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Journal of Analytical and Applied Pyrolysis 117 (2016) 1724

Contents lists available at ScienceDirect

Journal of Analytical and Applied Pyrolysis


journal homepage: www.elsevier.com/locate/jaap

Thermal and spectroscopic characterization, antioxidant evaluation


and pyrolysis of losartan with some bivalent metals
J.A. Teixeira a , A.B. Siqueira b,
a
b

Universidade Federal de Mato Grosso, Campus CuiabMT, CEP 78060-900, Brazil


Universidade Federal de Mato Grosso, Campus Vrzea GrandeMT, CEP 78156-105, Brazil

a r t i c l e

i n f o

Article history:
Received 17 November 2015
Received in revised form
26 December 2015
Accepted 29 December 2015
Available online 2 January 2016
Keywords:
Bivalent metals
Losartan
Evolved gas

a b s t r a c t
Solid state M-Los compounds, where M stands for bivalent Mn, Fe, Co, Ni, Cu or Zn and
Los is losartan. The materials were characterized by Fourier transform infrared spectroscopy
(FTIR), simultaneous termogravimetrydifferential scanning calorimetry (TGDSC), simultaneous
termogravimetrydifferential scanning calorimetry coupled with Fourier transform infrared spectroscopy (TG/DSCFTIR) and evaluating antioxidant activity with DPPH. The results can be to inform
the thermal behaviour, hydration, stoichiometric relationship, metal-ligand interaction, antioxidant
capacity and released gases during of the thermal decomposition of compounds. The thermal behavior of the compound showed similar thermal behavior in air atmosphere and nitrogen atmosphere. The
gaseous products released under dry air and nitrogen atmospheres were CO, CO2 , NH3 , CH3 NH2 , NO
and H2 O, CO, NH3 , CH3 NH2 , HCN, respectively. The DPPH test indicated that the scavenging free radicals
from MnLos2 4H2 O and HLos were c.a. 20% higher than the others compounds. These results indicate
MnLos2 . 4H2 O to others investigations as toxicological and pharmacological.
2015 Elsevier B.V. All rights reserved.

1. Introduction
Various applications have been reported in the literature about
association of drugs with organic and inorganic compounds. The
studies and development of news drugs are important to new treatment of diseases and production of cheaper drugs [1].
The
potassium
losartan
(Los)
(Potassium
salt
of
2-butyl-4-chloro-1-{[2-(1H-tetrazol-5-yl)biphenyl-4-yl]methyl}1H-imidazol-5-yl)methanol) is a relatively cheap antihypertensive
drug and it has free distribution in Brazil, according with Ordinance
971 of May 15, 2012 [2]. Although Los is effective in the treatment
of hypertension, it has low oral bioavailability and short half-life
(high clearance).
Studies of the association of phenol with Los showed that
the compound Los/phenol have antioxidant activity 30% increase,
when compared with Los alone. The Los/chlorhexidine showed
greater antimicrobial activity against Enterococcus faecalis than the
chlorhexidine, this association and others, as Los/chitosan/guar
gum were also studied as drug-delivery systems [35].

Corresponding author.
E-mail address: buzutti7@hotmail.com (A.B. Siqueira).
http://dx.doi.org/10.1016/j.jaap.2015.12.023
0165-2370/ 2015 Elsevier B.V. All rights reserved.

Los contains functional groups capable to bind a metal ion,


forming stable complexes. Pharmacological point of view, part of
the effect of medications could be connected with complexation
of metal ions and changes in homeostasis, this evaluation can
be carried out by free radical scavenging activity by 1,1-diphenyl
picrylhydrazyl (DPPH) [1,6]. The preparation and investigation of
several metal complexes with Los and Los alone have also been
investigated using thermoanalytical techniques, X-ray diffractometry, optical and infrared spectroscopy, elemental analysis and
biological or pharmaceutical activity [38]. The published papers
are concerned with elucidating of the possible structure polymorphic forms of Los [7], Los-Cu(II) complexes used for controlled drug
release [8], complexes [Cu(Los)2 (H2 O)3 ]2 has displayed a moderately superoxidedismutase activity, as deleterious agent when
tested on the tumoral osteoblasts (UMR106) [6] and positronium
formation in solid transition of Mn, Fe, Co, Ni, Zn with Los [9].
The literature does not report anything about thermoanalytical
studies under conditions of pyrolysis of losartan with Mn, Fe, Co,
Ni, Cu and Zn ions. Moreover, evolved gas analysis (EGA) allows for
a greater understanding of the mechanisms of pyrolysis because
these techniques are fast and highly sensitive in detecting organic
volatile matter [10].

