INTERNATIONAL JOURNAL OF RESEARCH AND SCIENTIFIC INNOVATION (IJRSI)
ISSN No. 2321-2705 | DOI: 10.51244/IJRSI |Volume XII Issue IX September 2025
Page 3668
Synthesis of Metal (II) Complexes of Co, Cu and Ni with Organic
Ligand (Maleic Acid) and Their Antioxidant Activities
Wadai Smith., Hassan B. Yesufu., Emeka Walter Ndubuisi and Lawrence Ocheme Akor
Department pharmaceutical chemistry, University of Maiduguri, Maiduguri ,Nigeria
DOI: https://doi.org/10.51244/IJRSI.2025.120800331
Received: 01 Sep 2025; Accepted: 08 Sep 2025; Published: 13 October 2025
ABSTRACT
Complexes of Co, Ni and Cu with maleic acid as ligand were synthesized using reported procedure and
characterized using UV spectrometry. The purity of the complexes was monitored and analyzed using
solubility, melting point test and the complexes were evaluated for anti-oxidant activities against 1,1-diphenyl-
2-picrylhydraxyl(DPPH) free radicals. All the complexes are of good yield, they are of different colors,
partially soluble in organic solvent and soluble in DMF. The result was analyzed and presented as mean± SEM.
The complex of Co, Ni and Cu at the concentration of 100ug/ml, 50ug/ml, 25ug/ml and 12.5ug/ml respectively
shows less scavenging activity compared to the standard (vitamin C) at all concentration. The EC
50
result
shows that all the complexes have less activity compared to the standard (Vit C.) but still showing notable
antioxidant capacity. On the bases of the above studies, an octahedral has been proposed for the complexes.
Key words: meliac acid, Co(II), Ni(II), Cu(II), Metal complexes, DPPH, Antioxidant activity, coordination
chemistry.
INTRODUCTION
Free radicals and reactive oxygen species (ROS) are unstable molecules that can cause oxidative damage to
biological macromolecules such as lipids, proteins, and DNA. This oxidative stress is linked to the
pathogenesis of numerous chronic diseases, including cancer, cardiovascular disorders, neurodegenerative
diseases, and diabetes mellitus (Halliwell & Gutteridge, 2015; Valko et al., 2007). Antioxidants are agents
capable of neutralizing these free radicals, thereby preventing or reducing the damage they cause. The need for
effective and safe antioxidants has prompted the exploration of various chemical compounds, including metal-
based complexes.
Coordination compounds, especially those involving transition metals, have attracted attention in
pharmaceutical and medicinal chemistry due to their structural diversity, redox potential, and ability to interact
with biological targets (Beraldo & Gambino, 2004; Chitrapriya & Joseph, 2014). Metal complexation often
enhances the biological activity of organic ligands, including their antioxidant capacity, by altering electron
distribution and enabling redox cycling (Abu-Dief & Mohamed, 2015). Among first-row transition metals,
cobalt (Co), nickel (Ni), and copper (Cu) form stable complexes with diverse ligands and exhibit a range of
biological activities (Karthikayen, 1992; Lee, 2009).
Maleic acid is a naturally occurring dicarboxylic acid with the ability to coordinate metal ions through its
carboxylate groups. It has been used in the synthesis of coordination complexes with known applications in
pharmaceuticals, agriculture, and materials chemistry (Khan & Abourashed, 2010; Shennara et al., 2014).
When chelated with metal ions, maleic acid can exhibit improved physicochemical properties, including
solubility and biological activity. Some metal-maleate complexes have demonstrated antimicrobial, anticancer,
or antioxidant properties (Turan et al., 2016).
In this study, we synthesized and characterized Co(II), Ni(II), and Cu(II) complexes of maleic acid and
evaluated their antioxidant activity using the DPPH (2,2-diphenyl-1-picrylhydrazyl) radical scavenging assay.
The DPPH method is widely used for assessing antioxidant potential due to its simplicity, sensitivity, and
INTERNATIONAL JOURNAL OF RESEARCH AND SCIENTIFIC INNOVATION (IJRSI)
ISSN No. 2321-2705 | DOI: 10.51244/IJRSI |Volume XII Issue IX September 2025
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reproducibility (Noipa et al., 2011). We hypothesize that metal coordination will enhance the antioxidant
activity of maleic acid by stabilizing its radical form and facilitating hydrogen donation.
