JOURNAL OF RARE EARTHS, Vol. 31, No. 10, Oct. 2013, P.

1009

Synthesis, characterization, cytotoxicity, DNA cleavage and antimicrobial

activity of homodinuclear lanthanide complexes of phenylthioacetic acid
T. F. Abbs Fen Reji1,*, A. Jeena Pearl2, Bojaxa A. Rosy3
(1. Department of Chemistry & Research Centre, Nesamony Memorial Christian College, Marthandam 629165, Tamilnadu, India; 2. Department of Chemistry
& Research Centre, Scott Christian College, Nagercoil 629003, Tamilnadu, India; 3. Department of Botany & Research Centre, Holy Cross College (Autono-
mous), Nagercoil 629004, Tamilnadu, India)

Received 15 November 2012; revised 25 July 2013

Abstract: Lanthanide complexes of Eu(III), Gd(III), Nd(III), Sm(III), and Tb(III) with phenylthioacetic acid were synthesized and
characterized by elemental analysis, mass, infrared radiation (IR), electronic spectra, molar conductance, thermogravimetric analysis
(TGA), and powder X-ray diffraction (XRD). The results showed that the lanthanide complexes were homodinuclear in nature. The
two lanthanide ions were bridged by eight oxygen atoms from four carboxylate groups. Thermal decomposition profiles were consis-
tent with the proposed formulations. Powder XRD studies showed that all the complexes were amorphous in nature. Antimicrobial
studies indicated that these complexes exhibited more activity than the ligand itself. The DNA cleavage activity of the ligand and its
complexes were assayed on CT DNA using gel electrophoresis in the presence of H2O2. The result showed that the Eu(III) and Nd(III)
complexes completely cleaved the DNA. The anticancer activities of the complexes were also studied towards human cervical cancer
cell line (HeLa) and colon cancer cells (HCT116) and it was found that the Eu(III) and Nd(III) complexes were more active than the
corresponding Gd(III), Sm(III), Tb(III) complexes and the free ligand on both the cancer cells.

Keywords: lanthanide complexes; phenylthioacetic acid; antimicrobial; DNA cleavage; anticancer; rare earths

Inner transition metal complexes attract considerable
interest in bioinorganic and coordination chemistry[1,2].
Some of the lanthanide complexes are used in biomedi-
cal analysis as magnetio resonance imaging (MRI) con-
trast agents[3] and also as effective catalysts for the hy-
drolytic cleavage of phosphate ester bonds[4]. Lanthanide
complexes with organic ligands have a great interest, not
only because owing to their structures, but also of poten-
tial applications of their luminescent properties[5–9].
These complexes have good physical and chemical
properties as well as anti-inflammation, antitumor, and
antithrombogenic properties because of their electron
configuration[11–12]. Because of special, photophysical
and biological properties, lanthanide complexes are used
as biological probes in the areas of clinical chemistry and
molecular biology[13]. Some lanthanide complexes have a
potential role in the treatment of tumor cell lines[14]. Be-
cause of their special electronic configuration, lanthanide
complexes have inspired many efforts on the design and
synthesis as potential anticancer and antibacterial
agents[15–24]. The lanthanide complexes have an ability to
interact with DNA directly or prevent the proper relaxa-
tion of DNA through the inhibition of topoisom-
erases[25,26]. Recently, aromatic carboxylate coordination
complexes that exhibit unique photophysical properties
and intriguing structural features have attracted consid-
erable interest[27,28]. Potential applications and fascinating
properties of lanthanide complexes with carboxylic acids
mooted us to synthesize and characterize a new series of
lanthanide complexes with phenylthioacetic acid ligand
and study their biological activity.
1 Experimental
1.1 Materials
Thiophenol and 2-chloroacetic acid were purchased
from Sigma-Aldrich. The human cervical cancer cell line
(HeLa) and colon cancer cells (HCT116) were obtained
from National Centre for Cell Science (NCCS), Pune,
India. The lanthanide nitrate salts were purchased from
Sigma-Aldrich and Merck. All other reagents and sol-
vents were obtained from commercial sources and were of
analytical grade. The ligand phenylthioacetic acid (PTPA)
was prepared according to the literature method[29].
1.2 Synthesis of the metal complexes
The ligand (PTPA) (3 mmol) in 20 mL of water was
taken in a 100 mL round botton flask. A solution of
NaOH (3 mmol) in 10 mL of water, was then added and
stirred well until the ligand completely dissolved. The
metal nitrate (1 mmol) in 10 mL of water was added
dropwise to the flask and the reaction mixture was stirred