18

J.A. Teixeira, A.B. Siqueira / Journal of Analytical and Applied Pyrolysis 117 (2016) 1724

The aim of the current work was to prepare, characterize


and evaluating antioxidant activity the association between
losartan and the metal ion Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and
Zn(II) to news applications. The compounds were investigated by
means of infrared spectroscopy, X-ray powder diffractometry,
simultaneous thermogravimetry and differential scanning
calorimetry (TGDSC), simultaneous thermogravimetry and differential scanning calorimetry coupled with infrared spectroscopy
(TGDSC coupled FTIR) and other methods of analysis.

mation of the respective oxides, as the nal residue has known


stoichiometry [1].
The EGA (TG-FTIR) experiments were perfomed using thermogravimetric analyzer (TGDSC 1) coupled to a FTIR spectrophotometer Nicolet, with a gas cell and DTGS KBr detector. The furnace
and the heated gas cell (523 K) were coupled through a heated
(T = 498 K) 120 cm stainless steel line transfer with diameter of
3 mm. The compounds were analyzed under the same conditions
of simultaneous TGDSC, using mass c.a.10 mg of samples.

2. Experimental

2.4. Determination of the reducing activity of the stable radical


1,1-diphenyl picrylhydrazyl (DPPH) [1]

2.1. Reagents
Potassium losartan (Los) was obtained from Pharmanostra Company, and it was used as received. The metal
ion were used from the chlorides (MnCl2 4H2 O/Isofar,
NiCl2 6H2 O/Vetec, CoCl2 6H2 O/Vetec, CuCl2 /Vetec) and sulfates (Zn(SO4 )2 7H2 O/Vetec, Fe(SO4 )2 7H2 O/Synth), they were
used as received.

The solution of DPPH in methanol (40 g L1 ) was prepared


daily; 1.0 mL of this solution was mixed with 2.5 mL of methanolic
solutions of H-Los, Los and metal-ligand at different concentrations (50.0, 100.0 and 150.0 g L1 ). After 30 min with continuous
stirring at room temperature, the absorbance was recorded at
515 nm on a UVvis spectrophotometer (Bel Photonics 2000 UV).
The absorbance lectures were obtained in triplicate.

2.2. Synthesis

3. Results and discussion

The losartan acid (H-Los) was obtained by addition of hydrochloric acid (HCl 0.5 mol L1 ) in Los solution until pH 1.0. The precipitate
formed was washed with distilled water until the chloride ions
were eliminated, ltered through on Whatman n 42 lter paper,
dried and kept in a desiccator over anhydrous calcium chloride.
The metal compounds in solid state were prepared with continuous stirring by slowly adding a solution of Los to the respective
metal chloride (Mn(II), Co(II) Ni(II) and CuII) or sulfate (Fe(II) and
Zn(II)) solutions. The precipitates were washed with distilled water
until the chloride or sulfate ions were eliminated, ltered through
on Whatman n 42 lter paper, dried and kept in a desiccator over
anhydrous calcium chloride.

3.1. TGDSC
The thermal stability of anhydrous compounds and nal temperature, in both atmospheres, occurs between 453 and 493 K and
9231073 K, respectively. The thermal stability of H-Los, M-Los
(M = Mn, Cu, Fe, Co, Ni, Cu or Zn) and Los were compared and Los
showed higher thermal stability due to strong interaction between
potassium ion and Los anion. The nal residues, in air atmospheres,
were Mn3 O4 , Fe2 O3 , Co3 O4 , NiO, CuO e ZnO to respectively metal
compounds and H-Los and K-Los were not obtained residues. The
volatilization of potassium (Los) probably occurs as chloride, suggesting reaction of chloro of the ligand with this metal ion during
the thermal decomposition. The qualitative test with silver nitrate
and mass values of TG curve of Los allow suggest the formation
of KCl as residue at 951 K (mTG = 84.46%; mcalcd . = 83.83%). DSC
curve of Los was observed a endothermic peak at 1043 K due to
KCl fusion. The exothermic peaks at 987 K and 1129 K were due to
oxidation of gases products evaporated, see Table 2 and Fig. 1.
In nitrogen atmosphere, the stable residues could not be formed
up to 1273 K due to presence of carbonaceous residues.

