar conductance was measured on the ELICO (CM82T) conductivity bridge. ESI-MS spectra
were obtained using a VG Biotech Quattrro mass spectrometer
equipped with an elctrospray ionization source in the mass range
of m/z 100 to m/z 1000. IR spectra (CsBr) were recorded on FTIR
spectrum BX-II spectrophotometer. NMR spectra were recorded
with a model Bruker Advance DPX-300 spectrometer operating at
400 MHz using DMSO-d6 as a solvent and TMS as internal
standard. The electronic spectra were recorded in DMSO on
Shimadzu UV mini-1240 spectrophotometer. Thermogravimetric
analysis (TGA) was carried out in dynamic nitrogen atmosphere
(30 ml/min) with a heating rate of 10 C/min using a Schimadzu
TGA-50H thermal analyzer.
DFT calculations
The DFT calculations were performed using the B3LYP three
parameter density functional, which includes Beckes gradient
exchange correction [18], the Lee, Yang, Parr correlation functional
[19] and the Vosko, Wilk, Nusair correlation functional [20]. The
gas phase geometries of Ligand L and metal complexes (C1AC8)
were fully optimized with respect to the energy using the
6-31+g(d,p) basis set using the Gaussian 09W suite [21]. Net
atomic charges had been obtained using natural bond orbital
(NBO) analysis of Weinhold and Carpenter [22].
In vitro studies (cell culturing)
The cell lines HepG2 (liver hepatocellular carcinoma) and MCF7 (human breast adenocarcinoma) were cultured as monolayers
and maintained in Dulbeccos modied Eagle medium (DMEM)
supplemented with 10% fetal bovine serum (FBS), 2 mM L-glutamine, 100 U/ml penicillin and 100 mg/ml streptomycin in a humid-
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H NMR spectra
The 1H NMR spectra have been recorded for ligand L and Zn(II)
complexes. The NMR spectra of the Zn(II) complexes indicated a
shift of electron density from ligand to metal. The ligand L showed
characteristic azomethine proton singlet at d 8.45 ppm (Fig. 3). The
characteristic signal, due to azomethine proton deshielded in the
spectra of metal complexes, suggest a coordination of azomethine
nitrogen atom. The azomethine proton of all zinc complexes
appears as a singlet between 8.36 and 8.28 ppm. In addition, CH3
hydrogen atoms of the acetate group appear as a singlet between
2.39 and 2.18 ppm for zinc complexes. The aromatic region is a
set of doublets, triplets and multiplets in the range 7.75
6.67 ppm for the complexes while it is 7.616.68 ppm for the
ligand. All the proton peaks were found to be in the expected
regions.
IR spectra
The IR spectrum of the ligand was compared with those of the
metal complexes in order to conrm the binding mode of the Schiff
base ligand to the corresponding metal ion. IR spectral data of the
ligand L and its corresponding metal complexes (C1AC8) are shown
in Table 2. Peak corresponding to m(C@O) stretching vibrations was
absent in IR spectra of L and, instead, a new band assigned to
azomethine m(HC@N) linkage appeared at 1612 cm1 conrming
the formation of Schiff base (Fig. 1). Band due to m(C@N) stretching
frequencies shift towards lower side (15901578 cm1) in all complexes indicating that the azomethine nitrogen atom was coordinated to metal ion [23]. This is also conrmed by the appearance
of new band in spectra of metal complexes in the range of 488
498 cm1, which has been assigned to the m(MAN) bond [23].
The m(C@O) stretching vibration of amide group at 1670 cm1 free
ligand shifts to a lower side (16681675 cm1) in all metal complexes, indicating the coordination of the ligand through the oxygen of amide group [15]. The same is also supported by the
appearance of band in region of 534540 cm1, which corresponds
to m(MAO) bond. A noteworthy point in the IR spectra of all metal
Table 2
Important infrared spectral bands (cm1) and their assignments.
Compound
m(HC@N)
m(CASAC)
m(C@O)
m(MAN)
m(MAO)
m(MAS)
m(MACl)
L
C1
C2
C3
C4
C5
C6
C7
C8
1612
1590
1584
1583
1578
1581
1585
1587
1581
830
842
838
845
840
829
830
828
830
1685
1672
1668
1671
1665
1665
1673
1672
1675
498
490
494
492
488
491
490
492
540
536
535
532
539
538
537
534
334
339
346
342
290
297
315
307
Table 3
Magnetic moment, electronic spectral bands (cm1) and ligand eld parameters of Ni(II) complexes.
