SYNTHESIS, CHARACTERIZATION AND BIOLOGICAL ACTIVITY OF SOME TARTARATES AND TRANSITION METAL COMPLEXES
HTML Full TextReceived on 20 November, 2013; received in revised form, 04 January, 2014; accepted, 26 March, 2014; published 01 April, 2014
SYNTHESIS, CHARACTERIZATION AND BIOLOGICAL ACTIVITY OF SOME TARTARATES AND TRANSITION METAL COMPLEXES
S.S. Pawar 1, C.S. Patil 2, V.B. Tadke 1, S.M. Vhankate 1, S.A. Dhanmane 1, G.R. Pathade 1 and R.P. Pawar*2
Department of Chemistry, Fergusson College 1, Pune, Maharashtra, India
Department of Chemistry, Deogiri College 2, Aurangabad, Maharashtra, India
ABSTRACT: Metal complexes having two or more different metal ions not only possess excellent catalytic applications but also have many biological activities. In the present work, some ligand tartarate based mixed transition metal complexes of type [MxMI1-x (C4H4O6)]. XH2O [Where M and MI are Cu and Ni, and x= 0.2, 0.4, 0.6 and 0.8] have been successfully synthesized and were characterized by different sophisticated analytical techniques such as elemental analysis, FT-IR, TGA and XRD. From the analytical data; it was observed that all the complexes exhibited 1:1 (methyl: ligand) ratio. IR data shows that the ligand co-ordinates with metal ions in a bidentate manner through the two oxygen atoms. Thermal analysis shows the degradation pattern of the complexes. The synthesized metal complexes were then tested in vitro for biological activities against Bacillus subtilis, Staphylococcus Aureus, and Escherichia coli to assess their antibacterial and antifungal effect. Some of them showed promising antimicrobial activity.
Keywords: |
3-{[(E)-(4-fluorophenyl) methylidene] amino} benzoic acid, Metal ion complexes, Biological activities
INTRODUCTION:Metal complexes containing two or more different metal ions are always of interest in different field like multimetallic enzymes 1 and catalysis 2, 3.A large number of Schiff bases and their complexes have been studied for its interesting and important properties such as catalytic activity 4 and transfer of the amino group, photochromic properties and complexing ability towards some toxic metals 5. A number of hydrazone derivatives possess interesting bioactivity towards anti-bacterial, antifungal 6 anti-convulsant 7, anti-inflammatory 8, anti-malerial 9, 10, analgesic 10, anti-platelets 11 anti-tuberculosis 12 and anticancer activities 13.
Although, much attention has been directed on the study of Schiff base complexes with ‘N’ and ‘O’ donor atoms; none of the investigation has appeared in literature which describing the metal complexes of ligand containing ‘O’ donor atoms.
In continuation of our work in synthesis and characterization of mixed metal oxalate complexes 14, the present investigation deals with the synthesis of different composition of copper nickel tartarates of the type [CuxNi1-x (C4H4O6)] H2O using co-precipitation technique.
Tartarate act as donor site of carboxyl oxygen atoms. The complexes were screened for their biological and catalytic activity.
EXPERIMENTAL:
Synthesis of Precursor: All the chemicals used were of the analytical grade (A.R.) and of high purity.
The copper-Nickel taratrates with different composition (X=0.2 to 1.0) were prepared by the co-precipitation method by taking high purity CuSO4.5H2O and NiSO4.6H2O in distilled water. The mixture of metal sulphate solution was prepared with respect to molar ratio of Cu and Ni and placed in a beaker. pH of the medium was adjusted to a low enough value (pH<6), so that hydroxide does not precipitate. The solution was stirred vigorously and sodium tartarate (10%) solution was added slowly with stirring till a permanent precipitate occurred. Further an acetone was added in equal amounts to metal salts to ensure a high yield of product. The resultant precipitate was light bluish-green. The solution was filtered after stirring it for 30 minutes. The filtrate was checked for Cu+2 and Ni+2 whose absence ensured complete coprecipitation. The residue was washed with cold distilled water and then with acetone to speed up drying. The solid was dried at ambient temperature.
Antimicrobial Activity: Mixed metal complexes are well known for their biological activity 15-16. All the synthesized mixed metal complexes were screened for antibacterial as well as antifungal activity.