Properties of coordination compound
Magnetism
Electron impairment makes metal complexes magnetic. Unpaired electrons occur when considering only
nonmetal complexes, either because electron pairing is unstable or because the complex contains an odd
number of electrons. Therefore, regardless of ligand geometry or type, monomeric Ti (III) species all have one
"d-electron" and must be (para) magnetic. .Ti (ll) with two d-electron forms some complexes that have two
unpaired electrons and others with none. This effects is illustrated by the compounds
TXi
2
[(CH
3
)
2
PCH
2
CH
2
P(CH
3
)
2
]. when X=CL, the complex is paramagnetic (high-spin configuration), whereas
X=CH
3
, it is diamagnetic (low-spin configuration). It is important to realized that ligand provide an important
means of adjusting the ground state properties. Some methods verifying the presence of complex ions include
studying it chemical behavior. This can be achieved by observing the compound's color, solubility, melting
point, absorption spectrum, magnetic properties etc. The characteristics of individual atoms are distinct from
those of complex compounds. Coordination compounds change the characteristics of the metal and the ligand
(Martell & Calvin, 1952).
Bonding in coordination compound
The term "ligand" refers to the ions or molecules that surround the center atom. Ligands are referred to as
coordinated to the atom when they are typically joined to it by a coordinate covalent connection, which
donates electrons from an ion pair into an empty metal orbital. There are also organic ligands such as alkenes
whose pi bond can coordinate to empty metals. Orbital complex can form many compound by bounding with
order complex ions in multiple ratios. This let many combinations of coordination compounds. The structures
have isomer, which can change their interaction with either chemical agent. Metal tetrahedral and octahedral
structures are used to study the binding between metal and ligand. Usually, two interactions are included while
discussing metal-ligand connections. Lewis base and Lewis acid (Schmidbaur et al., 2013).
Geometry
The coordination number, or the number of ligands attached to the metal (more precisely, the number of donor
atoms), is the first characteristic of a structure in coordination chemistry. Usually, the number of ligands
attached can be counted, but occasionally even this becomes unclear. Although a coordination number of two
to nine is typical, lanthanide and actinide compounds can have a considerable number of ligands. Metal ions
may have more than one coordinate number. Typically, the chemistry of transitional and metal complexes is
dominated by interaction between s and p molecular orbital of the ligands and the d-orbital of the ion. The s, p,
and d-orbital of the metal can accommodate 18 elections. The maximum coordination number for a certain
metal to the electron configuration of the metal ions and to the ratio of the size of ligand and the metal
ions .Large metals and small ligands lead to high coordination number, example [ Mo(CN)
8
]
4-,
small metal
with large ligands lead to low coordination number, example PT[P(Cme
3
)]
2
.Due to their large size, lanthanide,
actinides and early transition metal tend to have high coordination numbers .Different ligand structural
arrangements result from the coordination number. The following is the geometry that is most frequently seen:
Pentagonal bipyrimidal (seven-coordination), Octahedral (six-coordination), Tetrahedral (four-coordination),
Trigonal (three-coordination), and Linear (for two-coordination) (Khaled et al., 2014).
Maleic Acid
Almost every area of industrial chemistry uses fumaric acid (FA) and maleic acid (MA), two crucial chemical
intermediates. An essential raw material for the production of surface coatings, copolymers, lubricant additives,
unsaturated polyester resins, plasticizers, and agricultural chemicals is maleic acid (Klaus, 2008).
Maleic acid is a dicarboxylic acid that occurs in nature as L-malic acid. Another optically active isomer is D-
INTERNATIONAL JOURNAL OF RESEARCH AND SCIENTIFIC INNOVATION (IJRSI)
ISSN No. 2321-2705 | DOI: 10.51244/IJRSI |Volume XII Issue IX September 2025
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malic acid which can be synthesized as the racemic mixture of D L-malic acid. Malic acid is commonly
referred to as ‘apple acid’ because of its high concentration in apples (Malusdomestica). Other natural sources
of malic acid include acerola (Malpighiae marginata), alfalfa (Medicago sativa), angelica (Angelica
archangelica), blackhaw (Viburnum prunifolium), blood root (Sanguinaria Canadensis), cherries and others
tone fruit (Prunus spp.), cranberries (Vacciniumma crocarpon), horsetail (Equisetu marvense), jujube (Ziziphus
jujube), marigolds (Tagates spp.), rosehips (Rosa canina), schisandra (Schisandra chinensis), and tamarind
(Tamarindus indica), (Khan and Abourashed, 2010). Malic acid is produced in the metabolic cycles of humans,
plants, and animals. In the Krebs and glycosylate cycles, malic acid provides cells with the carbon skeleton and
energy necessary for amino acid formation. There are two enantiomers, the L-, which sometimes is referred to
as S-, and the D-,which is sometimes referred to as R-.Racemic DL-malic acid was first synthesized in 1923
(Mckenzie, 1923).
Biological production of L-malic acid from bacteria, including Lactobacillus L-malic acid is produced by the
fermentation of fumaric acid. Fumaric acid can be produced by the fermentation from glucose. Yeast (Aureo
basidium pullulans) can also be used to produce L-malic acid by fermentation (Zou et al., 2013). DL-Malic
acid can be commercially produced by several different synthetic processes. Most involve either maleic
anhydride or fumaric acid hydrated at high temperatures (Felthouse et al., 2000). Maleic anhydride is
converted to maleic acid, which in turn is converted to malic acid. Another process involves the mixing of
maleic acid, fumaric acid, and sodium hydrogen maleate in an aqueous solution (Ramsey and Schultz, 1993).