* Corresponding author: T.F. Abbs Fen Reji (E-mail: abbsfen@gmail.com; Tel.: 04651272059)
DOI: 10.1016/S1002-0721(12)60395-0
1010
for 5 h. The precipitate formed was filtered off, washed
several times with water and with a little cold chloroform,
and then dried in vacuo over anhydrous CaCl2. The yield
was found to be 62%–68%.
1.3 Physical measurements
Elemental analysis was done using a Perkin-Elmer
elemental analyzer. The metal contents in the complexes
were determined by standard EDTA titration using xy-
lenol-orange as an indicator[30]. Molar conductance of the
complexes was measured in DMF (10–3 mol/L) solutions
using a Coronation Digital Conductivity Meter. The
mass spectra were recorded on a JEOL JMS600H mass
spectrometer. IR (KBr) spectra were recorded on a
JASCO FT/IR-410 spectrometer in the 4000–400 cm–1 re-
gion. The electronic spectra were recorded on a Perkin
Elmer Lambda-25 UV-VIS spectrometer. Thermal analy-
sis was carried out on SDT Q 600/V8.3 build 101 thermal
analyzer with a heating rate of 20 ºC/min using nitrogen
atmosphere. Powder XRD was recorded on a Rigaku
Dmax X-ray diffractometer with Cu K radiation.
1.4 Antimicrobial activities
Antibacterial and antifungal properties of the ligand
and its complexes were tested in vitro against the bacte-
rial species Escherichia coli, Bacillus subtilis, Pseudo-
monas aeruginosa, and Staphylococcus aureus; fungal
species, Aspergillus niger, Aspergillus flavus, and Can-
dida albicans by the disc diffusion method. Amikacin,
Ofloxacin, and Ciprofloxacin were used as standards for
antibacterial activity and Nystatin was used as a standard
for antifungal activity. The test organisms were grown on
nutrient agar medium in petri plates. The compounds were
prepared in DMSO and soaked in filter paper disc of 5 mm
in diameter and 1 mm thick. The discs were placed on the
previously seeded plates and incubated at 37 ºC and the
diameter of inhibition zone around each disc was meas-
ured after 24 h for antibacterial and 72 h for antifungal ac-
tivities. The minimum inhibitory concentration (MIC) was
determined by ‘serial dilution technique’[31].
1.5 DNA cleavage analysis
A solution of CT DNA in 0.5 mmol/L NaCl/5 mmol/L
tris-HCl (pH 7.0) gave a ratio of UV absorbance in the
range of 1.8–1.9 at 260 and 280 nm (A260/A280), indi-
cating that the DNA was sufficiently free of proteins[32].
Cleavage reactions were run between the metal com-
plexes and DNA, and the solutions were diluted with
loading dye using 1% agarose gel. Then 3 mL of
ethidium bromide (0.5 mg/mL) was added to the above
solution and mixed well. The warmed agarose was
poured and clamped immediately with a comb to form
sample wells. The gel was mounted onto an electropho-
retic tank and enough electrophoretic buffers were added
to cover the gel to a depth of about 1 mm. The DNA
JOURNAL OF RARE EARTHS, Vol. 31, No. 10, Oct. 2013
sample (30 mmol/L), 50 mmol/L metal complex, and
500 mmol/L H2O2 in 50 mmol/L tris-HCl buffer (pH 7.1)
were mixed with loading dye and loaded into the well of
the submerged gel using a micropipette. Electric current
(50 mA) was passed into running buffer. After 1–2 h, the
gel was taken from the buffer. After electrophoresis, the
gel was photographed under a UV transilluminator (280
nm) and documented.
1.6 In vitro anti cancer activity
The human cervical cancer cell line (HeLa) and colon
cancer cells (HCT116) were grown in Eagle’s minimum
essential medium (EMEM) containing 10% fetal bovine
serum (FBS). The cells were maintained at 37 ºC, 5%
CO2, 95% air, and 100% relative humidity. Maintenance
cultures were passed weekly, and the culture medium
was changed twice a week. The monolayer cells were
detached with trypsin-ethylenediaminetetraacetic acid
(EDTA) to make single cell suspension and viable cells
were counted using a hemocytometer and diluted with a
medium containing 5% FBS to give a final density of
1×105 cells/mL. One hundred microlitres per well of cell
suspension were seeded into 96-well plates at a plating
density of 10000 cells/well and incubated to allow for
cell attachment at 37 ºC, 5% CO2, 95% air and 100%
relative humidity. After 24 h, the cells were treated with
serial concentrations of the test samples. They were ini-
tially dissolved in neat dimethylsulfoxide (DMSO) to
prepare the stock (200 mmol/L) and stored frozen prior
to use. At the time of sample addition, an aliquot of fro-
zen concentrate was thawed and diluted to twice the de-
sired final maximum test concentration with serum free
medium. Additional three, 2 fold serial dilutions were
made to provide a total of five sample concentrations.
Aliquots of 100 μL of these different sample dilutions
were added to the appropriate wells already containing
100 μL of medium, resulting in the required final sample
concentrations. Following sample addition, the plates
were incubated for an additional 48 h at 37 ºC, 5% CO2,
95% air, and 100% relative humidity. The medium
without samples served as control and a triplicate was
maintained for all concentrations[33].
1.7 MTT assay
MTT is a yellow water soluble tetrazolium salt
[(3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl-tetrazolium
bromide)]. Succinate-dehydrogenase, a mitochondrial
enzyme in living cells cleaves the tetrazolium ring, con-
verting the MTT to an insoluble purple formazan. Thus,
the amount of formazan produced is directly proportional
to the number of viable cells. After 48 h of incubation, 15
μL of MTT (5 mg/mL) in phosphate buffered saline
(PBS) was added to each well and incubated at 37 ºC for
4 h. The medium with MTT was then flicked off and
formazan crystals obtained were solubilized in 100 μL of
T.F. Abbs Fen Reji et al., Synthesis, characterization, cytotoxicity, DNA cleavage and antimicrobial activity of … 1011