MATERIALS AND METHODS: 1)Synthesized Chemicals: Set A: 1 to 6 and Set B: A1 to A6. 2) Diluents: Sterile distilled water [10 ml in each 7 tubes. 3) Nutrient agar medium [Cruickshank et al 1975] plates- 18 in numbers. 4) Fresh 24 Hrs old nutrient broth cultures of test bacterial organism. a) Bacillus subfilis – Gram positive in nature. b) Staphylococcus aureus - Gram positive in nature. c) Escherichia coli - Gram negative in nature. d) Yeast - Canadian albicaus. f) Molds- Aspergillus, Penecillium chrysogenum. 5) Well borer and glass spreader. 6) Sterile1 ml. capacity glass pipette/micropipette.
- Using sterile distilled water diluents 1% solution of each chemical was prepared.
- For every chemical solution three nutrient agar plates were used and labeled for above three bacterial cultures. In total 12 sets of plates [3 plates in each set] were prepared.
- In each set of plates 0.5 ml. of above bacterial cultures were spread, inoculated and incubated at 37oC for 30 minutes to adsorb the culture on medium surface.
- Using well borer, a well was bored at center of medium in each plate, aseptically.
- 0.1 ml. of each chemical solution was poured aseptically in each respective well and incubated for diffusion at 40C for 1 hrs.
- All the plates were incubated at 370C for 48 hrs and results were recorded.
RESULT AND DISCUSSION:
Characterization of precursors: Figure 1 shows the TGA curves of Cu-Ni Tartarate
FIGURE 1: TGA OF Cu-Ni TARTARATE
The elemental analysis made in Wt % of tartarate precursors are very well matched with the calculated ones (Table 1).
The X-ray powder diffraction pattern of these precursors (Fig. 2) showed broad as well as sharp line indicating that sample were polycrystalline in nature and the 'd' spacing values calculated for respective precursors are given in the table 3.
TABLE 1: ELEMENTAL ANALYSIS
Formula weight | C | H | Cu | Ni | |||||
Complex | Calcd | Found | Calcd | Found | Calcd | Found | Calcd | Found | |
A1
Cu(0.8)Ni(0.2) (C4H4O6)*H2O |
236.54 | 20.29 | 20.22 | 2.50 | 2.42 | 24.86 | 24.35 | 4.95 | 4.84 |
A2 Cu(0.6)-Ni(0.4) (C4H4O6)*H2O |
227.6 | 21.09 | 20.95 | 2.64 | 2.61 | 16.74 | 16.80 | 10.31 | 10.02 |
A3 Cu(0.4)-Ni(0.6) (C4H4O6)*H2O |
226.63 | 21.18 | 21.14 | 2.65 | 2.56 | 11.21 | 10.87 | 15.53 | 14.85 |
A4 Cu(0.2)-Ni(0.6) (C4H4O6)*H2O |
335.65 | 21.27 | 21.22 | 2.66 | 2.59 | 5.62 | 5.13 | 20.8 | 20.18 |
A5 Cu (C4H4O6)*H2O |
229.54 | 20.91 | 20.65 | 2.61 | 2.51 | 27.68 | 27.02 | -- | -- |
A6 Ni (C4H4O6)*H2O |
224.69 | 21.36 | 21.31 | 2.67 | 2.85 | -- | -- | 26.12 | 25.98 |
FIGURE 2: X-RAY DIFFRACTION PATTERNS OF Cu-Ni TARTARATES
The C, H analysis done on Thermoquest model FLASH EA 1112. Nicollet NEXUS 7000C spectrometer is used for taking IR of the precursors (A1-A6).
The infrared spectra showed (Fig. 3) frequencies corresponding to carboxylate group, hydroxyl group, metal-oxygen, carbon-hydrogen etc.
FIGURE-3: INFRA-RED SPECTRA OF TRANSITION METAL COMPLEXES A1-A6
The bidentate linkage of tartarate group with metal was confirmed on the basis of the difference between antisymmetric and symmetric stretching frequencies (Table 2).
The TGA data of Cu-Ni tartarates is summarized in Table 4. Table 5 describes the compositions of Cu-Ni tartarates.