Complex
leff BM
kmax (cm1)
m1
m2
m3
C1
C2
C3
C4
2.85
2.94
2.97
2.91
11,764
11,520
11,428
10,869
16,260
16,000
15,748
16,051
25,641
24,570
24,937
23,529
Dq (cm1)
B (cm1)
1176
1152
1142
1086
440
400
427
465
0.42
0.38
0.41
0.45
168
165
164
156
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P. Tyagi et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 134 (2015) 200209
Table 4
Thermal analysis data for the Schiffs base and its complexes.
Comp. no.
Molecular formula
Stages
Temp. (C)
Decomposition species
Residual species
Found
Calc.
C12H10N2OS
100
NiO
16.8
16.74
C2
[Ni(L)2](OAc)2
C28H26N4NiO6S2
NiO
11.5
11.63
C3
[Ni(L)(Cl)(H2O)2]ClH2O
C12H16Cl2N2NiO4S
NiO
18.65
17.96
C4
[Ni(L)2](Cl)22H2O
C24H24Cl2N4NiO4S2
NiO
12.74
11.85
C5
[Zn(L)(OAc)2]
C16H16N2O5SZn
[Zn(L)2](OAc)2
C28H26N4O6S2Zn
C4H3S
C8H7N2O
Loss of H2O
C8H11O5S
C8H7N2
C4H6O4
C8H6S2
C16H14N4O
HCl, 1/2O2
C5H9O2SNCl
C7H6N
Loss of 2HCl, H2O, 1/2O2
C8H6S2 (2 thiophene ring)
C16H14N4O (organic moiety)
C8H9O4S
C8H7N2
C4H6O4
C8H6S2
C16H14N4O
C4H3Cl2S
C8H7N2
Loss of H2O
Loss of C8H6OCl2S2
C16H14N4 (organic moiety)
100
[Ni(L)(OAc)2(H2O)](H2O)
C16H20N2NiO7S
150270
270460
80130
130320
320540
135230
230410
410555
70145
145360
360560
70195
195390
390550
125360
360600
110235
235390
390550
120375
357550
60110
110380
380545
C1
1st
2nd
1st
2nd
3rd
1st
2nd
3rd
1st
2nd
3rd
1st
2nd
3rd
1st
2nd
1st
2nd
3rd
1st
2nd
1st
2nd
3rd
ZnO
19.7
19.41
ZnO
12.47
12.46
ZnO
22.04
21.97
ZnO
13.21
13.07
C6
C7
C8
[Zn(L)(Cl)2]
C12H10Cl2N2OSZn
[Zn(L)2](Cl)2H2O
C24H22Cl2N4O3S2Zn
Fig. 5. TGA curves of (red) ligand (L), (voilet) [Ni(L1)(OAc)2(H2O)](H2O), (green) [Zn(L1)(OAc)2] complexes in nitrogen atmosphere. (For interpretation of the references to
color in this gure legend, the reader is referred to the web version of this article.)
P. Tyagi et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 134 (2015) 200209
205
Fig. 6. Geometry optimized structures of (a) ligand L, (b) complex C1, (c) complex C3, (d) complex C5, (e) complex C7 and (f) complex C6 (Color Code: H = White, C = Gray,
N = Blue, O = red Ni = Silver Gray, Zn = Gray). (For interpretation of the references to color in this gure legend, the reader is referred to the web version of this article.)
Magnetic moments
The magnetic moment observed for Ni(II) complexes lies in the
range 2.852.97 B.M suggesting a distorted octahedral geometry
[27]. Similarly, the Zn(II) complexes are found to be diamagnetic
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P. Tyagi et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 134 (2015) 200209
C2
C4
C7
C6
C5
C2
C8
N1
N2
C7
C1
N2
N2
C3
C9
C10
C1
C3
S
C12
C5
C2
Ni
C6
C4
C7
N1
C10
C11
(a)
C12
C11
M
X'
C6
C4
S
C9
C1
C3
Y'
C8
N1
C8
C5
C9
C10
C11
(b)
(c)
Scheme 1. Numbering scheme of the optimized structures (a) ligand L, (b) complex C1 & C3 and (c) complex C5 & C7.
Table 5
Optimized geometry of L and its metal complexes (bond length in Angstroms and bond angle in degree).