DMSO. The absorbance at 570 nm was measured using a 2.2 IR spectra

micro plate reader[34]. The cell inhibition percentage was
determined using the following formula.
cell inhibition percentage=
100–[Abs (sample)/Abs (control)]×100 (1)
Nonlinear regression graph was plotted between %
cell inhibition and log10 concentration and IC50 was de-
termined using GraphPad Prism software.
2 Results and discussion
2.1 Characterization of metal complexes
The analytical and physical characterization of Ln(III)-
PTAA complexes are given in Table 1. The analytical
data show that the metal to ligand ratio is 1:3 in all the
complex systems. And also all the complexes are
homodinuclear in nature. The composition of the com-
plexes is [Ln2L6(H2O)4], where L is the phenylthioacetic
acid ligand (PTAA). The Eu(III), Gd(III), Nd(III), Sm(III),
and Tb(III) complexes are soluble in THF and DMSO.
The mass spectra of the Eu(III), Gd(III), Nd(III), Sm(III),
and Tb(III) complexes show molecular ion peaks at m/z
1381 (M+1, 18%); 1391 (M+1, 14%); 1359 (M+1, 17%),
1379 (M+1, 15%); 1393 (M+1, 16%)], respectively,
which coincide with the formula weights of the lantha-
nide complexes. The mass spectrum of Gd(III) complex
is shown in Fig. 1. The low molar conductance values
(Table 1) of the metal complexes reveal their non-elec-
trolytic nature[35].
The important IR (KBr) spectral data are given in Ta-
ble 2. The band at 1707 cm–1 for the carboxylate group of
free ligand shifted to lower frequency in the range of
~1559–1583 cm–1 in the complexes is indicative of the
coordination of the carboxylate oxygen atom to the metal
ion. On complexation, the asymmetric and symmetric
stretching bands of carboxylato groups are shifted to
lower frequency for all the complexes, which reveals the
formation of a linkage between the metal ion and car-
boxylato oxygen atom. Moreover, the difference (<150
cm–1) between the asymmetric and symmetric stretching
modes indicates the bidentate binding of the carboxylato
group in the complexes[36]. The carboxylate stretching
frequency spectra is little broad because of the three dif-
ferent modes of coordination of the ligand to the lantha-
nide ions[37]. The new broad band that appeared at ~3400
cm–1 can be attributed to the stretching vibration of the
coordinated water molecules. The spectrum of all the
metal complexes show new bands in 472–475 cm–1 re-
gion, which may probably be due to the formation of
M–O bonds[35].
2.3 Electronic spectra
The UV absorption spectra of the free ligand and the
corresponding lanthanide complexes were measured in
THF solution (c=1×10–4 mol/L) and are shown in Fig. 2.
The spectrum displayed an absorption maximum at 248 nm
for the free ligand, which is attributable to singlet- singlet