Foods and drinks include malic acid as an ingredient. Because little children lack the ability to metabolize D-
form, the use of the less common D-recemic forms in infant meals is restricted. It functions as a chelating and
buffering agent (Merck, 2015).
Fig.1 showing maleic acid
Complexes of Maleic acid
The intricate chemical processes of an aparticular metal's solubility, binding, and complexation with the
elements of the aquatic phase of the environment determine its bioavailability (West et al., 1991).
Certain negative effects may lessen after complexation, and the metal complexes may be more active than the
free ligands. Furthermore, the complexes may have bioactivities that the free ligand does not. Binding to a
metal ion in vivo or using the metal complex as a carrier to activate the ligand as the cytotoxic agent are two
possible mechanisms of action. Additionally, coordination could result in a notable decrease in medication
resistance (Beraldo et al., 2004).
In biological fluids, the metal ions exist in non-exchangeable form as metalloproteins or loosely bound to some
biological ligands as in metal-activated proteins. The loosely bound metal ions are in equilibrium with similar
metal ions present in the bio-fluids. These simultaneous equilibria involving a variety of metal ions and ligands
are important in biological fluids (May et al., 1977). Hence, the chemical speciation of ligands with metal ions
has been studied in this laborator. (Ramanaiah et al 2013). Maleic acid is a dicarboxylic acid. It is the cis
isomer of butenedioic acid, whereas fumaric acid is the trans isomer. It is soluble in water and moderately
toxic. Inhalation causes irritating of nose and throat. Contact with eyes or skin causes irritation. It is used to
make other chemicals and for dyeing and finishing naturally occurring fibers. Speciation profoundly influences
both the toxicity and bioavailability of an element. The speciation studies of toxic metal ion complexes are
useful for understanding the role played by active site cavities in biological molecules and the binding
INTERNATIONAL JOURNAL OF RESEARCH AND SCIENTIFIC INNOVATION (IJRSI)
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behavior of protein residues with the metal ions and helpful to understand the interaction with other ligands
commonly exist in biological fluids. Chemical specification of metals is important for the understanding of
their distribution, mobility, bioavailability, toxicity, and for setting environmental quality standards.
Bioavailability of a particular metal depends on its complex chemical reactions of dissolution, binding, and
complexation with the constituents of the environmental aquatic media. Studies have been done on the
complex formation of maleic acid with Pb (II) and Cd (II) as a good example in modeling the bonding modes
of dicarboxylic acids to toxic metal ions in mixtures containing ethylene glycol (EG) and water in order to
uncover the effects of solvents on equilibrium processes involving charged species. The neurological,
reproductive, renal, and hematological systems of both humans and animals are negatively impacted by heavy
metals like lead, cadmium, and mercury. The central nervous system is toxically affected by organo-lead
compounds (Chang et al., 1990)
Antioxidants activities of maleic acid complexes
Because fruits and vegetables include a variety of antioxidants and other useful substances, increasing
consumption of these foods has been suggested as a crucial part of a balanced diet for lowering risks and
preventing diseases (Genkinger et al., 2004). This is also true of white button mushrooms (Agaricus
busporum), which are used as functional foods and medicines in addition to being used as food because of
their high protein and mineral content and low levels of starch and cholesterol. It is also thought to be a
significant source of a number of antioxidant compounds, including ascorbic acid, carotenoids, flavonoids,
tocopherols, and phenol (Wani et al., 2010). Although button mushroom is reported to possess considerably
higher levels of antioxidant properties, from the point of view of post-harvest physiology, mushroom is one of
the most sensitive agricultural crops after harvesting and these antioxidant properties of button mushroom tend
to decrease during post-harvest storage with the passage of time (Jahangir et al., 2011). In order to increase
metal solubilization, there has been a greater focus on the generation of organic acids by plant-associated
microorganisms, such as oxalic acid, maleic acid, tartaric acid, succinic acid, and formic acid (Mahmud et al.,
2017).
In Brassica juncea plants under Cr stress, maleic acid (MA) increased the amount of non-enzymatic
antioxidants (AsA, GSH) and the activities of enzymatic antioxidants (SOD, CAT, APOX, MDHAR, DHAR,
GR, and GPOX). This further improved the uptake of Cr in the roots, but at lower concentrations of Cr it
slightly reduced the translocation of Cr from roots to shoots, and at higher concentrations it significantly
reduced it. MA enhanced the plants' growth, biomass, hydration status, and chlorophyll content while reducing
the oxidative damage brought on by Cr (Mahmud et al., 2017). In-vitro studies with soil microbes have
elucidated to some level, in which the concentration of organic acid influx is directly normalized by the
external concentration (Jones et al., 1996). The rhizosphere's soil characteristics (sorption, biodegradation,
buffering capacity, and metal complexation) might alter the organic acid profile, making it difficult to forecast
how the acid will behave (Rajkumar et al.2012).