2.3. Characterization methods


The attenuate total reectance infrared spectra for H-Los, Los
and for its metal compounds were run on a Spectrum 100 FTIR spectrophotometer PerkinElmer, using ATR accessory diamond/ZnSe
window. The FTIR spectra were record with 16 scans per spectrum
at resolution of 4 cm1 .
Simultaneous TGDSC curves were obtained using a TGDSC 1
STARe system, from Mettler Toledo. The purge gases were dry nitrogen and air with ow of 60 mL min1 . A heating hate of 293 K min1
was adopted, with samples weighing about 7 mg. Alumina crucibles
were used for recording the TGDSC curves.
Carbon and hydrogen contents were determined by microanalytical procedures, with a CHN Elemental Analyzer from
PerkinElmer, model 2400 and by calculations based on the mass
losses observed in the TG curves, since the loss of hydration water
and the ligand during thermal decomposition occurs with the for-

4. Air atmosphere
The determination of Los purity was based on the assumption
that an impurity will depress the melting point of a pure material (To ) for which melting was characterized by a melting point
(Tf ) and an enthalpy of fusion (Hfus. ). The effect of an impurity
on To of the Los was determined by the DSC method based on
the Vant Hoff equation [1,11]. The obtained DSC curve exhibits
an endothermic event corresponding to the Los melting point at

Table 1
Analytical and thermoanalytical (TG*) data for M(Los)2 nH2 O compounds.
Compounds

Mn(Los)2 4H2 O
Fe(Los)2 2.5H2 O
Co(Los)2 3H2 O
Ni(Los)2 2.5H2 O
Cu(Los)2 2H2 O
Zn(Los)2 H2 O

M (oxide)/ %

Los (Lost)/ %

Water/ %

C/ %

Calcd

TG

Calcd.

TG

Calcd.

TG

Calcd.

EA

TG

Calcd.

EA

TG

Calcd.

EA

TG

7.86
8.49
8.39
7.89
8.43
8.79

7.93
8.13
8.30
8.05
7.51
9.33

84.72
86.74
85.96
87.36
87.75
89.28

84.73
86.85
85.74
87.21
88.44
88.78

7.42
4.77
5.65
4.75
3.82
1.94

7.35
5.02
5.96
4.74
4.05
1.89

54.44
55.94
55.23
55.77
56.02
57.00

54.25
55.28
55.85
55.23
55.87
56.62

54.22
56.17
55.29
55.68
56.02
56.59

17.31
17.79
17.57
17.74
17.82
18.13

17.15
17.54
17.82
17.48
17.81
17.85

17.28
17.60
17.72
17.51
17.82
17.61

5.40
5.23
5.27
5.22
5.14
5.00

5.41
5.31
5.07
5.01
5.11
5.11

5.38
5.25
5.27
5.20
5.13
4.96

M = bivalents metals *TG in air atmosphere, Los = Losartan, n = H2 O number.

N/ %

H/ %

Final Residue

Mn3 O4
Fe2 O3
CoO
NiO
CuO
ZnO

J.A. Teixeira, A.B. Siqueira / Journal of Analytical and Applied Pyrolysis 117 (2016) 1724

19

Table 2
Temperature ranges (), mass losses (m), and peak temperatures observed for each step of the TGDSC curves in air atmosphere of the compounds.
Compounds

Steps

Phase

First

Second

Third

Fourth

Fifth

(K)
m (%)
Peak (K)

459478
4.0
453 (endo)

478558
10.56
526 (exo)

558833
38.67

8331063
46.5
8321002 (exo)

(K)

558627
20.58
606 (exo)

62796
24.87

796974
40.72
893 (exo)

9741210
14.31
987 (exo)
1129 (exo)

Mn(Los)2 4H2 O (K)


m (%)
Peak (K)

358446
7.35
438 (endo)

490541
6.64
523 (exo)

541783
23.50
553613 (exo)
662694 (exo)

7831063
54.59
755 (exo)
878 (exo), 9051068 (exo)

Fe(Los)2 2.5H2 O (K)


m (%)
Peak (K)

