SYNTHESIS, CHARACTERIZATION AND BIOLOGICAL ACTIVITY OF SOME TARTARATES AND TRANSITION METAL COMPLEXES

Received 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 [M_xM^I_1-x (C₄H₄O₆)]. XH₂O [Where M and M^I 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.

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 [Cu_xNi_1-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. p^H 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.

1. Using sterile distilled water diluents 1% solution of each chemical was prepared.
2. 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.
3. In each set of plates 0.5 ml. of above bacterial cultures were spread, inoculated and incubated at 37^oC for 30 minutes to adsorb the culture on medium surface.
4. Using well borer, a well was bored at center of medium in each plate, aseptically.
5. 0.1 ml. of each chemical solution was poured aseptically in each respective well and incubated for diffusion at 4⁰C for 1 hrs.
6. 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

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

TABLE 3: OBSERVED D-SPACING VALUES (A˚):

Observed particle size (D=0.89λ/B.cosθ):

TABLE 4: TGA DATA OF CU-NI TARTARATES UNDER STATIC AIR

TABLE-5: Cu-Ni TARTARATES COMPLEX COMPOSITIONS

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 100^oC. 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 400^oC.

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]

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:

1. The elemental analysis for complexes (A₁ to A₆) is well matched with expected ones.
2. The Infra-Red study suggests that the tartarate ligand is a bidentate ligand.
3. The -ray patterns of these complexes (A₁ to A₆) suggest that they are polycrystalline in nature.
4. Thermogram provides the information about the presence of one water molecule and oxidative decomposition of the ligand.
5. Above study suggest that the metal chelate exhibited polymeric octahedral structure (Fig-4).
6. 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.

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    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

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