Table 1 Analytical and physical data of the ligand (PTAA) (L) and its complexes
Melting point/ Elemental analysis Found (calcd) (%) c max/
Compound Empirical formula Yield
ºC C H S M (/cm2mol–1) nm
PTAA (L) C8H8O2S 142–144 72 56.40 (57.12) 4.23 (4.79) 18.42 (19.06) – 248
[Eu2L6(H2O)4] C48H56O16S6Eu2 184–186 63 40.68 (41.62) 4.65 (4.07) 12.98 (13.89) 20.89 (21.94) 3.1 253
[Gd2L6(H2O)4] C48H56O16S6Gd2 208–210 61 40.85 (41.30) 4.46 (4.04) 14.14 (13.78) 21.69 (22.53) 2.6 256
[Nd2L6(H2O)4] C48H56O16S6Nd2 187–190 62 41.42 (42.09) 4.52 (4.12) 13.87 (14.04) 21.85 (21.06) 2.8 254
[Sm2L6(H2O)4] C48H56O16S6Sm2 178–180 66 42.26 (41.71) 4.39 (4.08) 13.18 (13.92) 21.06 (21.76) 3.4 252
[Tb2L6(H2O)4] C48H56O16S6Tb2 192–195 64 41.83 (41.20) 4.78 (4.03) 12.95 (13.75) 23.12 (22.72) 2.8 254

Table 2 IR spectral data of the Schiff base ligand (PTAA)

(L) and its complexes (cm–1)
Compound asym.(COO–) sym.(COO–) (H2O) (M–O)
PTAA (L) 1707 1425 – –
[Eu2L6(H2O)4] 1569 1420 3445(b) 473
[Gd2L6(H2O)4] 1583 1427 3421(b) 475
[Nd2L6(H2O)4] 1562 1426 3436(b) 472
[Sm2L6(H2O)4] 1559 1424 3429(b) 474
[Tb2L6(H2O)4] 1565 1422 3437(b) 475

