Sie sind auf Seite 1von 6

Journal of Chemistry and Chemical Sciences, Vol.

5(6), 311-316, June 2015


(An International Research Journal), www.chemistry-journal.org

ISSN 2229-760X (Print)


ISSN 2319-7625 (Online)

Ultrasound Assisted Synthesis and Physiochemical


Investigation of Nickel Dimethyl Glyoxime Complex
Sunil Jadhav1, Shrikaant Kulkarni2 and Shujat Quadri3
1

Ramkrishna Paramhansa Mahavidyalaya,


Osmanabad, INDIA.
2
Vishwakarma Institute of Technology,
Pune, M.S., INDIA.
3
Maulana Azad College of Arts, Commerce, Science,
Aurangabad, M. S., INDIA.
(Received on: June 7, 2015)
ABSTRACT
In this work the complex, Nickel-dimethyl glyoxime complex (abbreviated
as Ni(II)(DMG)2) has been synthesized assisted by ultrasound and the effect of the
same is studied as against conventional method. The complex on its preparation is
characterized using analytical tools like UV-Vis Spectroscopy, FTIR, SEM so as to
throw light on the structural features of the complex as well as its morphology and
other physical characteristics. The UV absorption spectrum for the Ni(II)(DMG)2
complex shows absorption maximum at 570 nm which is in tandem with the
reported data in the earlier literature. Further, FTIR shows prominent band attributed
to N-O-H prior to ligation with Ni and further after ligation a band attributed to NiN gets prominent while the former gets weakened. SEM image shows square ice,
flake like particles although there is a lot much of dispersity in the particles and in
turn its morphology. Disc diffusion test is employed for microbiological testing
which shows that the Ni-DMG complex shows excellent inhibition to microbial
species under examination from the results.
Keywords: Nickel-dimethyl glyoxime complex, UV-Vis Spectroscopy, Ni-DMG
complex.

INTRODUCTION
Nickel and nickel compounds have attracted interest in catalyzing electrooxidation
of small organic molecules. Recently hollow nickel spheres have been effectively and
efficiently used as catalysts for the oxidation of methanol and ethanol6, further kinetic studies
June, 2015 | Journal of Chemistry and Chemical Sciences | www.chemistry-journal.org

312

Sunil Jadhav, et al., J. Chem. & Cheml. Sci. Vol.5 (6), 311-316 (2015)

of ethanol oxidation on CuNi alloy supported PtRu and PtMo catalysts have also been
investigated7. Nickel oxide/hydroxides and nickel-tetraazamacrocyclic complexes too have
proved to be capable of catalyzing alcohol oxidation in an alkaline medium. Taraszewska8,
ElShafei9, and Fleischmann et al.10 have reported the electro-oxidation of methanol catalyzed
by Ni hydroxide coated on glassy carbon electrodes or on Ni electrodes. NiOOH was found
to be the active species responsible for the catalytic activity. This catalytic activity has been
used in liquid chromatographic detection of aliphatic alcohols11. Ni complexes demonstrated
higher catalytic activity than NiOOH. Roslonek and Taraszewska12 and Bae et al.13
investigated catalytic activity of Ni tetraaza macrocycle towards alcohol and L-ascorbic
oxidations, and found that Ni tetraazamacrocyclic complexes showed lower overpotential
(0.1 V lower) than NiOOH, Nickel porphyrine-catalyzed methanol electro-oxidation has also
been reported by Golabi and Nozad14, and Ciszewski and Milczarek15. Other nickel
coordination compounds such as Ni-1-(2-pyridylazo)-naphthol have also been investigated16.
Diamethyglyoxime is one of the most commonly used ligands coordinating nickel
ions in preference, which forms Ni-DMG complexe due to characteristic sensitivity and
stability. The ligand can adsorb on an electrode surface and significantly enhance the
electrochemical response to Ni metal ions. This property has been used to the advantage in
the detection of Ni ions in natural water1719. In the previous work, nickel hydroxide, or
nickel complex, modified electrodes, were prepared successfully by oxidizing nickel
electrodes in an alkaline medium10, running scans with the nickel rod in solutions which
contain the ligand and with the working electrode in nickel complex alkaline solutions20,
21.22.23
, deposit nickel salt solutions to the electrode surface followed by cycling it in alkaline
solution, alternate immersion of the working electrode in nickel salt followed by alkaline
solutions, directly depositing nickel complex solution onto the electrode surface24.
MATERIALS AND METHODS
Dimethylglyoxime (CH3C(=NOH)C(=NOH)CH3, abbreviated as DMG), nickel(II)
sulphate, sodium hydroxide, and ethanol used were all AR grade reagents, and used as
received. All aqueous solutions were prepared with Milli Q water. Bis-(dimethylglyoxime)
nickel(II) complex (abbreviated as Ni(II)(DMG)2)) was prepared in accordance with the
reported procedure. An Ethanolic solution 50 mL of 0.02 mol L-1 DMG was mixed with 50
mL of Ni(II) sulphate aqueous solution, added upon by 5 mL of 1.0 mol L-1 aq.NaOH
solution. The addition of OH- anions was to maintain PH in the range of 9-10 which
facilitates the formation of Ni(II)(DMG)2. The reaction mixture was subjected to sonication
to hasten the process of complex formation as well as to observe its effect on morphology of
the complex which is obtained.in the form of a scarlet-red product. The reaction of such a
synthesis can be described as reaction (I):