313463
5.02
318411 (endo)

463549
6.50
523 (exo)

548939
80.35
624965 (exo)

Co(Los)2 3H2 O (K)


m (%)
Peak (K)

306460
5.96
306417 (endo)

460543
6.49
501543 (exo)

Ni(Los)2 2.5H2 O (K)


m (%)
Peak (K)

323481
4.74
333463

Cu(Los)2 2H2 O (K)


m (%)
Peak (K)

(K)
m (%)
Peak (K)

HLos

Los

m (%)
Peak (K)

Zn(Los)2 H2 O

Transition

453 (endo)

516 (endo)
54 7(endo)
1043 (endo)

543796
28.35
548594 (exo)
757 (exo)

796967
50.38
796974 (exo)

11601180
0.52
1170 (endo)

481556
6.55
515588 (exo)

556762
33.67
600640 (exo)
640698 (exo)
745 (exo)

762929
46.99
766939 (exo)

312459
4.05
313392 (endo)

459529
7.34
458498 (exo)
524 (exo), 533 (exo)

529647
12.19
555628 (exo)

647957
68.91
844 (exo)

313477
1.89
303423 (endo)

477560
6.70
536 (exo)

560863
28.80
598 (exo)
630760(exo), 792(exo)

8631070
53.28
8751070 (exo)

547 K (Hfus = +21.7 kJ mol1 ); the purity was found to be 99.5%,


indicating high purity of the material.

The fusion H-Los shows Tonset = 453 K but this event occurs concomitantly thermal decomposition, Tonset = 459 K, so it was not
possible to determine the purity of H-Los by DSC.

Fig. 1. Simultaneous TGDSC curves in dynamic dry air and nitrogen* atmospheres of the Los (a) (m(air) = 6.7958, m(N2) = 6.7530 mg) and HLos (b) (m(air) = 6.8280,
m(N2) = 7.0682 mg).

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J.A. Teixeira, A.B. Siqueira / Journal of Analytical and Applied Pyrolysis 117 (2016) 1724

Fig. 2. Simultaneous TGDSC curves of the synthesized compounds in dynamic dry air atmosphere of the synthesized compounds: (a) Mn(Los)2 4H2 O (7.1540 mg); (b)
Fe(Los)2 2.5H2 O (6.8500 mg); (c) Co(Los)2 3H2 O (6.7980 mg); (d) Ni(Los)2 2.5H2 O (6.8158 mg); (e) Cu(Los)2 2H2 O (7.1344 mg); (f) Zn(Los)2 H2 O (6.7950 mg).

The total mass losses of Los and H-Los were 100.48% and 99.73%
at four (Los) and ve (H-Los) consecutive steps, respectively, see
Table 2 and Fig. 1. The percentages indicated that the compounds
have not inorganic impurities in both compounds as well as the
volatization of potassium residue in Los compound.
The DSC curve of Los shows the polymorphic transition at 516 K
(polymorph I) and melting at 547 K as reported by literature [7,12].
The H-Los have not polymorphic transition during the heating
process due to hydrogen interactions between tetrazole ring. The
formation of hydrogen bonds hinder the twist of biphenyl rings
causing the transitions solid [7,13].
The hydrogen interactions between hydroxyl group and imidazole group [13] and TG curves values of (mTG = 20.58%;
mcalcd . = 20.62) indicate the output of these groups in the rst step
of thermal decomposition. The different interactions and reactions
solid-gas allowed not suggest the thermal decomposition mechanism of Los.
Carbon and hydrogen contents, degree of hydration, stoichiometric ratio between M-Los and the residues formed could be
determined by the TGDSC curves in an air atmosphere and
microanalytical procedures, see Table 1. The general formula
M(Los)2 nH2 O was established as stoichiometry ratio of these compounds, where M represents Mn(II), Fe (II), Co (II), Ni (II) Cu (II) or
Zn (II), Los is losartan and n = 4, 2.5, 3, 2.5, 2 and 1, respectively.

