Synthesis of 3-[3-Phenylpyrazylazo]-2, 7-naphthalendiol as new chromogenic reagent for the determination of Nickel (II) in nails of human.

 

Abdulhameed M. Abdulhameed, Hussain J. Mohammed^*

 

ABSTRACT:

The procedure was found to be convenient for the routine analysis of trace amount of Nickel (II) in aqueous media. The method is based on the formation of a 1:2 complex with 3-(3-phenylpyrazylazo)2, 7-naphthalendiol (3PPAN) as a new reagent is advanced. The complex has a maximum absorption at 501 nm and ε max of 4x10 ⁴ L. mol^-1. cm^-1 A linear correlation (2.5 –20. 0 μg. ml^-1) was found between absorbance at λ max and concentration. The accuracy and reproducibility of the determination method for various known amounts of Nickel (II) were tested. The results obtained are both precise (RSD was 2.50%) and accurate (relative error was 2.50 %). The effect of diverse ions on the determination of Nickel (II) to investigate the selectivity of the method were also studied. The stability constant of the product was 0.41X10 ¹⁰ L. mol^-1. The method was successfully utilized to the limitation of Ni (II) ion in analytical and nails samples.

 

 

 

INTRODUCTION:

Heterocyclic azo dyes are a versatile class of colored compounds that have attracted the interest of many researchers, due to of their multiple applications in the fields of industries such as papers, textiles, additives, foodstuffs, cosmetics, leather, laser materials, organic solar cells and as materials for xerography^1-3. Literature date show that pyrozolone azo derivative compounds containing N, O donor atoms have the ability to configure the complexes with transition and non-transition metal ions due to sensitive colour, stability and very good chelatogenic characteristics^4-8.

 

Nickel play great role in the biological systems and used in many industries. Nickel forms many complexes the biological systems, ingredient of some bioactive molecules of enzymes and also in the storage and transport of active substances^9-11.

 

The biological complexes of nickel are important bioenzymes and have role in the biological systems. Important coenzymes studied are: methyl coenzyme, urease and acetyl coenzyme¹². Several device methods are present in the letters used to determine ion, and these method electrochemical methods¹³¹⁴, spectrophotometric techniques^15-20, inductively coupled plasma atomic emissions spectrometry.^21,22 and flame and electro thermal absorption spectrometry^23,24 show good sensitivity but is limited because of expensive instrumentation and high cost for routine analysis.

 

According to the best of our knowledge, this reagent has not been reported in the literature as being used for any cation determination. In this study, we wish  introduce a new chromogenic reagent the 3-(3-phenylpyrazylazo)2, 7-naphthalendiol (3PPAN) as a selective reagent in spectrophotometric determination of micro a mounts of Nickel (II).

 

MATERIALS AND METHODS:

I/ Preparation of the reagent ((3PPAN))

The reagent was prepared by coupling 2, 7-naphthlendiol with diazotate 3-amino-5-phenylpyrazole solution. A diazonium solution was prepared by taking 0.4922 g of 3-amino-5-phenylpyrazole in 50 mL of ethanol and concentrated hydrochloric acid with 5 mL of distilled water and adding sodium nitrite solution drop wise at 0-5°C. 2, 7-naphthlendiol 0.5013 g was dissolved in 100 mL of ethanol and 30 mL of 0. 1 M were added at (0-5^oC). The mixture was left to stand overnight. The precipitate was filtered off and recrystallized from ethanol ²⁵ Scheme1.

 

 

Scheme 1: Preparation of reagent (3PPAN)

 

Preparation of Nickel (II)complex:

The complex was prepared by stoichiometric amount from ligand in 50 mL of ethanol then added drop wise with stirring to a stoichiometric amount 1:2 for Nicke salt in 25 mL hot distilled water. The solid greenish black product thus formed off, washed with ethanol and dried.