This Ni(II)(DMG)2 was filtered, exhaustively washed with Milli Q water three times,
and then dried at room temperature.
June, 2015 | Journal of Chemistry and Chemical Sciences | www.chemistry-journal.org

Sunil Jadhav, et al., J. Chem. & Cheml. Sci. Vol.5 (6), 311-316 (2015)

313

RESULTS AND DISCUSSIONS


Fig 1 shows the structure of Nickel-dimethyl glyoxime complex (abbreviated as
Ni(II)(DMG)2) .

Fig.1. Structure of Ni DMG complex

Fig.2. Scarlet red coloured complex of Ni-DMG


complex

Fig. 2 shows the product in the form of Scarlet red coloured complex of Ni-DMG
complex synthesized by subjecting the reaction mixture to sonication.

Fig. 3. Absorption spectrum for Nickel Dimethyl Glyoxime Complex

Fig. 3 shows the electronic or UV-Visible spectrum for the reaction product
(Ni(II)(DMG)2) in ethanol recorded with Shimadzu make, UV-1650PC and was found to
show a sharp absorption maximum at 570 nm in tandem with the reported value which can
be attributed to its d-d transition.
June, 2015 | Journal of Chemistry and Chemical Sciences | www.chemistry-journal.org

314

Sunil Jadhav, et al., J. Chem. & Cheml. Sci. Vol.5 (6), 311-316 (2015)

Fig.4 shows the SEM image of the sample is


shown showing an ice square-like shape although
there is change in the morphology among different
particles as observed in the complex with the
particle size of 30nm which is found to be smaller
than that obtained using conventional process.

Fig.4. SEM image of Nickel Dimethyl Glyoxime Complex

ANTIMICROBIAL TEST
The antimicrobial activity results for Ni-DMG complex reveal that it shows fairly
good activity against all the tested bacterial strains. The higher activity of the metal
complexes may be ascribed to the effect of metal ions on the normal cell membrane. Metal
chelates bear polar and nonpolar properties together; makes them suitable to permeate to the
cells and tissues. In addition, chelation may either enhance or suppress the biochemical
potential of bioactive organic species. Further, lipophilicity, which controls the rate of entry
of molecules into the cell, is modified by coordination, so the metal complex can become
more active than the free ligand. Therefore, the metal complexes show greater antimicrobial
activities than the uncoordinated ligand and free metal ion which in fact is in agreement with
the literature.
The antibacterial activities of the complex was interpreted based upon its resistance
or sensitivity following the interpretative chart of the Kirby-Bauer sensitivity methods
(Cheesbrough, 2000). The inhibition of the fungal growth, expressed in terms of percentage,
was determined on basis of the average diameter of the colony compared to the respective
control cultures.
  