Parametersa
Ligand (L)
Complex C1b
Complex C3c
Complex C5d
Complex C7e
MAN1
MAO
MAS
MAX
MAX0
MAY
MAY0
C7AO
C6AN1
N1AC8
C8AC9
C9AS
OMY
OMN1
YMX
XMS
SMY0
N1MY0
XMX0
XMO
XMN1
N1MX0
1.22
1.40
1.27
1.54
1.67
1.86
2.69
2.71
1.91
2.04
2.12
1.27
1.48
1.35
1.45
1.77
63.73
96.20
85.25
96.57
86.21
91.67
1.87
2.42
2.54
2.29
1.92
1.87
1.25
1.50
1.34
1.42
1.79
72.4
95.2
87.4
94.2
83.5
92.2
2.14
2.19
2.1
2.13
1.27
1.49
1.32
1.42
1.76
112.1
109.8
107.3
110.1
2.15
2.13
2.36
2.25
1.26
1.42
1.30
1.44
1.82
114.2
111.2
103.3
109.2
L = 2-((thiophen-2-ylmethylene)amino)benzamide.
a
See Scheme 1 for numbering.
b
[M(L)(YY0 )X], M = Ni, X = H2O, Y = Y0 = OAc.
c
[M(L)(YY0 )X], M = Ni, X = Cl, Y = Y0 = H2O.
d
[M(L)(XX0 )], M = Zn, X = X0 = OAc.
e
[M(L)(XX0 )], M = Zn, X = X0 = Cl.
207
P. Tyagi et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 134 (2015) 200209
5). The ligand L interacts with metal ion through azomethine nitrogen, oxygen of amide group and through sulfur of thiophene moiety in a tridendate fashion. The thiophene moiety is bent out of the
coordination plane and move far from Ni(II) ion, which results in
the elongation of NiAS bond length. Similarly, the C@O bond of
the amide group moves out of the plane, which results in increase
of NiAO bond length. The NiAS and NiAO bond lengths in complexes C1 and C3 lies in the range of 2.542.71 and 2.422.69
respectively. This elongation in NiAS bond length caused a distortion from the regular octahedral geometries. It is due to distortion
that bond angle OANiAY reduces from 90 to 63.73 in complex C1
and 72.4 in complex C3 respectively. The two axial positions in
complex C1 are occupied by acetate ion, while at the sixth position
a water molecule is coordinated. Similarly, in complex C3 the two
axial positions are occupied by water molecule and chloride ion
coordinates at the sixth position. Attempt to optimize the complexes C2 & C4 was not successful.
Similarly, the Zn(II) complexes were fully optimized in gas
phase and the molecular structure revealed a tetrahedral environment around the Zn(II) ion. The ligand L interacts with metal ion in
a bidendate fashion through azomethine nitrogen and oxygen of
amide group. The remaining two positions are occupied by anions
(acetate/chloride) in complexes C5 & C7. The complex C6, which is
M(L)2 type has all the four position occupied by nitrogen and sulfur
atoms of the ligand L. The bond angles in the Zn(II) complexes are
found near to the approximate value. The XAZnAX0 , XAZnAN1,
XAZnAO, N1AZnAX0 bond angles in complex C5 are 112.1,
101.1, 109.8 and 110.1 respectively. Similarly the calculated
bond angles XAZnAX0 , XAZnAN1, XAZnAO, N1AZnAX0 in complex
C7 are 114.4, 103.3, 111.2 and 109.2 respectively.
Table 6
Occupancy (e) and polarity (%) of natural bond orbitals (NBOs) and hybrids calculated for complex C1 and complex C7.
Moleculea
NBO orbitala,b
Occupancy (e)
[Ni(L)(OAc)2(H2O)]H2O
r(NiAY)
1.812
(Complex C1)
r(NiAY0 )
1.756
[Zn(L)Cl2]
LP(N1)
LP(O)
LP(S)
LP(X)
r(ZnAX0 )
1.797
1.936
1.797
1.986
1.987
(Complex C7)
r(ZnAX)
1.984
LP(N1)
LP(O)
1.893
1.808
Polarity (%)c
11.64 (Ni)
88.36 (Y)
4.69 (Ni)
95.31 (Y0 )
15.57
84.43
15.67
84.33
(Zn)
(X0 )
(Zn)
(X)
NBO hybrid
1.61
pd
sp8.6
sp2.74 d1.44
sp5.5
sp3.73
sp0.69
sp3.73
Sp5.47
sp1.47 (Zn)
sp1.85 (X0 )
sp1.36 (Zn)
sp2.01 (X)
sp4.40
sp3.46
HOMO
Fig. 7. Plot of HOMO and LUMO of ligand L.