Cobalt
Cobalt is the main component of vitamin B12 (cobalamin), which serves as a co-enzyme in protein synthesis.
It is located in the third period of the periodic table, between iron and nickel (Amudat, 2010). Cobalt is a white
lustrous metal, having a grayish tinge. It has a melting point of 1497
o
C, boiling point of 2880
o
C and has a
density of 8.90 g/cm3. The electrical conductivity is 10.8 Ω
-1
m
-1
ΔHo sublime at 298K, is 425 KJ/mol, Ѕ298 is
30.04 J/kmol. Its atomic mass is 58.933, metallic atomic radius, is 0.125 nm, and valence electrons [Ar] 3d
7
4s
2
(Karthikyan, 1992).
The oxidation states of cobalt are +1, +2, +3, and +4. These two are the most popular: +2 and +3. The cobalt
(II) ion is octahedrally coordinated in the structures of all anhydrous halides. Many complexes of different
stereochemical kinds are formed by divalent cobalt. The most prevalent ones are octagonal and tetrahedral, but
there are also several square planar and five-coordinated ones. No other transition metal ion generates as many
tetrahedral complexes as cobalt (II), for example. where X = C1-, Br-, OH-, and SCN- in [CoX4]2- (Amudat,
2010). Cobalt (II) forms numerous complexes mostly either octahedral or tetrahedral. Five coordinate and
square planar complexes are also known. Tetrahedral complexes of cobalt (II) are more in number than for
INTERNATIONAL JOURNAL OF RESEARCH AND SCIENTIFIC INNOVATION (IJRSI)
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other transition metal ions. This is mainly due to the fact that, for the d
7
ion, ligand stabilization energies
disfavour the tetrahedral configuration relative to the octahedral one to a smaller extent than for any other
configuration. Magnetic moment values for the high spin octahedral complexes lie between 4.7 and 5.2 BM.
Because of the intrinsic orbital angular momentum in the octahedral ground state, there is considerable orbital
contribution to the magnetic moment (Karthikyan, 1992). Low spin cobalt (II) octahedral complexes are rare.
These species posses t
2g
6
eg
1
configuration and because of the presence of an electron in antibonding e*g
orbitals they would be unstable. Furthermore, the complexes are subject to strong Jahn-Teller distortions. Thus
they tend to lose ligands and form low spin four or five coordinate species (Lee, 2009).
Square planar complexes are low spin with magnetic moments of 2.2-2.7 BM. Their spectra are complex and
neither magnetic nor spectral properties of such compounds have been studied in detail. Five coordinate high
spin (with three unpaired electrons) and low spin (with one unpaired electron) complexes are found to have
either trigonal bipyramidal or square pyramidal structures. The strength of the ligand field, which determines
the magnitude of the splitting, is important in determining the spin state (Lee, 2009).
Cobalt (II) has a d
7
configuration and the ground state configuration in an octahedral ligand field is t
2
g
5
eg
2
in
weak field or t
2
g
6
eg
1
in strong field. Octahedral coordinated cobalt (II) should have three spin-allowed d-d
transitions. The visible absorption spectra of cobalt (III) complexes consist of transitions from A
2
g ground
state to other singlet states. It is possible to observe spin-allowed, d-d bands in the visible region of the spectra
of low-spin. Thus, the strong field ligands that do not cause the low-energy charge-transfer bands, often dictate
the spectra of low-spin complexes. Consequently, the two absorption bands found in the visible spectra of
regular octahedral cobalt (II) complexes represent transition to the upper states T
1
g and T
2
g i.e. A
2
gT
1
g and
A
2
gT
2
g (Karthikyan, 1992).
The complexes of Co (III) are numerous. Almost all Co (III) complexes are octahedral, though a few
tetrahedral, square planar and square antiprismatic complexes are known. Six coordinate complexes of cobalt
(III) which make up over 99% of known cobalt (III) complexes are invariably low spin and diamagnetic (with
l
A
Ig
ground state term) (Karthikyan, 1992). Animals must have trace amounts of cobalt in their food, but
higher concentrations are dangerous. In certain enzymes, cobalt plays a crucial biological role. One cobalt
molecule that is extracted from the liver is vitamin B12. Consuming more raw liver has proven to be a
successful treatment for pernicious anemia (Golding, 1983; Lee, 2009).
Nickel
Nickel has a silvery shine and is a bright white metal. It has a density of 8.91 g/cm3 and melts at 1455 oC.