 

Apparatus :

Spectrophotometric measurement were made with UV-Vis Spectrophotometer (LIBRA S60)double beam spectrophotometer using 1. 00 cm glass cells. Vibrational spectra were recorded on Test scan Testscan, (FTIR 8000 Series), Japan. Measurements of pH were made using an Hanna, HI9811-5 pH – meter equipped with a glass – saturated calomel combined electrode Melting points of both ligand and complex were obtained with an electrothermal melting point apparatus. Conductivity was measured in DMSO (10-3) solution with an Alpha digital conductivity model -800.

 

Reagents:

All chemicals used were of analytical grades

Nickel (II) stock solution (100 μg. ml-1)

prepared by dissolving 0. 05 g of Nickel chloride in 500 ml of distilled water, working standard of Ni (II) solutions were prepared by simple dilution of the appropriate volume of the standard Ni (II) solution (100 μg. ml-1) with distilled water. 3-(3-phenylpyrazylazo)2, 7-naphthalendiol (3PPAN) (1 mM) 0. 1048 g of reagent was dissolved in 250 ml of ethanol

 

 

Foreign ion solutions (10 μg. ml-1):

These solutions were prepared by dissolved an amount of the compound in distilled water completing the volume in a volumetric flask.

 

General Procedure:

In to a series of 10 ml calibrated flask, transfer increasing volumes of Ni(II) working solution 10 ppm to cover the range of calibration curve, add 2. 0 ml of 1Mm of (3PPAN) solution and pH was adjusted to 4.5. The complexes formed were solubilized in water and diluted up to 10 ml in a standard flask. The absorbance of the resulting solution was measured at the respective absorption maxima against a reagent blank prepared under similar condition.

 

RESULTS AND DISCUSSION:

Spectra:

The result of this work indicated that the reaction of Ni (II) with (3PPAN) at pH 4.5 yield highly soluble product which can be utilized as a suitable assay procedure for Ni (II). This product has a maximum absorption at 458 nm at which the blank at this wavelength shows zero absorbance. The spectrum of (3PPAN)solution gives strong absorption band belongs to n→π* of +nm and with shoulder band due to transition π→π* of C=N group Fig. 1.

 

The bands of N=N and C=N were shifted to broad peak at high wavelength with high intensity at 501. 0 nm upon complexation due to transition of π→π* charge transfer²⁶. Fig. 2

 

Figure 1: Absorption spectrum of the reagent (3PPAN) against ethanol as blank

 

 

Figure 2: Absorption spectrum of [Ni (3PPAN)₂] complex treated as described under procedure and against a reagent blank.

 

Solvatochromism study of 3-(3-phenylpyrazylazo)2, 7-naphthalendio Compound:

To determination of solvate chromic range of azo dyes according to sensitivity to solvent change by using UV-Visible, more than (18) empirical scales of solvent polarity has been used, i. e Et (30) scale has more comprehensive applications for characterization of the chromatographic materials and polarity of polymers in addition of measurements of the polarity of all type of solvents, electrolyte solution and binary solvent mixture^27-29. The popular comparison methods of solvatochromic, demonstrated by Kamlet and Taft and improved by Abraham, Carr and Abbound has been to explain the solvent effect. A solvatochromic equation with three parameters л*, β and, α can be used to determine two type hydrogen bonding ²⁸. The absorption spectra of dye carried out over the range between 190-600 nm in various selected solvent and the results are summarized in Table 1. The effect of the solvents on the azo-hydrazone tautomeric equilibrium was investigated Scheme.2. Dye of 3-(3-phenylpyrazylazo)2, 7-naphthalendio showed a week peak at region 190-300 nm assigned to hydrazone tautomeric form at 370-600 nm ²⁹. Dye showed the positive solvatochromism due to the absorbance of the first band was decreased via increasing solvent polarity. This mean that the excitation state more stable and have polarity different form ground state. It was also observed that the negative solvatochromism exhibit by the second band absorbance it was increase via increasing solvent polarity and it shifted to lower wavelength³⁰ Fig. 3.