LUMO
AO (%)d
s(0.92) p(41.26) d(61.12)
s(10.4) p(89.6)
s(19.32) p(52.91) d(27.76)
s(15.3) p(84.2) d(0.5)
s(21.13) p(78.87)
s(59.34) p(40.66)
s(21.13) p(78.87)
s(15.46) p(84.54)
s(40.22) p(59.09) d(0.69)
s(35.06) p(64.94)
s(42.06 p(57.15) d(0.02)
s(33.26) p(66.74)
s(18.53) p(81.47)
s(22.44) p(77.56)
208
P. Tyagi et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 134 (2015) 200209
Table 7
Effect of a ligand L, and series of metal complexes (C1AC8) at two concentrations of 1 and 10 lM on the HepG2 and MCF-7 cell proliferation.a
Compound
Control
L
C1
C2
C3
C4
C5
C6
C7
C8
a
b
HepG2
MCF-7
HepG2
MCF-7
HepG2
MCF-7
HepG2
MCF-7
100 2
98 2
97 5
96 4
97 3
92 8
98 2
95 5
98 2
94 6
100 2
99 2
98 2
93 7
96 4
94 6
99 1
97 3
97 3
95 5
2
3
4
3
8b
2
5
2
6
1
2
7b
4
6
1
3
3
5
100 2
97 3
90 10
87 13
84 16
52 48
91 9
80 10
86 14
72 28
100 2
95 5
92 8
85 15
72 21
58 42
86 14
83 13
81 19
61 39
3
10
13
16b
48b
9
20b
14
28b
5
8
15
28b
42 b
14
17b
19b
39b
The results are expressed as the percentage of viable cells with respect to the control and are presented as mean SD.
Signicantly different from the control.
Conclusion
Fig. 9. Ligand L and complexes (C1AC8) inhibited the cell viability of HEP-G2 &
MCF-7 cells (Data were assayed by ANOVA and Students t-test. Differences
between means were considered signicant when yielding a P < 0.05. Results are
presented as means S.D.).
P. Tyagi et al. / Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy 134 (2015) 200209
6-31+g(d,p) for this type of work and conrms the suggested structure. Results of the antitumor activity screening indicated that the
ligand L has very less effect on the % inhibition on cell proliferation
at the two tested concentrations on HepG2 & MCF-7. Interestingly,
the complex C4 shows a 48% inhibition on cell proliferation against
HepG2, whereas complexes C4 and C8 greatly reduce the malignant
MCF-7 cell growth by 42% & 29% respectively. Further structural
optimization studies might thus represent a rationale for further
investigation.
Acknowledgement
We thank the Principal, Zakir Husain Delhi College for providing
lab facilities, Jamia Hamdard, New Delhi for Anticancer cell line
activities. Authors are thankful to DRDO, for nancial assistance.
References
[1] (a) V. Alexander, Chem. Rev. 95 (1995) 273;
(b) A.D. Granvoskii, A.L. Nivorozhkin, V.I. Minkin, Coord. Chem. Rev. 126
(1993) 1.
[2] D. Carbonnelle, F. Ebstein, C. Rabu, J.Y. Petit, M. Gregoire, F. Lang, Eur. J.
Immunol. 35 (2005) 546.
[3] K. Suzuki, H. Nagasawa, Y. Uto, Y. Sugimoto, K. Noguchi, M. Wakida, K.
Wierzba, T. Terada, T. Asao, Y. Yamada, K. Kitazato, H. Hori, Bioorg. Med. Chem.
13 (2005) 4014.
[4] M.V. Simonini, L.M. Camargo, E. Dong, E. Maloku, M. Veldic, E. Costa, A.
Guidotti, Proc. Natl. Acad. Sci. USA 103 (2006) 1587.
[5] E.A. Sener, K.K. Bingol, I. Oren, O.T. Arpaci, I. Yacin, N. Altanlar, Farmaco 55
(2000) 469.
[6] Y.F. Xiang, C.W. Qian, G.W. Xing, J. Hao, M. Xia, Y.F. Wang, Bioorg. Med. Chem.
Lett. 22 (2012) 4703.
[7] Y. Nagaoka, T. Maeda, Y. Kawai, D. Nakashima, T. Oikawa, K. Shimoke, T.
Ikeuchi, H. Kuwajima, S. Uesato, Eur. J. Med. Chem. 41 (2006) 697.
[8] (a) E.M. Hodnett, W.J. Dunn, J. Med. Chem. 13 (1970) 768770;
E.M. Hodnett, W.J. Dunn, J. Med. Chem. 15 (1972) 339;
(b) D. Kessel, A.F.A. Sayyab, E.M.H. Jaffar, A.H.H.A. Lanil, Iraqian J. Sci. 22 (1981)
312;
(c) J. Chakraborty, R.N. Patel, J. Indian Chem. Soc. 73 (1996) 191.