% Inhibition =

Where C = diameter of the fungus colony in the control plate; T = diameter of the fungus
colony in the treated plate, after three days.
FTIR spectrum
The infrared spectrum of the dimethylglyoxime complex (Ni(II)(DMG)2) shows that
there are some characteristic absorption bands namely 3,200 cm-1 corresponding to N OH
stretching vibrational mode. A weak band at 1,790 cm-1 indicates a strong intramolecular
hydrogen bonding in the Ni(II)(DMG)2 complex. Another absorption band at 1,442 cm-1 ,
can be assigned to the C=N stretching mode. Further the adsorption band at 1,367 cm-1 and
1,234 cm-1 is attributed to the NOH bending vibrational and N-O stretching modes resply.
All these features confirmed the formation and structure of Ni(DMG)2.
June, 2015 | Journal of Chemistry and Chemical Sciences | www.chemistry-journal.org

Sunil Jadhav, et al., J. Chem. & Cheml. Sci. Vol.5 (6), 311-316 (2015)

315

CONCLUSIONS
The coordination ability of the Dimethyl glyoxime with Ni(II)l has been proved
under the influence of ultrasound. IR, UV-Vis spectrum of the metal complex Ni(DMG)2
confirmed the suggested coordination of the ligand through Nitrogen of N-OH group, and
nitrogen of the N-O group. The process of chelation dominantly affects the biological
activity of the complex which exhibit excellent inhibition against microbes and are potent
against pathogens. Ultrasonication is found to be an effective and efficient tool which hastens
the process of chelation and is also found to reduce the particle size as shown by SEM image.
FTIR too is found to justify structural features of the complex, Thus, the complex
synthesized is of vital importance given its property profile and the method of sonication can
be extended for the synthesis of other metal complexes too quite effectively.
REFERENCES
1. Adkhis A, Benali-Baitich O, Khan MA, Bouet G. Synthesis, Characterization and
thermal behviour of mixed ligand complexes of Cobalt (III) with dimethylglyoxime and
some amino acids. Synth. React. Inorg. Met.Org. Chem., 30(10): 1849-1858 (2000).
2. Adkhis A, Djebbar-Sid S, Benali-Baiatich O, Kadri A, Khan MA, Bouet G. Synthesis,
characterization and electrochemical behaviour of mixed-ligand complexes of cobalt(III)
with dimethylglyoxime and some amino acids. Synth. React. Inorg. Met. Org. Chem.,
33(1): 35-50 (2003).
3. Aggarwal RC, Surya Narayana DS, Vallabhanerial CS. Phenylenediamine complexes of
Co(II), Ni(II) and Zn(II) acetylacetonates. Indian J. Chem., 20A(4): 419-420 (1981).
4. Bruce MR, Ronaldo P. Some Factors influencing Mixed Complex Formation. J. Inorg.
Nucl. Chem., 36: 1665-1670 (1974).
5. Burger K, Ruff I, Ruff F. Some theoretical and practical problems in the use of organic
reagents in chemical analysis IV. Infrared and ultraviolet spectrophotometric study of the
dimethylglyoxime complexes of transition metals. J. Inorg. Nucl. Chem., 27: 179-190 (1965).
6. Canpolat E, Kaya M. Synthesis, characterization of some cobalt(III) complexes with VicDioxime Ligands and their antimicrobial properties. Turk J. Chem. 28: 235-242 (2004).
7. Cheesbrough M. District Laboratory Practice in Tropical Country. Part 2. Cambridge
University press, p. 133 (2000).
8. Cotton FA, Wilkinson G. Advance Inorganic Chemistry. 3rd Edition, Wiley Eastern, Ltd.,
pp. 893-897 (1986).
9. Hamrit H, Djebbar-Sid S, Benli-Baitich O, Khan MA, Bouet GM. Potentiometric Studies.,
Synthesis and Characterization of Mixedligand Complexes of Cu(II), Ni(II), Co(II) and
Mn(II) with N-(2-acetamidioiminodiacetic)acid as the primary ligand and histidine as the
secondary one. Synth. React. Inorg. Met.-Org. Chem., 30(10): 1835-1848 (2000).
10. Khadikar PV, Saxena R, Khaddar T, Feraqiu MA. Salicylhydroxamic acid and their
metal Chelates as antifungal agents. J. Indian Chem. Soc., 56: 215 (1994).
June, 2015 | Journal of Chemistry and Chemical Sciences | www.chemistry-journal.org