TABLE 2: INFRA-RED SPECTRAL BANDS AND THEIR PROBABLE ASSIGNMENTS
S. no. | A1 | A2 | A3 | A4 | A5 | A6 | ASSIGNMENT |
Cu0.8Ni0.2 (C4H4O6)*H2O |
Cu0.6-Ni0.4 (C4H4O6)*H2O |
Cu0.4-Ni0.6 (C4H4O6)*H2O |
Cu0.2-Ni0.6 (C4H4O6)*H2O |
Cu (C4H4O6)*H2O | Ni (C4H4O6)*H2O | ||
1 | 3416 | 3192 | 3408 | 3433 | 3115 | 3169 | ν(O-H)- stretch |
2976 | ν(C-H) | ||||||
2644 | 2650 | 2664 | 2630 | 2646 | 2320 | ν(O-H) carboxylic acid | |
2097 | 2355 | ν | |||||
2037 | ν | ||||||
1630 | 1630 | 1614 | 1599 | 1616 | 1607 | ν(C-O) | |
1333 | 1431 | 1389 | 1387 | 1431 | 1447 | ν(C=O) | |
1369 | 1333 | 1387 | ν | ||||
1238 | 1292 | ν | |||||
1059 | 1107 | 1121 | 1123 | 1078 | 1115 | νC-O(alcohol) | |
885 | 877 | 930 | 930 | 885 | 987 | ν C-O(sym) | |
825 | 824 | 823 | |||||
748 | 744 | 725 | 719 | 748 | 752 | νsym(C-C) | |
642 | 642 | 617 | 615 | 646 | 631 | ν(C-H) | |
492 | 495 | 497 | 515 | 482 | 436 | ν(M-O) | |
434 | 428 | 424 | 434 | 420 | ν |
TABLE 3: OBSERVED D-SPACING VALUES (A˚):
A1 Cu0.8Ni0.2 (C4H4O6)*H2O |
A2 Cu0.6Ni0.4 (C4H4O6)*H2O |
A3 Cu0.4Ni0.6 (C4H4O6)*H2O |
A4 Cu0.2Ni0.6 (C4H4O6)*H2O |
A5 Cu (C4H4O6)*H2O |
A6 Ni (C4H4O6)*H2O |
0.77856 | 1.1613 | 1.1613 | 1.2323 | 1.1613 | 4.3718 |
16.6149 | 5.7831 | 4.2185 | 0.7711 | 4.5419 | 0.7719 |
2.1986 | 0.8965 | 0.7776 | 4.2185 | 3.573 | 4.093 |
0.8266 | 3.2136 | 1.1516 | 0.7776 | 0.9253 | 3.5046 |
1.9802 | 0.8473 | 2.2967 | 13.304 | 3.246 | 0.8966 |
0.92069 | 0.7733 | 0.8139 | 2.2967 | 2.7609 | 3.4824 |
0.79266 | 1.6867 | 1.6055 | 0.8139 | 0.8266 | 2.8551 |
1.6869 | 0.8682 | 1.605 | 2.6953 | 0.8291 | |
1.1516 | 1.1936 | 2.15 | 2.505 | ||
0.9311 | 0.7749 | 1.9282 | |||
1.8215 | 1.3025 | ||||
1.9874 |
Observed particle size (D=0.89λ/B.cosθ):
A1
287.153 A˚ |
A2
631.87 A˚ |
A3
442.31 A˚ |
A4 175.59 A˚ |
A5
541.96 A˚ |
A6
629.03 A˚ |
TABLE 4: TGA DATA OF CU-NI TARTARATES UNDER STATIC AIR
Complex | % mass loss | % mass loss2 | Temp. Range ˚C |
Obsd | Calcd | ||
A1-> Cu0.8-Ni0.2(C4H4O6)*H2O | 11
19.5 |
7.60% | 30-150 150-240 240-320 |
A2-> Cu0.6-Ni0.4(C4H4O6)*H2O | 8.5 25.5 35.5 |
7.60% | 30-95 95-175 175-320 |
A3-> Cu0.4-Ni0.6(C4H4O6)*H2O | 18.5 28.5 31.2 |
7.60% | 30-145 145-220 220-280 |
A4-> Cu0.2-Ni0.6(C4H4O6)*H2O | 16.5 19.8 24.0 |
7.60% | 30-130 130-175 175-240 |
A5-> Cu(C4H4O6)*H2O | 9.0 15.0 38.0 |
7.60% | 30-80 80-135 135-255 |
A6-> Ni(C4H4O6)*H2O | 9.5 15.5 24.8 |
7.60% | 30-100 100-190 190-280 |
TABLE-5: Cu-Ni TARTARATES COMPLEX COMPOSITIONS
Complex/ Composites | Molecular Weight | Amount of CuSO4.5H2O taken | Amount of NiSO4 7H2O taken | Tartarate solution added |
A1 Copper Nickel
Cu0.8Ni0.2(C4H4O6).H2O
|
236.54 | 4.02 gm | 1.12 gm | 10 % |
A2 Copper Nickel
Cu0.6Ni0.4(C4H4O6).H2O
|