The TGDSC curves (Fig. 2) show which the thermal dehydration


of the compounds occurred in a single step at 358 K (Mn), 313 K (Fe),
306 K (Co), 323 K (Ni), 312 K (Cu) and 313 K (Zn). The Mn(Los)2 . 4H2 O
compound showed greater amount of hydrated water, yet he had
the higher temperature of thermal dehydration, and an endothermic peak at 438 K, see Table 2. The small endothermic events were
observed between 318 and 411 K (Fe), 306417 K (Co), 333463 K
(Ni), 313392 K (Cu) and 303423 K (Zn) due to thermal dehydration. This event does not match the amount of water lost probably
because the mass loss occurs so slowly that the heat absorbed in
this step is not sufcient to produce a thermal event in DSC curve
[14].
The thermal stability of anhydrous compounds (I) as shown by
the TGDSC curves depended on the nature of the metal ion in the
following order:
K >> Mn > Ni > Zn > Fe > Co > Cu = H-Los

(I)

The thermal decomposition of anhydrous compounds


occurs in two (Fe), three (Mn, Ni, Cu and Zn) and ve (Co)
consecutive steps. Probably, in the rst step of the thermal decomposition occurs due to the output of methanol
group (MnmTG = 6.64%; mcalcd . = 6.45%; FemTG = 6.50%;
mcalcd . = 7.36%;
ComTG = 6.49%;
mcalcd . = 7.31%;
mcalcd . = 6.25%;
CumTG = 7.34%;
NimTG = 6.55%;

J.A. Teixeira, A.B. Siqueira / Journal of Analytical and Applied Pyrolysis 117 (2016) 1724

21

Fig. 3. Simultaneous TGDSC curves of the synthesized compounds in dynamic nitrogen atmosphere of the synthesized compounds: (a) Mn(Los)2 4H2 O (7.1959 mg); (b)
Fe(Los)2 2.5H2 O (7.1790 mg); (c) Co(Los)2 3H2 O (7.2409 mg); (d) Ni(Los)2 2.5H2 O (6.8299 mg); (e) Cu(Los)2 2H2 O (7.0998 mg); (f) Zn(Los)2 H2 O (6.9646 mg).

mcalcd . = 6.79%;
ZnmTG = 6.70%;
mcalcd . = 5.91%).
The
exothermic peak indicated the oxidation of this evolved group.
The similarity of the TGDSC curves were observed until c.a.
683 K (Mn and Fe) and 763 K (Ni, Co and Zn). The difference
observed after these temperatures were due to intermediates
products formed with metal ion. The nal temperature
of thermal decomposition of compounds follow the order
Zn > Mn > Co > Cu > Fe > Ni suggesting dependence characteristics of ionic radius of the metal ions (Zn > Co > Ni). The exothermic
peaks observed in DSC curve, see Table 2 and Fig. 2, indicate
oxidative degradation of Los.
The color change during the heating and cooling of the residue,
and results obtained by TGDSC curves indicate that the residue
formed at 967 K to Co(Los)2 3H2 O was reduced to CoO at 1160 K.
An endothermic peak at 1170 K was observed in DSC curve. The CoO
was stable at higher temperature as it was partially oxidized in cooling (CoO Co3 O4 ). The residues were formed at 1063 K (Mn3 O4 ),
939 K (Fe2 O3 ), 929 K (NiO), 957 K (CuO) and 1070 K (ZnO) were
stable up to 1273 K.

5. N2 atmosphere
The thermal decomposition of compounds at nitrogen atmosphere occurred in two (Los) and four (H-Los, Mn(Los)2 4H2 O,
Fe(Los)2 2.5H2 O, Co(Los)2 3H2 O, Ni(Los)2 2.5H2 O, Cu(Los)2 2H2 O
and Zn(Los)2 H2 O) consecutive steps, see Fig. 3 and Table 3.
The TGDSC curves showed similar prole up to 623 K (Los
and H-Los) and 773 K (Mn, Fe, Co, Ni, Cu and Zn). The similarities
between TGDSC curves of metal compounds in inert atmosphere
indicates that all metals have the same interaction with the Los.
The exothermic peaks at 524 K (H-Los), 602 K (Los), 527 K
(Mn, Fe, Co, Cu and Zn) and 543 K (Ni) are attributed intrinsic
reaction of ligand during thermal decomposition. Probably the
energy released was caused by reaction between products evolved
during the thermal decomposition mainly due to methanol group
evolved. The others steps occurred as expected, they observed
only endothermic peaks. The carbonaceous residue could not be
degraded up to 1273 K (res.(Los) = 25,84%; res.(H-Los) = 17,50%;
res.(Mn(Los) 2 .4H2O) = 31.88%;
res.(Fe(Los) 2 .2.5H2O) = 32.53%;
res.(Ni(Los) 2 .2.5H2O) = 38.46%;
res.(Co(Los) 2 .3H2O) = 30.15%;