–* absorption of the aromatic ring. The max value of

the Eu(III), Gd(III), Nd(III), Sm(III), and Tb(III) com-
plexes are 253, 256, 254, 252, 254 nm respectively (Ta-
Fig. 1 Mass spectrum of Gd(III) complex ble 1) which slightly red-shifted with respect to that of
1012
Fig. 2 UV absorption spectra in THF (c=1×10–4 mol/L)
the free ligand (248 nm). The UV bands of the lanthanide
complexes spectra are similar to that of the free ligand,
suggesting that the coordination of the lanthanide ion
does not have a significant effect on the –* transition.
The molar absorption coefficient value for the complexes
are about six times than that of the free ligand, which in-
dicats the presence of six PTAA molecules in the
homodinuclear lanthanide complexes[37].
2.4 Thermal analysis
The thermal stability data of the complexes are listed
in Table 3. The [Eu 2 L 6 (H 2 O) 4 ], [Gd 2 L 6 (H 2 O) 4 ],
[Nd2L6(H2O)4], [Sm2L6(H2O)4], and [Tb2L6(H2O)4] com-
plexes undergo the same type of decompositions mainly
in two stages. The first stage taking place in the 115–170
ºC range corresponds to the dehydration of four coordi-
nated water molecules. The final decomposition step is
represented by the total removal of the organic ligand
moiety in the 380–630 ºC range with the formation of the
corresponding metal oxide as the final product. The TG
curve of the complex [Eu2L6(H2O)4] shows a mass loss
of 6.2% (calculated, 5.2%) in the temperature range of
125–150 ºC. This is due to the loss of four coordinated
water molecules. The second decomposition step of the
complex is in the temperature range of 395–55 ºC bring-
ing a mass loss of 67.6 (calculated, 69.5%) which corre-
lates with the loss of coordinated organic ligand. Above
Table 3 Thrmogravimetric data of lanthanide complexes
Complex Temperature range T/ºC Mass loss Obs.(calcd) (%)
[Eu2L6(H2O)4] 125–150, 395–575, >600 6.2(5.2), 67.6(69.5), 26.2(25.3)
[Gd2L6(H2O)4] 115–150, 380–510, >550 6.4(5.1), 67.1(69.0), 26.5(25.9)
[Nd2L6(H2O)4] 130–170, 400–610, >610 6.7(5.2), 67.5(72.2), 25.8(24.6)
[Sm2L6(H2O)4] 120–170, 410–600, >600 6.1(5.2), 67.3(69.7), 26.6(25.1)
[Tb2L6(H2O)4] 115–145, 450–630, >650 6.2(5.1), 66,4(68.8), 27.4(26.1)
JOURNAL OF RARE EARTHS, Vol. 31, No. 10, Oct. 2013
this temperature, a horizontal thermal curve has been
observed due to the formation of the metal oxide. The
TG curves of the complexes [Gd2L6(H2O)4] shows a
mass loss of 6.4% (calculated, 5.1%) in the temperature
range 115–150 ºC showing the elimination of four coor-
dinated water molecules. The second mass loss of 67.1%
(calculated, 69.0%) in the 380–510 ºC corresponds to the
coordinated organic ligand. Above this temperature, a
horizontal curve has been observed due to the formation
of a metal oxide. The complexes [Nd2L6(H2O)4] and
[Sm2L6(H2O)4] show a similar trend of two decomposi-
tion steps. The first stage taking place in the 120–170 ºC
range is attributed to the expulsion of four coordinated
water molecules. The second stage starts from 400 to 610
ºC for [Nd2L6(H2O)4] and from 410 to 600 ºC for
[Sm2L6(H2O)4] complexes. The corresponding mass loss
is due to the decomposition of the organic ligand mole-
cule and it is in agreement with the calculated mass loss.
The final residue is qualitatively proved to be anhydrous
metal oxides. The first step takes place in the temperature
range of 115–145 ºC for [Tb2L6(H2O)4] complex. The
second stage starts from 450 to 630 ºC, corresponding to
the loss of organic ligand. Above this temperature a hori-
zontal thermal curve has been observed due to the forma-
tion of the metal oxide. Based on the above studies, the
proposed structure of the metal complex is shown in Fig.
3. This type of structures has been reported previously[38].
2.5 Powder XRD
Powder XRD patterns of the Eu(III), Gd(III), Nd(III),
Sm(III), and Tb(III) complexes were recorded over the
2=0º–80º range. There were no well defined crystalline
peaks in the spectra. From this, it is observed that all
these complexes are amorphous in nature.
3 Biological studies
3.1 Antimicrobial activity
The results of the antimicrobial activities are summa-
rized in Table 4. The standard error for the experiment is
±0.001 cm and the experiment was repeated three times
under similar conditions. DMSO was used as a negative
control and amikacin, ofloxacin, and ciprofloxacin were
used as positive standards for antibacterial studies. Nys-
tatin was used as a reference for antifungal studies. These
Process
–4H2O (coord), loss of organic moiety, Eu2O3
–4H2O (coord), loss of organic moiety, Gd2O3
–4H2O (coord), loss of organic moiety, Nd2O3
–4H2O (coord), loss of organic moiety, Sm2O3
–4H2O (coord), loss of organic moiety, Tb2O3
T.F. Abbs Fen Reji et al., Synthesis, characterization, cytotoxicity, DNA cleavage and antimicrobial activity of … 1013