227.6 | 4.53 gm | 3.36 gm | 10 % |
A3 Copper Nickel
Cu0.4Ni0.6(C4H4O6).H2O
|
226.63 | 2.51 gm | 4.21 gm | 10 % |
A4 Copper Nickel
Cu0.2Ni0.8(C4H4O6).H2O
|
335.65 | 1.255 gm | 5.6 gm | 10 % |
A5 Copper Nickel
Cu1.0Ni0.0(C4H4O6).H2O
|
229.54 | 7 gm | 0 gm | 10 % |
A6 Copper Nickel
Cu0.0Ni1.0(C4H4O6).H2O |
224.69 | 0 gm | 7 gm | 10 % |
Rigaku D/Max-2A Diffractometer with Cu, K alpha radiation and Ni filter is used for taking XRD of these precursors. Particle size is also calculated using formula (D=0.89λ/B Cos θ). The probable structure of compound Copper Nickel Tartarate is shown by figure 4.
FIGURE 4:
All the precursors shows loss of water molecule at about 100oC. The percentage loss for one water molecule is well matched with the theoretical loss. The oxidative decomposition of the ligand is observed between 150 to 400oC.
Biological Activity: All these complexes (i.e. A1 to A6) showed antibacterial and antifungal activity against microorganism (Table 6).
Table 6: Antibacterial and antifungal activity studies of synthesized chemicals: Zone of Inhibition [in mms]
S. No. | Complex | E. coli | B. subtilis | S. aureus | C. albicans | A. niger | P. chrysogenum |
1 | A1 | 30 | 21 | 17 | 9 | 19 | 7 |
2 | A2 | 25 | 25 | 19 | 22 | 28 | 8 |
3 | A3 | 16 | 19 | 17 | 25 | 10 | 22 |
4 | A4 | 15 | 16 | 22 | 14 | 8 | 17 |
5 | A5 | 14 | 34 | 27 | 34 | 5 | 9 |
6 | A6 | 16 | 12 | 20 | 17 | 17 | 17 |
7 | Control [Sterile distilled water] | 0 | 0 | 0 | 0 | 0 | 0 |
PHOTOGRAPHS OF SOME ACTIVITY PETRI-DISHES:
All these complexes (A1 to A6) possess potential to inhibit gram positive as well as gram negative bacteria selected indicating their possible to use as bacterial agent. Out of these, sample A5 showed highest antibacterial and antifungal effects.
CONCLUSION:
- The elemental analysis for complexes (A1 to A6) is well matched with expected ones.
- The Infra-Red study suggests that the tartarate ligand is a bidentate ligand.
- The -ray patterns of these complexes (A1 to A6) suggest that they are polycrystalline in nature.
- Thermogram provides the information about the presence of one water molecule and oxidative decomposition of the ligand.
- Above study suggest that the metal chelate exhibited polymeric octahedral structure (Fig-4).
- Antimicrobial and Antifungal activity: The study reveals that these complexes possess antimicrobial as well as antifungal activity.
ACKNOWLEDGEMENT: Authors are thankful to the Principal Deogiri College, Aurangabad (MS) India for providing laboratory facilities.
REFERENCES:
- Siegbahn PEM, Blomberg MRA: Transition-metal systems in biochemistry studied by high-accuracy quantum chemical methods. Chemical Reviews 2000; 100: 421-43.