22

J.A. Teixeira, A.B. Siqueira / Journal of Analytical and Applied Pyrolysis 117 (2016) 1724

Table 3
Temperature ranges (), mass losses (m), and peak temperatures observed for each step of the TGDSC curves in nitrogen atmosphere of the compounds.
Compounds

HLos

Steps
First

Second

Third

Fourth

Transition

459485
4.66
469 (endo)

485558
9.64
524 (exo)

558863
55.25
6141009 (endo)

863 > 1273


4.61

469 (endo)

m (%)
Peak (K)

558850
61.15
602 (exo)

557 > 1273


21.35

(K)
m (%)
Peak (K)

359446
7.35
444 (endo)

490624
14.22
527 (exo)
573622 (exo)

624 832
33.18
622703 (exo)

832 > 1273


13.37

 ( C)
m (%)
Peak ( C)

320466
4.96
316 426 (endo)

466590
11.71
527 (exo)
555597 (exo)

590856
33.48
621728 (exo)

856 > 1273


17.32

(K)
m (%)
Peak (K)

318460
5.17
320421 (endo)

460617
14.4
527 (exo)
548619 (exo)

617818
29.68
619670 (exo)

818 > 1273


20.60

(K)
m (%)
Peak (K)

328481
4.44
310463 (endo)

481564
6.37
543 (exo)

564853
41.08
591 (exo)
618 (exo)

853 > 1273


9.65

(K)
m (%)
Peak (K)

312459
3.65

459567
10.70
527 (exo)

567793
33.96
553 (exo)
597 (exo)

793 > 1273


11.54

(K)
m (%)
Peak (K)

313477
1.81

477629
15.77
527 (exo)
558625 (exo)

629818
30.47
630679 (exo)

818 > 1273


16.73

(K)
m (%)
Peak (K)

Los

Mn(Los)2 4H2 O

Fe(Los)2 2.5H2 O

Co(Los)2 3H2 O

Ni(Los)2 2.5H2 O

Cu(Los)2 2H2 O

Zn(Los)2 H2 O

Phase

(K)

res.(Cu(Los) 2 .2H2O) = 40.15%; res.(Zn(Los) 2 .H2O) = 35.22%),


the residues could be not determined.

516 (endo)
547 (endo
1043 (endo)

therefore

5.1. Evolved gas analysis


The gaseous products evolved during the thermal decomposition of compounds were studied in nitrogen and air atmospheres
by TG/DSC coupled to FTIR. The IR spectra selected at different
temperatures for the gaseous products evolved during the thermal decomposition of the manganese compound (N2 ) and Los (air)
are presented in Figs. 4 and 5, respectively, as representative of all
compounds in both atmospheres, once the gases released are the
same. See Figs. 4 and 5.
The thermal decomposition of H-Los and Los showed the
released of nitrogen compounds and carbon oxides (CH3 NH2, NH3,
NO, CO and CO2 ) at 610 K proved thermal degradation of methanol
group and imidazole group as suggested in previous sections.
The wavenumber at 1503 cm1 , 968 cm1 , 932 cm1 and
3332 cm1 are assignments of vibration modes due to angular
deformation and stretching of ammonia and methylamine compounds. These bands were detected in IR spectra at all steps of
thermal decomposition until c.a. 873 K. The released nitrogen compounds in all steps of thermal decomposition indicate that the
thermal degradation of tetrazole ring occur immediately after the
thermal decomposition of imidazole group.
The
compounds
Mn(Los)2 4H2 O,
Fe(Los)2 2.5H2 O,
Co(Los)2 3H2 O, Ni(Los)2 2.5H2 O, Cu(Los)2 2H2 O and Zn(Los)2 H2 O
indicated the similar IR spectra of products gaseous evolved
during thermal decomposition. The mainly released gaseous
products were CO, CO2 , NH3 and CH3 NH2 as observed during
thermal decomposition of Los and H-los. However, the thermal

Fig. 4. IR spectra from the gaseous products evolved during the thermal decomposition of Mn(Los)2 4H2 O in dynamic nitrogen atmosphere.