Table 4 In vitro antimicrobial activity (MIC, μg/mL) of the compounds and standard reagents
Bacterial species Fungal species
Compound
E. coli B. subtilis P. aeruginosa S. aureus A. niger A. flavus C. albicans
PTAA (L) 16 64 53 71 31 59 78
[Eu2L6(H2O)4] 10 32 11 25 21 25 12
[Gd2L6(H2O)4 13 15 10 19 31 15 13
[Nd2L6(H2O)4] 06 08 15 13 12 14 06
[Sm2L6(H2O)4] >100 47 21 53 61 88 72
[Tb2L6(H2O)4] 58 42 38 >100 >100 65 68
a
Amikacin 05 06 05 07 – – –
Ciprofloxacinb 04 05 05 05 – – –
Ofloxacinc 10 04 04 05 – – –
Nystatind – – – – 07 05 05
a, b, c, d
Standard

dipole moment that are affected by the presence of metal

ions may also be the possible reasons for increasing the
biological activity of the metal complexes as compared
to the ligand from which they are derived[40].

3.2 DNA cleavage analysis

Fig. 3 Proposed structure of Ln(III)-PTPA complexes
compounds exhibit moderate to strong antimicrobial ac-
tivity. Comparatively a better activity is found for the
bacteria rather than the fungi. The Nd(III) complex ex-
hibits a higher activity than the other metal complexes
towards fungal species. The Nd(II) complex shows a
good activity, especially against the gram-negative bac-
teria such as E. coli. and B. subtilis. The Nd(II) complex
shows equal or better activity compared to the negative
controls such as amikacin, ofloxacin, and ciprofloxacin.
The Eu(III) and Gd(III) complexes display moderate ac-
tivity against the bacteria. The antimicrobial activity of
the complexes is greater than those of the free ligand, this
indicates that the complexation to metal enhances the ac-
tivity of the ligand. This is explained on the basis of
Overtone’s concept and chelation theory[39]. Chelation
tends to make the ligand a more powerful and potent
bacterial agent. A possible explanation for this increase
in the activity upon chelation is that, in a chelated com-
plex, the positive charge of the metal is partially shared
with donor atoms present in the ligands and there is an
electron delocalization over the whole chelated ring.
Generally, it is suggested that the chelated complexes
deactivate various cellular enzymes, which play a vital
role in various metabolic pathways of these microorgan-
isms. Other factors such as solubility, conductivity, and
Gel electrophoresis experiment using CT DNA was
performed with the ligand and its complexes in the pres-
ence and absence of H2O2 as an oxidant. The results (Fig.
4) indicate that all the complexes could interact with CT
DNA in the presence of H2O2. Eu(III) and Nd(III) com-
plexes cleave DNA completely compared to other sys-
tems. The lanthanide complexes seem to catalyze the
generation of highly reactive hydroxyl radicals from
H2O2. These hydroxyl radicals participate in the oxida-
tion of the deoxyribose moiety, followed by the hydro-
lytic cleavage of the sugar-phosphate backbone. Gd(III),
Sm(III) and Tb(III) complexes partially cleave the DNA.
It is observed that most cleavage cases are due to the
metal ions reacting with H2O2 to produce diffusible hy-
droxyl radicals or molecular oxygen, which may damage
DNA through a Fenton type chemistry[41]. In addition,
the nuclease activity of the complexes has also been in-
Fig. 4 DNA cleavage studies of ligand and its metal complexes
(M–Marker, C–Control CT DNA (untreated sample), S1–
Ligand (L)+DNA, S2–[Eu2L6(H2O)4]+DNA, S3–[Gd2L6(H2O)4]
+DNA, S4–[Nd2L6(H2O)4]+DNA, S5–[Sm2L6(H2O)4]+DNA,
S6–[Tb2L6(H2O)4]+DNA)
1014
vestigated in the absence of the oxidant H2O2. This ex-
periment did not help cleaving the DNA, thus confirming
