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647-Article Text-739-1-10-20210908
647-Article Text-739-1-10-20210908
647-Article Text-739-1-10-20210908
1
Department of Chemistry, College of Physical Sciences, Federal University of Agriculture, Abeokuta,
Nigeria.
2
Chemistry Department, Faculty of Sciences, Obafemi Awolowo University, Ile Ife, Nigeria.
ABSTRACT
Hydrazones and their coordinated compounds were prepared for antimicrobial activi ties
investigation while hydrazides were prepared from their esters. The hydrazides were reacted with
benzaldehyde to produce benzoylhydrazone, m-nitrobenzoylhyd razone, p-nitrobezoylhydrazone,
3,5 dinitrobenzoylhydrazone, p-aminobenzoylhyd razone and m-aminobenzoylhydrazone in white,
off white, light-yellow, deep-yellow and light-brown colours. Complexes were synthesized from
strontium chloride and the hydrazones which produced off-white, grey, light-brown and dark-brown
complexes. The ligand-metal compounds were analyzed through complexometric titration while
characterization of all the samples were based on spectra data. Metal to hydrazone stoichiometry of
1:0.5 to 1:3 were proposed for the complexes. Relevant assignments were made in the hydrazones
and complexes for possible points of coordination. Physicochemical properties of the ligands and
their coordinated compounds were determined. Antimicrobial Properties of the compounds
demonstrated good performance on Streptococcus faecalis, Clostridium sporosenes, Baccillus
anthracis, Pseudomonas fluorescenes, Saccharomyces cerevisiae and Hansenula anomala.
Nanohybrid study of the samples is recommended for future studies on the antimicrobial activities.
INTRODUCTION
Strontium is a main group element with Hydrazone is a ketone and aldehyde related
atomic number 38. It is important in living class of organic compound where oxygen is
system due to its cellular function in substituted for NNH₂. Its structure is R ₁R
biochemical processes [1]. It is essential for ₂C=NNH₂. Hydrazone has been reported for
maintaining and sustaining bone healthy its coupling with drugs against cancer cell
ability like calcium [1]. Strontium chloride is where stable hydrazone bonds at neutral PH
vital for cleaning lead contaminants from were destroyed in acidic cell environment
toothpastes through zinc refining for teeth resulting in release of the drug to perform its
sensitivity [2]. The element is essential for action [5, 6].
strengthening human skeleton. It binds with Complexes are obtained as a result of ligand -
protein and nucleic acid via electronic charge metal polymerization system. Concentration
distribution which results into inactivation of and interaction of ions are significant in
microorganisms [3]. It is therefore useful in analysis of metal-ligand complexes against
treatment of bone thinning called microorganisms [7, 8]. Enhancement in
osteoporosis, joint swelling known as biological activities and industrial application
arthritis, prostate cancer, bone cancer and potential of ligands by complexes has
treatment of teeth pain through toothpaste increased interest in their studies [7].
addition as strontium chloride hexahydrate Complexes have demonstrated activities
[4]. against smallpox, tumor and virus diseases
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causing microorganisms [8]. Antimicrobial and the ligand metal coordinated compounds.
prevention of food spoilage through the use of Ethylenediaminetetraaceticacid
complexes has been reported [9]. Biological complexmetric titration method was used for
activities of complexes due to structural the estimation of the strontium metal ion [12,
composition have also been described [10]. 15]. Elemental analyses were carried out. The
Antimicrobial potential of strontium- hydrazones and coordinated compounds
hydrazone complexes are yet to be reported. showed levels of solubility in acetone,
This work therefore studied syntheses of the toluene, petroleum ether, benzene, n-hexane,
ligand-metal complexes through the reactions trichloromethane, ethylacetate, ethanol,
between the hydrazones and strontium for methanol and water.
investigation of their antimicrobial activities. Infrared spectroscopy measurement of the
The study also examined effect of vary hydrazones and complexes were performed
ligands with a single metal in complexes and through the use of PYE-UNICAM SP300
monitor their effects by microorganism Spectrophotometer.