J.A. Teixeira, A.B. Siqueira / Journal of Analytical and Applied Pyrolysis 117 (2016) 1724

23

Table 4
Main vibrational data (IR) for the Los, HLos and bivalent metal compounds.
Compounds

A(cm1 )

B(cm1 )

C(cm1 )

D(cm1 )

E(cm1 )

F(cm1 )

G(cm1 )

H(cm1 )

I(cm1 )

J(cm1 )

HLos
Los
Mn(Los)2 4H2 O
Fe(Los)2 2,5H2 O
Co(Los)2 3H2 O
Ni(Los)2 2.5H2 O
Cu(Los)2 2H2 O
Zn(Los)2 H2 O

3366

1468
1459
1457
1460
1460
1460
1460
1461

1436
1422
1425
1425
1425
1423
1426
1427

1358
1358
1357
1353
1356
1356
1354
1353

1263
1258
1259
1255
1255
1254
1256
1257

1121
1113
1111
1105
1104
1103
1104
1095

1086
1074
1077
1074
1073
1071
1073
1073

1007
1007
1013
1006
1006
1006
1007
1006

837
841
843
822
823
824
824
824

715

A = NH (acid); B = CC + CN (Imid) + vNCN(tetra) + (NH for acid) (arom); C = CN(imid) + CC +out CH2 + CH + CCH + COH; D = CH2 (Isob) + CH2 + OH + as NCN;
E = OH + t CH2 (Isob) + CN (imid) + CC (Bif); F = NN (tetr.) + sNCN (tetr.) + CH*; G = NN (tetr.) + as NCN (tetr.) + NNN; H = CO + CH2 ; I = CH + NCN + CCC + NNN;
J = out NH.
: stretching vibrations; as : asymmetrical stretching vibration; : in plane bending vibration; out : out of plane bending vibration.

Fig. 6. IR spectra of (a) Los, (b) HLos, (c) Mn(Los)2 4H2 O, (d) Fe(Los)2 2.5H2 O, (e)
Co(Los)2 3H2 O, (f) Ni(Los)2 2.5H2 O, (g) Cu(Los)2 2H2 O and (h) Zn(Los)2 H2 O.

Fig. 5. IR spectra from the gaseous products evolved during the thermal decomposition of Los in dynamic dry air atmosphere.

decomposition of metal compounds synthesized could be observed


the released water during thermal dehydration and hydrocyanic
acid during thermal decomposition, see Fig. 4. In N2 atmosphere,
the CO2 was the only products gaseous did not observed due to
absence of oxygen gas.
5.2. Infrared spectra
IR spectra show bands related to vibration modes of Los, H-Los
and M-Los, see Fig. 6. The assignments of IR spectra Los is shown in

Table 4. The IR spectra of H-Los and M-Los are only discussed the
differences observed with Los spectra due to this similarity.
The main characteristics observed in IR spectra of Los are
bands at 1074 cm1 and 1113 cm1 , due to stretching vibrational
and angular deformation of N N and N C N of tetrazole group,
respectively. Bands at 995 cm1 and 1007 cm1 were attributed to
stretching CO inasmuch as strong intensities, disagreeing with a
literature report [15], Another important band in the region above
3187 cm1 corresponds to hydrogen interactions of solid Los.
The some bands of H-Los were displaced when compared to
Los spectra due to protonation of tetrazole group by hydrochloric
acid, see Table 4. The absence or lower intensities of vibrational
mode of tetrazole group could be occurred by lower interaction

24

J.A. Teixeira, A.B. Siqueira / Journal of Analytical and Applied Pyrolysis 117 (2016) 1724

Table 5
Antioxidant capacity (%) with DPPH of Los, H-Los and bivalent metal compounds.
Compounds