the involvement of hydroxyl radicals in the cleavage
process.
3.3 In vitro anti-cancer activity
The reliable criteria for judging the efficacy of any
anticancer drug are prolongation of life span, improving
the clinical, haematological, biochemical profile, and re-
duction in viable tumour cell count in the host[42]. In or-
der to evaluate the biological effects of the ligand, PTAA
and its Eu(III), Gd(III), Nd(III), Sm(III), and Tb(III)
complexes on cancer cells, we used the compounds to
treat HeLa (human cervical cancer cells) and HCT116
(colon cancer cells) at the concentrations of 6.25, 12.5,
25, 50, and 100 mol/L for 48 h (Figs. 5(a) and (b)). The
untreated cells were used as a control. Cell growth inhi-
bition was analyzed by MTT assay and the results
showed that the complexes and the ligand exhibited an
inhibitory effect on the proliferation of HeLa and
HCT116 cells in a dose-dependent manner (Table 5).
Among them, Eu(III) and Nd(III) complexes showed the
most potent inhibitory effect on the growth of both the
cells compared to the Gd(III), Sm(III), and Tb(III) com-
plexes and the free ligand. Values for Eu(III), Gd(III),
Nd(III), Sm(III), and Tb(III) complexes for HeLa cancer
cells are better than some previously reported values[43].
The IC50 values for our metal complexes and the free
ligand against HCT116 cancer cells show moderate ac-
tivity compared to the IC50 value of the clinically used
drug such as etoposide (29.6 mol/L)[44]. The activity of
the metal complexes and the free ligand towards HeLa
cancer cells are not much significant, compared to the
known metal-free anticancer agents such as estramustine
Fig. 5 Growth inhibition based on concentration (HeLa) (a) and
based on concentration (HCT116) (b)
JOURNAL OF RARE EARTHS, Vol. 31, No. 10, Oct. 2013
Table 5 IC50 values of the compounds on the cancer cells
IC50 (μmol/L)
Compound
HeLa HCT116
PTPA (L) 60.71 56.66
[Eu2L6(H2O)4] 47.91 45.53
[Gd2L6(H2O)4] >100 52.65
[Nd2L6(H2O)4] 43.83 28.33
[Sm2L6(H2O)4] 98.63 87.72
[Tb2L6(H2O)4] >100 77.52
(IC50, ~1.5 to 3.0 mol/L)[45], noscapine (IC50, ~22
mol/L)[46] as well as metal-bound anticancer reagents
such as cisplatin (IC50, ~8 mol/L)[47]. From the IC50
values of Eu(III) and Nd(III) complexes on both the
cancer cells, it is understood that these complexes are
more active on HCT116 cancer cells than on the HeLa
cancer cells.
4 Conclusions
Eu(III), Gd(III), Nd(III), Sm(III), and Tb(III) com-
plexes with the phenylthioacetic acid ligand were syn-
thesized and characterized by elemental analysis, mass,
IR, electronic spectra, molar conductance, TGA, and
powder XRD. From the IR data, the coordination of the
ligand to the metal atom was found to be bidentate. A
two-stage process was shown in the thermogravimetric
spectra of all the complexes. Powder XRD results
showed that the complexes were amorphous in nature.
The antimicrobial studies revealed that the complexes
showed higher activity than the ligand. The Nd(III) com-
plex showed better activity against gram negative bacte-
ria such as E-coli compared to the other complexes and
the free ligand. DNA cleavage studies indicated that the
Eu(III) and Nd(III) complexes had completely cleaved
the DNA. In vitro anticancer activity was not significant
compared to the known anticancer agents such as estra-
mustine, noscapine, and cisplatin[48]. The Eu(III) and
Nd(III) complexes were more active than the other three
complexes and the free ligand on both the cancer cells
(HeLa and HCT116).
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