inhibitory studies. Antimicrobial test were investigated on
Streptococcus faecalis, Clostridium
2. MATERIALS AND METHODS sporosenes, Bacillus anthracis, Pseudo
monas fluorescenes, Saccharomyces
Aldrich, Fluka and Merck chemicals were cerevisiae and hensenula anomala. Culture
used. composition and preservation method on
Esters were synthesized from parent acids by medium was adopted [6]. Broth medium
dissolving a measured amount of benzoic acid bacteria cultured was done at 40 0C for 24 hr
in ethanol in presence of concentrated and stored at 8 0C [16] while the yeast were
sulphuric acid [11]. The composition was cultured at 30 0C for two days and stored at 8
0
refluxed for 4 hr and the product was purified C [6, 16]. Medial in the experimental and
by using methanol and distilled deionized control dishes were inoculated with
water. Synthesis of hydrazides were carried microorganisms to be tested. Addition of the
out by reacting the ester with hydra zine synthesized samples and the benzoic acid
hydrate at 1g per 1 ml proportion and refluxed used as reference was made to experimental
for 3 hr [9]. Hydrazones were synthesized by dishes at PH of 7.2 for bacteria and 5.5 for the
the reaction between 0.05 equimolar of yeast in three replicates for each inoculation.
benzaldehyde and hydrazides. The mixture The effect of the samples were studied from
was stirred magnetically and refluxed for 3 hr. comparing the microorganisms growth in the
The resulted crystals were purified by using control with the experimental samples and the
distilled-deionized water [12, 13]. Complexes reference. Difference between the control and
of 0.05m SrCl2. 6H2O with 0.05m the experimental samples was divided by
Benzoylhydrazine (BH), m-Nitrobenzoyl colonies in the control and obtained the results
hydrazine(m-NBH), p- in percentage to evaluate the microorganism
Nitrobezoylhydrazone(p-NBH), 3,5 Di inhibition. Effective doses to inhibit 50%
nitrobenzoylhydrazone (3,5-DNBH), m- (ED50) of the microorganism’s growth was
Aminobenzoylhydrazone (m-ABH) and p- obtained statistically from percentage
Aminobezoylhydrazone (pABH) in 40 ml of inhibition versus log of compound
methanol were synthesized [14]. The concentration. Analysis was done for both the
composition was stirred for 16 hr using bacteria and yeast and the means compared.
Griffin Minimag magnetic stirrer and refluxed
for 2 hr. Methanol was used to rinse the 3. RESULTS AND DISCUSSIONS
products, recrystallized and left to dry over
silica gel [14]. Looking at Table 1, the results of Melting
Physicochemical measurement was carried point of the hydrazone (Ligands) ranged
out. Philip Harris melting point apparatus was between 180-312 0C and colours were
used to obtain points of melting in hydrazones yellowish, brownish and whitish. Percentage
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These results show a good comparison with showed agreeable results from literature [14].
other ligands [17]. The hydra zones were Most complexes were brownish with
sparingly soluble in some organic solvents as exception of Sr(BH)3/2Cl2H2O and Sr(m-
demonstrated by m-aminobenzoylhydrazone NBH)Cl2 H2O which were off-white and grey
(mAB H) and p-aminobezoylhydrazone (p- respectively. Formation of colour complexes
ABH) in n-hexane and petroleum ether. by non-transition element had earlier been
However, most of the ligands are soluble in documented in literature [6]. The coordinated
tetrachloromethane. m-Nitro compounds melted between 210 and 312 0C
benzoylhydrazone(m-NBH) p-Nitrobe- which agreed with literature [6]. The
nzoylhydrazone(p-NBH) and mAmino- complexes were insoluble in water while
benzoylhydrazone (m-ABH) solubilize ed in nonaqueous gave different solubility
ethanol and benzene while 3,5- properties. Complexes of Sr(mNBH)Cl2.H2O,
dinitrobenzoylhydrazone(3,5-DN BH), m- Sr(p-NBH)3Cl2 H2 O and Sr(3,5-DNB
aminobenzoyl hydrazone(m-ABH) and p- H)3/2Cl2.H2O were soluble in benzene,
aminobezoylhydrazone (p-AB H) were tetrachloromethane and acetone compared to
soluble in methanol and acetone. These Sr(m-ABH)1/2Cl2.H2O and Sr(p-ABH)3/2Cl2
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.H2O that were soluble in benzene, ethanol, of the complexes. Complexes of magnesium
methanol and acetone. Sparingly solubility of and cadmium have shown similar
the complexes in some nonaqueous liquids stoichiometries [12].
could be an indication of polymerization Assignments of IR bands for the ligands and
effect [18, 19]. complexes are shown in Table 2.