316

Sunil Jadhav, et al., J. Chem. & Cheml. Sci. Vol.5 (6), 311-316 (2015)

11. Khanol Kar VD, Jahagirdar DV, Khanolkar DD. Mixed Ligand Cheates of Uranyl ion.
J. Inorg. Nucl., Chem. 35(3): 931- 940 (1973).
12. Kolawole GA, Ndahi NP. Cobalt(III) complexes of dimethylglyoxme with no direct
cobalt-carbon bond as possible nonorgano metallic models for vitamin B12. Synth.
React. Inorg. Met Org. Chem. 34(9): 1563-1580 (2004).
13. Kudirat e-Zahan, Shamin H, Shuranjan S, Aslam H. Evaluation of in vitro antimicrobial
and in vitro cytotoxic properties of peroxo coordination complexes of Mg(II), Mn(II),
Fe(II) and Ni(II). Dhaka University J. Pharm. Sci., 3: 1-2 (1994).
14. Malik GS, Singh SP, Tandon JP. Studies on the Mixed-ligand Complexes involving
Ligands of Biological Importance [Ni(II) 1, 10. phenan throline - -amino acids] J.
Inorg. Nucl. Chem. 39(7): 1279-1982 (1977).
15. Manavathu EK, Suryanarayana K, Hesnani SE, Leung W. DNAmediated transformation
in the aquatic filamentous fungus Achlya ambisexualis. J. Gen., Microbiol. 134: 20192028 (1988).
16. Nadira W, Singh HB, Gajana A, Raichowdhary AV. Synthesis of metal complexes of
antimalaria drugs and in vitro evaluation of their activity against Plasmodium
falciparium. Inorg. Chim. Acta, 135: 133-137 (1987).
17. Nakamoto K. Infrared and Raman spectra of Inorganic and Coordination Compounds.
Wiley Interscience, New York, p. 194-197 (1986).
18. Obaleye JA, Famurewa O. Inhibitory effect of some inorganic boron trifluorde
complexes on some microorganisms. Biosci. Res. Comm. 1(2): 87-93 (1989).
19. Perrin DD, Agarwal RP. Metal ions in Biological System. New York, Vol.2. p.167 (1973).
20. Peter AA, Kolawole GA. Metal complexes in the management of Chloroquine Resistant
malaria parasites: synthesis, characterization and in vitro studies of metal (II) complexes
of sulfadine. Proceeding of Chemical Society of Nigeria, Yerwa 2005 International
Hotel, Maiduguri Borno State (2005).
21. Ramanujam VV, Krishnan U. Studies on Mixed-Ligand Complexes of Copper. Part1.
Copper-Malonateamino Carboxylate Complexes. J. Indian Chem. Soc. VIII, 425-429 (1981).
22. Robert AS, Ellen SR. Introduction to Food-Borne Fungi. (3rd edition). Cetraalbureau
Voor Schcimmel Cultures, the Netherlands, pp. 56, 62, 66, 287 (1988).
23. Schnauzer GN. Organo Chemistry of Vitamin B12 model compounds (cobaloximes).
Acc. Chem. Res., 1(4): 97-103 (1968).
24. Taura DW, Okoli AC, Bichi AH. In vitro antibacterial activities of ethanolic extracts of
Annona Cosmosus L. Alliums Sativum L. and Aloe barbadensis L. in Comparison with
Ciprofloxacin. Best J. 1(1): 36-41 (2004).
25. Vogel AI. A Text-book of Inorganic Analysis including elemental analysis (3rd edition),
Longman group LTD. London, pp. 415-456 (1971).
26. Yeamin R, Belayet H, Saidul I, Shahidil A. Antimicrobial studies of Mixed-Ligand
Transition metal complexes of maleic acid and heterocyclic bases. Pak. J. Biol. Sci.
6(15): 1314-1316 (2003).

June, 2015 | Journal of Chemistry and Chemical Sciences | www.chemistry-journal.org