Nickel has an atomic mass of 58.71, a boiling point of 2840 0C, and valence electrons [Ar] 3d
8
4s
2
. 14 Ω-1m-1
is the electrical conductivity. It has more chemical activity than cobalt or iron. Like iron and cobalt, nickel is
an element in group VIIIB. (Karthikyan, 1992).
Nickel has oxidation states of +2 and +3. Nickel (II) forms a large number of complexes encompassing
coordination numbers 4,5 and 6. An example of 6-coordinates are [Ni(H
2
O)
6
]
2+
, [Ni(NH
3
)
6
]
2+
, [Ni(en)
3
]
2+
etc.
[Ni(CN)
5
]
3-
is an example of 5-coordinate, and exists as a trigonal bipyramidal. Some of the 4-coordinates are
square planar, an example is (Ni(CN)
4
)
2
- tetracyanonickelate (II) (Amudat, 2010). Nickel (II) has a d
8
configuration. Octahedral Ni
2+
complexes showed three spin-allowed transitions, which are 3A
2
g 3T
2
g,
3A
2
g 3TIg(P), 3A
2
g3TI g (F), with the presence of two unpaired electrons, given a magnetic moment of
two 2.9 3.4 BM. For regular tetrahedral complexes, the magnetic moment values are in the range 3.5-4.0 BM
and for the more distorted ones the moments are in the range 3.0-3.5 BM (Karthikyan,1992). The +2 oxidation
state is undoubtedly the most prolific oxidation state for nickel. The primary stereochemistries of Ni (II)
include octahedral, tetrahedral, square planar, square pyramidal, and trigonal bipyramidal. Its coordination
number hardly ever rises over 5. Depending on the size of the orbital contribution, the magnetic moments of
octahedral nickel (II) complexes, which contain two unpaired electrons, vary from 2.9 to 3.4 BM. The most
prevalent of the five coordinate complexes of Ni (II) is square planar stereochemistry (Golding, 1983; Lee,
2009; Amudat, 2010).
INTERNATIONAL JOURNAL OF RESEARCH AND SCIENTIFIC INNOVATION (IJRSI)
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Copper
In nature, copper is found in large quantities as metals in carbonates (CuCO3), sulphides (CuS), and chlorides
(CuCl2). Copper is frequently found in the oxidation states +1 and +2. As a result, copper (II) compounds are
typically paramagnetic and colorful. CuSO4, CuCl2, and CuO are a few examples. The active ingredient in
Fehling's and Benedict's solutions, which are the traditional test solutions for reducing sugars, is copper (II)
sulphate. In water treatment, Cupper (II) sulphate is employed as an algaecide (Golding, 1983; Lee, 2009).
The majority of Cu (I) compounds can be readily oxidized to Cu (II) compounds, but it is more challenging to
further oxidize to Cu (III). If placed in a cubic symmetry environment, Copper (II)'s d
9
configuration with one
unpaired electron exposes it to John-Teller distortion, which has a significant impact on all of its
stereochemistry. It is impossible to distinguish between square coordination and tetragonal deformed
octahedral coordination. The Cu
2+
ion is generally found in an environment with rather low symmetry, making
it somewhat difficult to analyze the spectra and magnetic characteristics in detail. The magnetic moments of
Cu (II) complexes are in the range 1.75-2.20 BM regardless of stereochemistry and independently of
temperature except at extremely low temperature. Majority of the complex exhibits single absorption band in
the region 11,000-16,000 cm
-1
. The d
9
ion is characterized by large distortion from octahedral symmetry and
the band is unsymmetrical being the result of a number of transitions which are by no means easy to assign
unambiguously. An orbital contribution to the magnetic moment is implied by the T ground term of the
tetrahedrally coordinated ion, and a value greater than the spin-only value (1.73 BM) is produced (Karthikyan,
1992).
All the copper (II) complexes are either blue or green. These colors are due to the presence of bands at 600-900
nm region of the spectrum. Cu(H
2
O)
6
2+
is the most familiar complex of copper. It possesses a tetragonal
distorted octahedral structure in which two of the water molecules are situated further from the copper ion than
the other four. An example of tetrahedral complex is CuCl
4
2-
, which is orange in color in the tetrahedral form
but yellow when square planar (Golding, 1983; Lee, 2009).
In the chemical and medicinal sciences, copper is extremely important. Among transition metals, it is the third
most important element. Both plants and the human body need it in varying amounts. After iron (4 g) and zinc
(2 g), copper is the third largest transition metal in human bodies (approximately 100 mg in adults) (Amudat,
2010).