Metal-ligand stoichiometries of 1:3/2 looking
at Table 1 proposed polymeric phenomenon
The assignments are due to bands difference These were proofs for phenolic oxygen
between the complexes and free ligands. The involvement in chelation with ion of the metal
characteristic peak changes between the which agreed with literature [4, 21]. The
complexes and the ligands suggested the bands at 1678-1698 cm-1 and 1668-1690 cm-1
binding involvement in the complexes [6]. were assigned to vC=O absorption of the
Appearance of some peaks in complexes and ligands and complexes, Table 2. Shifts
disappearance of others from the ligands occurred in the bands from 1689 to 1676,
suggested formation of the complexes. IR 1692 to 1668, 1698 to 1671, 1698 to 1683,
spectrum of the benzoylhydrazone (BH) 1692 to 1670 and 1678 to 1690) cm-1 of the
revealed peak at 3669 cm-1 which was benzoylhydrazone to Sr(BH)3/2Cl2H2O, m-
assigned to v(OH). There was a shift in the nitrobenzoylhy drazone to Sr(m-
band to 3652 cm-1 for the Sr(BH)3/2Cl2.H2O NBH)Cl2H2O p-nitro bezoylhydrazone to
complex indicating binding formation Sr(p-NBH)3Cl2 10H2O, 3,5–
between the metal and ligand oxygen after dinitrobenzoylhydrazone to Sr(3,5-
deprotonation in agreement with literature DNBH)3/2Cl2H2O, m-amino
[20]. There were also band shifts from 3659 benzoylhydrazone to [Sr(m-ABH)]1/2 Cl2H2O
cm-1 of m-Nitrobenzoylhydrazine(m-NBH) to and p-aminobezoylhydrazone to Sr(p-
3650 cm-1 of the Sr(m-NBH) Cl2.H2 O, 3668 ABH)3/2 respectively. Suggesting metal ion
cm-1 of 3,5-Dinitrobenzoylhy drazone(3,5- coordination with carbo nyl [4,14, 15]. The
DNBH) to 3650 cm-1 of Sr(3,5- bands at 1612 cm-1 to 1688 cm-1 were assigned
DNBH)3/2Cl2.H2O and 3666 cm-1 of p- to the CN stretching of the ligands and
Aminobezoylhydrazone(p-ABH) to 3652 cm- complexes. Bond coordinations were
1
of the Sr(p-ABH)3/2Cl2 .H2 O complexes. observed in Sr(m-NBH)) Cl2.H2O, Sr(3,5-DN
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S. C. B. P. S. H.
faecalis sporosenes anthracis fluorescenes cerevisiae anomala
(BH)3/2Cl2H2O 52.22 48.18 58.44 41.64 ±2.36 50.34 43.14
±2.28 ±2.14 ±2.15 ±2.44 ±3.29
Sr(BH)3/2Cl2H2O 84.24 ± 72.11 82.58 66.24 ±3.31 90.10 68.66
±3.18 ±2.46 ±3.13 ±2.14 ±3.29
(mNBH)Cl2H2O 44.23 ± 55.38 54.11 51.31 ±2.16 49.67 55.11
±2.62 ±2.26 ±2.26 ±3.29 ±2.65
Sr(mNBH)Cl2H2O 66.31 73.52 89.58 80.63 61.37 89.83
±2.88 ±3.12 ±3.33 ±2.88 ±3.80 ±2.19
(pNBH)3Cl210H2O 52.36 40.55 55.44 58.99 49.89 53.69
±3.14 ±2.11 ±2.36 ±2.33 ±2.65 ±2.32
Sr(p-NBH)3Cl2 10H2O 79.88 68.30 88.58 81.77 65.55 84.24
±2.22 ±2.33 ±3.33 ±2.32 ±2.15 ±3.32
(3,5-DNBH)3/2 Cl2H2O 46.41 61.20 58.88 50.55 48.02 55.11
±2.14 ±2.29 ±3.12 ±2.18 ±2.41 ±2.22
The values indicated degree of restric tion inhibited C. sporosenes (73.52 ± 3.12) and B.
after 96 hr of incubation. Control were anthracis (91.65 ± 3.16) at 70 and 88 ppm.