Concentration in methanol of compounds/mg mL1


200 g mL1

150 g mL-1

100 g mL-1

50 g mL-1

Los
5.86 (0.25) 5.86 (0.25) 5.86 (0.25) 5.86 (0.25)
21.53 (2.06) 18.53 (1.25) 13.77 (1.25) 10.46 (1.79)
HLos
Mn(Los)2 . 4H2 O 26.94 (3.36) 18.06 (3.18) 12.08 (1.10) 1.39 (0.48)
Fe(Los)2 . 2.5H2 O 10.62 (0.77) 8.27 (0.93) 6.30 (0.37) 4.07 (0.64)
Co(Los)2 . 3H2 O
9.63 (1.28) 6.04 (1.19) 4.70 (0.43) 3.95 (0.57)
Ni(Los)2 . 2.5H-2 O 7.32 (0.27) 2.49 (0.27) 2.33 (0.46) 2.04 (0.47)
5.32 (0.32) 4.71 (0.41) 3.10 (0.21) 2.97 (0.28)
Cu(Los)2 . 2H2 O
5.00 (0.72) 4.58 (0.72) 2.63 (0.64) 0.13 (0.24)
Zn(Los)2 . H-2 O

(hydrogen interaction) and lower mass (atomic mass of hydrogen)


as compared vibrational modes of Los. The new absorption band at
3366 cm1 assigned to the vN-H of tetrazole group.
With exception of Mn(Los)2 4H2 O, the wavenumbers of angular
deformation NNN and NCN of the tetrazole metallic compounds
were displaced to lower values in the region above 841 cm1
(Los). Another displaced of vibrational modes observed by tetrazole
metallic compounds, see Table 4. These results strongly indicate that occurs the metal interaction with tetrazole group. The
wavenumbers values may be related with bonding strength, and
they are inversely proportional. So it can be suggested M-L interaction in the following order:
K-Los > Mn-Los> Fe-Los >Co-Los = Cu-Los>Ni-Los >Zn-Los
The lesser difference vN-N between K-Los and Mn(Los)2 4H2 O
as compared (vNNKLos vNNMnLos ) others metallic compounds is
due to these two metals are considered as hard acids by Pearson
Theory [16].
Fernndez et al. [13] showed that K have coordination sphere
with six tetrazoyl N atoms, the methanol O atom and the cloud
of one of the phenyl rings. The band attributed to vCO shown difference between MnO as compared with others compounds. This
difference can be explained by weak interaction between Mn and O.
So the literature data and IR data suggest the interaction of bivalent
metals with N and O of the Ligand.
5.3. Antioxidant evaluation with 1,1-diphenyl-1-picrylhydrazyl
(DPPH)
The model of scavenging the stable DPPH radical is extensively
used to evaluate antioxidant activities in less time than is required
for other methods [1]. Qualitative comparison indicated that the
reaction of Los with DPPH radical and Los with ABTS [3] were similar
results.
With Los exception, the results showed that increase concentration is directly proportional to increase the antioxidant capacity.
Table 5 shows that the Mn(Los)2 4H2 O and H-Los higher antioxidant capacity at all concentrations (50 g mL1 , 100 g mL1 ,
150 g mL1 , 200 g mL1 ) as compared with others compounds.
The protonation of N tetrazoyl Los could to use this hydrogen atom
(protonation) to a DPPH radical [17]. Probably, the weak interaction of hydroxyl ( OH) with Mn suggest the reaction this methanol
group with DPPH have agreeing with higher antioxidant capacity.
6. Conclusion
The TGDSC curves in both atmosphere show that the manganese, iron, cobalt, copper, nickel and zinc compounds were
hydrated while the Los and H-Los were anhydrous. The results
provided information on the composition, dehydration, thermal
stability, thermal decomposition, as well as the gaseous products
that evolved during the thermal decomposition of these compounds.

The metal center is bound to the ligand through the nitrogen


atoms of the tetrazolate moiety and oxygen atom of the hydroxyl
group as determined by vibrational spectroscopy. The relationship
of bonding strength M-N observed by IR spectrum could not compared with thermal stability because of the M-O interactions.
The antioxidant activity assessment indicated that the
Los, Fe(Los)2 2.5H2 O, Co(Los)2 3H2 O, Co(Los)2 2.5H2 O and
Zn(Los)2 H-2 O have lower antioxidant activity. The Mn(Los)2 4H2 O
and H-Los have moderate antioxidant activity wherein
Mn(Los)2 4H2 O exhibited the highest antioxidant activity. These
compounds may prove useful for treating a variety of diseases and
may lead to the development of new drugs.
Acknowledgements
The authors thank LATIG (Laboratrio de Anlise Trmica
Ivo Giolito) IQ-UNESP, LACANM (Laboratrio de Caracterizaco
de Novos Materiais),FAPEMAT, CNPq and CAPES Foundations for
nancial support.
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