Even though larger concentrations of copper are harmful, humans still need to consume roughly 4-5 mg of
copper every day. Animals that lack this metal are able to use the iron that is stored in their livers. Various
oxidases and blue proteins, such as amine oxidases, ascorbate oxidases, cytochrome oxidases, and galactose
oxidases, are examples of copper-binding enzymes or metalloproteinases found in animals (Golding, 1983; Lee,
2009). Protonation and stability constants of complexes they form with different metal ions, and copper in
particular, are among these characteristics. Crucially, the determination of the bio-ligands' protonation
constants and stability constants with different metal ions in media akin to those of biological systems is
necessary for the clarification and comprehension of the many events in biological systems. It is often accepted
in this context that aqueous solution can serve as a representation of "in vivo" media. Non-aqueous media have
been developed as an alternative since biological media have lipophilic characteristics, although it has been
demonstrated in recent years that aqueous media are not entirely appropriate for in vivo biological interactions
(Amudat, 2010).
MATERIALS AND METHOD
Materials
Nickel (II) chloride,Ferric Chloride, Cobolt (II), Sodium hydroxide (NaOH). Ligand molecule (Maleic acid).
Solvent: dimethyl formamide (DMF), ethanol and chlorofoam. Beaker, test-tube, magnetic stirrer conical flask,
measuring cylinder, spatula, weighing balance, filter paper, funnel, desiccators, melting point apparatus,
thermometer, UV- spectrophotometer
INTERNATIONAL JOURNAL OF RESEARCH AND SCIENTIFIC INNOVATION (IJRSI)
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Method
All glass wares used in this work were washed with detergent after sucking in Conc. HNO
3
rinsed with
distilled and dried in an oven. Weighing was conducted using electrical analytical balance model J A 203H.
Melting point was determined using gallen kemp melting point apparatus. Electronic spectra of metal were
recorded using Perkin-Elmer lambda 35 UV- Vis spectrometer. Percentage of metal was determined using
AAS. Percentage composition of carbon, hydrogen and oxygen for the complexes and ligand were determined
using micro analytical techniques.
Synthesis of cobalt (ii) complexes
The complexes were prepared following reported procedure (Nadira et al., 2010; Ogunniran et al., 2008).
Ibrahim et al 1995). Maleic acid (0.416g, 161.1g/Mol) was dissolved in 10ml of ethanol and stirred until
homogeneous solution is obtained. To this miscible solution (Co(NO
2
)
2.
2H
2
O) (1.168g) dissolved in 10ml of
ethanol was added dropped twice with constant stirring. The resulting mixture was stirred for three hours using
magnetic stirrer at room temperature. The complexes were precipitated by adjusting the pH
to 6-8 using buffer
7 by adding very dilute NaOH solution (5ml, 0.001M), drop wise and stirred using magnetic stirrer for 5-10
minutes, after which the solid complexes formed were poured into a beaker and left to stand for 24 hours. The
precipitate was filtered and washed with equal volume of water and ethanol and dried over CaCl
2
in desecrator.
Equation for reaction is presented as
C
4
H
4
O
4
+ Co(NO
3
)
2
.6H
2
O [Co(C
4
H
4
O
4
).H
2
O] + NO
3
Synthesis of Nickel (II) Chloride
The complexes were prepared following reported procedure (Nadira et al., 2010; Ogunniran et al 2008).
Ibrahim et al 1995). Maleic acid (0.416g, 161.1g/Mol) was dissolved in 10ml of ethanol and stirred until
homogeneous solution is obtained. To this miscible solution (NiCl
2
.2H
2
O) dissolved in ethanol 10ml was
added dropped twice with constant stirring. The resulting mixture was stirred for three hours using magnetic
stirrer at room temperature. The complexes were precipitated by adjusting the pH
to 6-8 using buffer 7 by
adding very dilute NaOH solution (5ml, 0.001M), drop wise and stirred using magnetic stirrer for 5-10 minutes,
after which the solid complexes formed were poured into a beaker and left to stand for 24 hours. The
precipitate was filtered, washed with equal volume of water and ethanol and dried over CaCl
2
in desecrator.
Equation for reaction is presented as
NiCl
2
.2H
2
O + C
4
H
4
O
4
[Ni(C
4
H
4
O
4
).2H
2
O] +Cl
2
Synthesis of Copper Sulphate
The complexes were prepared following reported procedure (Nadira et al 2010; Ogunniran et al 2008).
Ibrahim et al 1995). Maleic acid (0.416g, 161.1g/Mol) was dissolved in 10ml of ethanol and prepared in 100ml
three necked round bottom flask provides with electromagnetic stirrer and stirred until homogeneous solution
is obtained. To this miscible solution (CuSO
4
.2H
2
0) (2.988g) dissolved in ethanol 10ml was added dropped
twice with constant stirring. The resulting mixture was stirred for three hours using magnetic stirrer at room
temperature. The complexes were precipitated by adjusting the pH to 6-8 using buffer 7 by adding very dilute
NaOH solution (5ml, 0.001M), drop wise and stirred using magnetic stirrer for 5-10 minutes, after which the
solid complexes formed were poured into a beaker and left to stand for 24 hours. The precipitate was filtered,
washed with equal volume of water and ethanol and dried over CaCl
2
in desecrator.