examined in the same manner. Mortality The (m-NBH)Cl2.H2O and (3,5-
efficacy of the hydrazones and complexes DNBH)3/2Cl2.H2O inhibited the micro
were observed between 50 and 250 ppm organisms at 101 and 108 ppm which also
concentration while 0 to 100% gave degree of proved that their complexes relatively require
growth inhibi tion. Complexes of low concentration for the microorganism
Sr(BH)3/2Cl2H2O and Sr(p-ABH)3/2Cl2.H2O growth inhibition. This correlates with similar
hindered growth of S. faecalis (84.24 ± 3.18) report [24]. The difference between complex
at 59 and 65 ppm (68.32 ± 2.61) while their concentration and ligand observed for the
benzoylhydrazone and p-amino microorganism hindrance could be attributed
benzoylhydrazone demonstrate inhibi tion to the cationic environment created by the
52.22 ± 2.28 and 43.12 ± 2.45 at 105 and 116 complexes. Inhibitory effect of Sr(m-
ppm respectively, suggesting that the ABH)1/2Cl2.H2O and Sr(pNBH)3)Cl2 10H2O
complexes show effectiveness at lower were observed at 69 ppm (from S. faecalis
concentration than the ligands. Sr(m- 75.18 ± 2.65 to H. anomala 86.54 ± 2.51 and
NBH)Cl2.H2O and Sr(3,5-DNBH)3/2Cl2.H2O
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78ppm (79.88 ± 2.22, 68.30 ± 2.33, 88.58 ± ABH)3/2Cl2.H2O were promi nent at 112 ppm.
3.33, 81.77 ± 2.32, 65.55 ± 2.15 and 84.24 ± Growth hindrance ability of Sr(p–
3.32) while their (m-ABH)1/2 Cl2.H2O and (p- NBH)3Cl2.10H2O was also evident at 118
NBH)3)Cl2.10H2O hydrazones showed ppm. The microor ganisms reacted to degree
effectiveness at 112 and 125 ppm as of inhibition of Sr(BH)3/2Cl2H2O and Sr(m-
demonstrated. Significant hindrance ability ABH)1/2 Cl2.H2O at 98 ppm and 105 ppm
was evident for the Sr(m-NBH)Cl2. H2O (table 4).
against the C. sporosenes at 70 ppm compared
with that 101 ppm of its ligand (m- 4. CONCLUSION
NBH)Cl2.H2O while Sr(p-ABH)3/2Cl2.H2O
showed activity again st the microorganism New compounds which demonstrated
growth at 116 ppm. Complexes of different properties from reactants were
Sr(BH)3/2)Cl2H2O and Sr(m–NBH))Cl2.H2O produced and purified for better utilization.
showed strong effect against B. anthracis at Preliminary constituents of the coordinated
86 ppm and 88 ppm respectively whereas compounds were established. However,
Sr(p–NBH)3Cl210H2O and Sr(3, 5–DN BH Structural determination of the complexes
)3/2Cl2.H2O gave 88.58 ± 3.33 and 91.65 ± were tentative pending future studies by X–
3.16 inhibitory activities on the B. anthracis ray to pursue further search for more
compared to Sr(m–ABH)1/2Cl2.H2O and Sr(p– effectiveness.
ABH )3/2Cl2. H2O which inhibited the Studies were carried out on antimicrobial
microorga nism (63.82 ± 2.02, 81.00 ± 3.16) properties of complexes against
at 125 ppm. Complexes of Sr(m NBH)Cl2 microorganisms. The ligands and complexes
.H2O and Sr(m ABH)1/2Cl2 .H2O were also demonstrated antimicrobial effect on the
effective at 105 and 99 ppm while growth microorganisms studied. Improved results can
inhibition 68.32 ± 2.61, 84.61 ± 3.52, 81.00 ± further be achieved through application of
3.16, 79.81 ± 2.71, 87.96 ± 3.65 and 92.27 ± nanotechnology both in preparation and
3.62 were observed at 144 ppm for Sr(p– antimicrobial effectiveness of the compounds
NBH)3Cl2.10H2O. Complex of Sr(m– on further research.
NBH)Cl2.H2O produce growth inhibi tion Minimum effective concentration values were
against the bacteria and the yeast at 120 ppm estimated statistically through percentage
while the inhibition poten cy of inhibition versus log of sample concentration
Sr(BH)3/2Cl2H2O, Sr(m–ABH)1/2 Cl2.H2O, to determine effective dose for inhibition at 50
Sr(3, 5–DNBH)3/2Cl2. H2O and Sr(p– % (ED50) microorganism growth.
REFERENCES
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