- Hu X: Base Metal complexes as homogeneous catalysts and enzyme mimics. Chimia 2011; 65: 646-648.
- Shivankar VS, Burungale AS, Rajmane MM, Gavali LV: Synthesis, characterization and catalytic activity of mixed ligand transition metal complexes. Archives of Applied Science Research 2012; 4 (5): 2289-2298.
- Rezaeifard A, Jafarpour M, Nasseri MA, Haddad R: Pronounced catalytic activity of manganese(III) Schiff base complexes in the oxidation of alcohols by tetrabutylammonium peroxomonosulfate. Helvetica Chimica Acta 2010; 93:711-717.
- Karipcin F, Cengiz M: Novel homo- and hetero-nuclear copper(II) complexes of tetradentate Schiff bases: Synthesis, characterization, solvent-extraction and catalase-like activity studies. Journal of Hazardous materials 2009; 163(2-3): 1148-1156.
- Wu J, Wang J, Hu D, He M, Jin L, Song B: Synthesis and antifungal activity of novel pyrazolecarboxamide derivatives containing a hydrazone moiety. Chemistry Central Journal 2012; 6(51): 1-5.
- Kumar S, Bawa S, Drabu S, Kumar R, Machawal L: Synthesis and in vivo anticonvulsant evaluation of 2-chloroquinolinyl hydrazone derivatives. Acta Pol Pharmaceutica 2010; 67 (5): 567-73.
- Kaplancikli ZA, Altintop MD, Ozdemir A, Turan-Zitouni G, Khan SI, Tabanc N: Synthesis and Biological Evaluation of Some Hydrazone derivatives as anti-inflammatory agents. Letters in Drug Design & Discovery 2012; 9: 310-315.
- Sahu NK, Sharma M, Mourya V, Kohli DV: Qsar study of some substituted 4-quinolinyl and 9-acridinyl hydrazones as antimalarial agents. Acta Pol Pharmaceutica 2012; Dec ;69 (6):1153-65.
- Le TT, Hoang XT, Vu DH, Tran KV: Design, Synthesis and in vitro antimalarial evaluation of new quinolinylhydrazone derivatives. Letters in Drug Design & Discovery 2012; 9(2):163-168.
- Baytas S, Nermin N, Dural T, Ozkan Y, Hasan BS¸ Ims E, Turkiz G, Serdar U: Synthesis, anti-inflammatory, antiplatelet and in silico evaluations of (E)-3-(3-(2,3-dihydro-3-methyl-2-oxo-3H-benzoxazole-6-yl)-1-phenyl-1H-pyrazole-4-yl)acrylamides Turk Journal of Chemistry 2012; 36: 367- 382.
- Adibi H, Zaker S, Monkaresi H: Synthesis and characterization of hydrazide-hydrazone derivatives of 3-pyridine carboxylic acid as antimycobacterial tuberculosis agents. Journal of Reports in Pharmaceutical Sciences 2012; 1(1): 60-66.
- WW, Eid E-SNN, Mohareb RM: Synthesis and anti-tumor evaluation of novel hydrazide and hydrazide-hydrazone derivatives. Acta Pharmaceutica 2013; 63(1): 45- 57.
How to cite this article:
Pawar SS, Patil CS, Tadke VB, Vhankate SM, Dhanmane SA, Pathade GR and Pawar RP: Synthesis, characterization and biological activity of some tartarates and transition metal complexes.Int J Pharm Sci Res 2014; 5(4): 1557-65.doi: 10.13040/IJPSR.0975-8232.5(4).1557-65
All © 2013 are reserved by International Journal of Pharmaceutical Sciences and Research. This Journal licensed under a Creative Commons Attribution-NonCommercial-ShareAlike 3.0 Unported License.
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English
IJPSR
S.S. Pawar , C.S. Patil , V.B. Tadke , S.M. Vhankate , S.A. Dhanmane , G.R. Pathade and R.P. Pawar*
Department of Chemistry, Deogiri College, Aurangabad, Maharashtra, India
rppawar@yahoo.com
20 November, 2013
04 January, 2014
26 March, 2014
http://dx.doi.org/10.13040/IJPSR.0975-8232.5(4).1557-65
01 April, 2014