Equation for reaction is presented as
C
4
H
4
O
4
+CuSO
4
+ 2H
2
O [Cu(C
4
H
4
O
4
).2H
2
O] +SO
4
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Analysis of purity
Determination of melting point
The melting points of the synthesized complexes were determined gallenkemp melting point apparatus fitted
with a thermometer at Pharmaceutical Chemistry Laboratory, Department of Pharmaceutical Chemistry,
Faculty of Pharmacy, University of Maiduguri along Bama road Maiduguri, Borno State, Nigeria.
Solubility
The solubility of complexes was determined in some polar and non-polar solvent such as methanol, ethanol,
chloroform and dimethyl sulformide (DMF)
Diphenyl-2-pickryl hydrazyl (DPPH).
The DPPH free radical scavenging potential of the ligands and their complexes relating to the standard i.e.
ascorbic acid (VIT.C) was determined using reported procedure as described by Khan et al 2013. In the assay,
ligands and their complexes at different concentrations (6.25µg/ml, 12.5 µg/ml, 25 µg/ml, 50 µg/ml, 100
µg/ml,) dissolved in ethanol were prepared in a test tube using serial dilution method and 2ml of freshly
prepared 0.004mg DPPH in ethanol is added to each concentration the resulting mixture was allowed to stay in
a dark at room temperature, after which, absorbance of the mixture was taken at 517nm using UV
spectrophotometer. The absorbent was decreased by conversion of DPPH to the more stable DPPH molecule
which serve as indication of the capacity of antioxidant compounds to donates H ion (Noipa, 2011).All
measurement was taken in triplicates DPPH radical scavenging activities was calculated using the formula :
Scavenging activity (%) =
AcAs × 100
𝐴𝑐
Where Ac =Absorbance control and As = Absorbance of sample
Determination of EC
50
The EC
50
value required for 50% of the DPPH free radicals scavenging by the complexes were determined
from, a series of dose response data, (sample and DPPH free radical scavenging (%)). Using an X and Y plot
fitted with a linear regretion line and the EC
50
was estimated using the following relationship
EC
50
=
50𝐶
𝑀
Where C rep. the intercept
M rep. the gradient of the line
RESULTS, DISCUSSION AND CONCLUSION
Results
Physical properties of the ligands and their and their complexes
The physical properties of the complexes were analyzed by physical observation, computation and
instrumentation such as melting point determination, determination of percentage yield, color identification
and molecular weight determination. The results were presented in table 4.1.
INTERNATIONAL JOURNAL OF RESEARCH AND SCIENTIFIC INNOVATION (IJRSI)
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Page 3676
Table 4.1 Analytical Data and other Physical Properties of Maleic Acid and Complexes.
Empherical formula
Molecular
Weight (g)
Color
Melting Point
C
Actual yield
(g)
%Yield
[Co(C
4
H
4
O
4
).2H
2
O]
317.0
Ash
178
0.128
66.3
[Ni(C
4
H
4
O
4
).2H
2
O]
263.8
Grey
180
0.300
41.1
[Cu(C
4
H
4
O
4
).2H
2
O]
293.7
Light green
165
0.100
50.5
Physical Properties: The complexes were colored solids with melting points in the range of 165180 °C,
indicating stability. Yields were moderate (41.166.3%).
Solubility
The test of solubility of the ligands and their complexes were carried out in different solvent to know the best
solvent to be used for purification and characterizations of the complexes, the result were represented in table
4.2.
Table 4.2: Solubility of the ligands and complexes in different solvent.
Complexes
Ethanol
chloroform
DMF
[Co(C
4
H
4
O
4
).2H
2
O]
S
SS
SS
[Ni(C
4
H
4
O
4
).2H
2
O]
SS
SS
S
[Cu(C
4
H
4
O
4
).2H
2
O]
S
SS
SS
C
4
H
4
O
4
S
S
IS
SS
Key : Soluble (S), Slightly soluble (SS), Insoluble (IS), Dimethylformide (DMF).
Solubility: Complexes were soluble in ethanol and partially soluble in methanol, chloroform, and DMF.
DPPH (Diphenyl-2-pickryl hydrazyl)
The % scavenging activity against DPPH free radicals of the ligands and their complexes were determined and
presented in table 4.3
Table 4.3: DPPH Radical scavenging activities (%) of complexes, ligands and standards
Conc (µg/ml)
Co complexes ± SEM
NiCl
2
complexes ± SEM
Ascorbic Acid (Vit C)
100
70.6 ± 0.09
68.8 ± 22
96.32 ± 0.1
50
60.4 ± 0.12
65.4 ± 0.08
96.78 ± 80
25
66.2 ± 0.08
64.6 ± 0.17
96.70 ± 12
12.5
63.5 ± 0.12
64.5 ± 0.05
96.52 ± 06
Antioxidant Activity: The complexes showed moderate scavenging activity but consistently less than Vitamin
C across all concentrations..