[9] A.P. Singh, N.K. Kaushik, A.K. Verma, R. Gupta, Indian J. Chem. 50 (2011) 474.
209
[10] A.P. Singh, N.K. Kaushik, A.K. Verma, G. Hundal, R. Gupta, Eur. J. Med. Chem. 44
(2009) 1607.
[11] F. Lebon, M. Ledecq, Z. Benatallah, S. Sicsic, R. Lapouyade, O. Kahn, A. Garcon,
M.R. Ravaux, F. Durant, J. Chem. Soc. Perkin Trans. 2 (1999) 795.
[12] F. Lebon, M. Ledecq, M. Dieu, C. Demazy, J. Remacle, R. Lapouyade, O. Kahn, F.
Durant, J. Inorg. Biochem. 86 (2001) 547.
[13] F. Lebon, E. de Rosny, M. Reboud-Ravaux, F. Durant, Eur. J. Med. Chem. 33
(1998) 733.
[14] A. Mishra, N.K. Kaushik, A.K. Verma, R. Gupta, Eur. J. Med. Chem. 43 (2008)
21892196.
[15] S. Ebrahimi, M. Mahdavi, S. Emami, M. Saeedi, M. Asadi, L. Firoozpour, M.
Khoobi, K. Divsalar, A. Shaee, A. Foroumadi, Syn. Commun. 44 (2014) 665.
[16] J. Dharmaraja, T. Esakkidurai, P. Subbaraj, S. Shobana, Spectrochim. Acta A 114
(2013) 607.
[17] S. Chandra, S. Raizada, M. Tyagi, P. Sharma, Spectrochim. Acta A 69 (2008) 816.
[18] M.A.D. Becke, Phys. Rev. A 38 (1988) 3098.
[19] C. Lee, W. Yang, R.G. Parr, Phys. Rev. B 37 (1988) 785.
[20] S.H. Vosko, L. Wilk, M. Nusair, Can. J. Chem. 58 (1980) 1200.
[21] M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E. Scuseria, M.A. Robb, J.R. Cheeseman,
G. Scalmani, V. Barone, B. Mennucci, G.A. Petersson, H. Nakatsuji, M. Caricato,
X. Li, H.P. Hratchian, A.F. Izmaylov, J. Bloino, G. Zheng, J.L. Sonnenberg, M.
Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y.
Honda, O. Kitao, H. Nakai, T. Vreven, J.A. Montgomery, Jr., J.E. Peralta, F. Ogliaro,
M. Bearpark, J.J. Heyd, E. Brothers, K.N. Kudin, V.N. Staroverov, R. Kobayashi, J.
Normand, K. Raghavachari, A. Rendell, J.C. Burant, S.S. Iyengar, J. Tomasi, M.
Cossi, N. Rega, J.M. Millam, M. Klene, J.E. Knox, J.B. Cross, V. Bakken, C. Adamo,
J. Jaramillo, R. Gomperts, R.E. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C.
Pomelli, J.W. Ochterski, R.L. Martin, K. Morokuma, V.G. Zakrzewski, G.A. Voth,
P. Salvador, J.J. Dannenberg, S. Dapprich, A.D. Daniels, O. Farkas, J.B. Foresman,
J.V. Ortiz, J. Cioslowski, D.J. Fox, Gaussian Inc, Wallingford CT, 2009.
[22] F. Weinhold, J.E. Carpenter, The Structure of Small Molecules and Ions, Plenum,
New York, 1988. p. 227.
[23] M. Tyagi, S. Chandra, P. Tyagi, Spectrochim. Acta A 117 (2014) 1.
[24] K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination
Compounds, Wiley, New York, 1986.
[25] M.A. Neelakantan, F. Russal Raj, J. Dharmaraja, J. Johnsonraja, T. Jeyakumar, M.
Sankaranarayana Pillai, Spectrochim. Acta A 71 (2008) 1599.
[26] G.G. Mohamed, M.M. Omar, A.M. Hindy, Turk. J. Chem. 30 (2006) 361.
[27] S. Chandra, Ruchi, K. Qanungo, S.K. Sharma, Spectrochim. Acta A 79 (2011)
1326.
[28] M.A. Neelakantan, F. Rusalraj, J. Dharmaraja, S. Johnsonraja, T. Jeyakumar, M.
Sankaranarayana Pillai, Spectrochim. Acta A 71 (2008) 1599.
[29] M. Tyagi, S. Chandra, A. Akhtar, D. Chand, Spectrochim. Acta A 118 (2014)
1056.