INTERNATIONAL JOURNAL OF RESEARCH AND SCIENTIFIC INNOVATION (IJRSI)
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Page 3677
EC
50
The EC
50
results determined from linear regression analysis of the ligands and their complex were presented in
table 4.4
Table 4.4 EC
50
result of the complexes, ligand and standard
Compound
EC
50
Cobalt complexes
1.31
Nickel Complexes
1.14
Ascorbic acid
0.55
EC50 values (Co = 1.31, Ni = 1.14,) were higher than that of Vitamin C (0.55 µg/ml), confirming that Vitamin
C had superior antioxidant activity
Table 4.5: showing ligand and complexes
Complex
Empherical Formula
% C
%H
%Metal
C
4
H
4
O
4
-
41.34
3.45
-
[Co(C
4
H
4
O
4
).2H
2
O]
C
4
H
8
O
6
Co
24.86
4.14
30.5
[Ni(C
4
H
4
O
4
).2H
2
O]
C
4
H
8
O
6
Ni
24.94
4.25
30.4
[Cu(C
4
H
4
O
4
).2H
2
O]
C
4
H
8
O
6
Cu
24.29
4.05
32.16
Where: Hydrogen (H), Carbon (C).
Electronic absorption spectra
The electronic spectra of the ligand and their corresponding complexes were analyzed and presented in table
4.6 between the wavelength 200-800 nm.
Table 4.6 Electronic abortion spectra (UV) of Maleic acid and complexes.
Complexes
Absorption (nm)
CM
-1
Proposed geometry
C
4
H
4
O
4
250
370
[Co(C
4
H
4
O
4
).2H
2
O]
440
490
590
25641
20408
16949
Octahedral
[Ni(C
4
H
4
O
4
).2H
2
O]
380
530
670
26316
18869
14925
Octahedral
INTERNATIONAL JOURNAL OF RESEARCH AND SCIENTIFIC INNOVATION (IJRSI)
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Page 3678
[Cu(C
4
H
4
O
4
).2H
2
O]
340
470
490
29412
21276
20408
Square
Pyramidal
(Khaled et al., 2014)
DISCUSSION
The result of physical properties of the complexes showed that all our complexes are colored, have high
melting points (165,178 and 180)
o
C which indicates the strong bonding between the ligand and the metals.
The percentage yields of the complexes were also calculated in which Co have the highest yields 63.3%,
followed by Cu and Ni with yields of 50.5% and 41.1% respectively which are of good yields. From the
solubility results obtained (table 4.2), it indicates that all the complexes are soluble in ethanol while slightly
soluble in methanol, chloroform and DMF. The ligand is soluble in ethanol, methanol and insoluble in
chloroform while slightly soluble in DMF. The antioxidant study (table 4.3), shows that the complexes of Co
and Ni at conc of 100 μg/ml, 50 μg/ml, 25 μg/ml and 12.5 μg/ml have less scavenging activities compared to
the Vitamin C which has high scavenging activities at all the concentration (96.78) as reported by this
literature (Harinath et al., 2015). Table 4.4 shows that the EC
50
of the complexes Co and Ni with EC
50
(1.14
and 1.31) has weaker antioxidants activities compared to the Vitamin C which serve as a standard with EC
50
of
0.55 but still showing notable antioxidant capacity. The percentage of carbon, hydrogen and metal was
calculated, the percentage of carbon and hydrogen has been observed to reduce compared to the initials
because some hydrogen have been lost during formation of the complexes as well as carbon while there is
slightly increase the percentage of the metals from its initials.as shown in (table 4.6)
Table 4.6 show the various absorption Spectra the complexes and bands which was calculated and was used in
the proposing the geometry of the complexes that was obtained as compared with some literatures Khaled et
al., (2014), Nevin et al., (2016).
CONCLUSION
All the complexes are colored and possess high melting point which indicate good thermal stability of the
complexes and strong metal ligand bonding. They show good percentage yields (41.1%, 50.5%, and 66.3%).
The complexes are soluble in ethanol and partially soluble in common organic solvents such as, methanol,
chloroform and dimethylformamide (DMF).
The elemental analysis of the metal complexes is consistent with their general formula as 1:2, ligand: metal
ratio. This is quite in agreement with the proposed geometry of the complexes which also indicate the
presences of complexes.
RECOMMENDATION
Future studies should include detailed mechanistic investigations using multiple antioxidant assays and cell-
based models to clarify how the complexes exert their activity. Cytotoxicity testing on normal and cancer cell
lines, along with in vivo validation of safety and bioavailability, will be essential before proposing biomedical
applications.
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