 

Table 1: Influence of solvent on maximum wavelength of (3PPAN)

 

 

 

Scheme 2 The equilibrium between the azo form and the hydrazone form of 3-(3-phenylpyrazylazo)2, 7-naphthalendio

 

 

 

 

 

Figure 3: Absorption spectra of the reagent (3PPAN) in different solvents

 

The effect of various parameters on the absorbance intensity of the formed products were studied and the reaction conditions were optimized

 

Effect of pH:

The pH of metal complex solutions was adjusted using dilute buffer solutions (0. 01M) CH₃COONH₂, NH₄OH and CH₃COOH and the effect on absorbance was studied Fig. 4. The absorbance of the complex was maximum and constant in the pH range given in Table 2.

 

 

Figure 4: Effect of pH

 

Table 2: Analytical characteristics of Ni[(3PPAN)2] complex.

Characteristic Ni (II) – complex
Absorption maximum (nm)	501
Beer’s law range (ppm)	(2.5– 20.0)
pH	-4.5
Sandell’s sensitivity (μg. cm-2)	1 x 10-2
Molar absorptivity (L. mol-1. cm-1)	4 x 104
Stability constant (L. mol-1)	0.41 x 10 10
Melting point for reagent	345-347 C
Melting point for Ni (II) – complex	240-242 C

 

 

Figure 5: Effect of (3PPAN) concentration

Effect of (3PPAN) concentration:

Various concentration of (3PPAN) was added to fixed concentration of Ni (II). 2. 0 ml of 1. 0mM (3PPAN) solution was sufficient and gave minimum blank value was increased causing a decrease in the absorbance of the sample. Therefore, 2ml of 1 mM of (3PPAN) was usedin all subsequent experiment Fig. 5.

 

Effect of reaction time:

The colour intensity reached a maximum after the Ni (II) has been reacted immediately with (3PPAN) and became stable after one minute, therefore one-minute development time was selected as optimum in the general procedure. The colour obtained was stable for a least 24 hours.

 

Effect of temperature:

The effect of temperature on the colour intensity of the product was studied. In practice, the same absorbance was obtained when the colour was developed at room temperature (25 – 30°C), but when the volumetric flask were placed in a water –bath at (40-60°C) a loss in colour intensity and stability were observed, therefore it is recommended that the colour reaction should be carried out at room temperature form 25-45 C° for complex Figure 6.

 

 

Figure 6: Effect of temperatures on Ni [(3PPAN)₂] complex

 

Calibration graph:

The calibration equation for (2.5– 20.0 μg per ml)Ni (II) is Y = 0. 0792x + 0. 0049 (R2 = 0. 9993). Since the coloured complex is stable for 24 hrs, the method can be applied to large series of samples. The molar absorptivity and sandell٫ sensitivity are given in Table 2.

 

Composition of the complex:

The composition of complex was studied in the excess of reagent solution by the mole-ratio and Job s methods Fig. 7, 8. A break at a 1:2 (M:L)mole ratio suggested the formation of complex where M= Ni(II) and L= (3PPAN) under the given condition.

 

Conductivity measurements:

The solubility of the complexes in dimethyl sulfoxide and methanol permitted of the molar conductivity of 10^-3 M solution at 25°C and by comparison, the electrolytic nature for complexes. The low values of the molar conductance data listed in Table. 3 indicate that the complexes are non-electrolytes.

 

Table 3: Conductivity values of Ni[(3PPAN)₂] complex, s.mol^-1.cm²

Molar conductivity in methanol	Molar conductivity in methanol	Molar conductivity in methanol
12.2	10.3	8.1

FT. IR of reagent and its complex:

 

The FT. IR of the free ligand and it’s metal chelate were carried out in the (400-4000) cm-1Range. The IR bands of the (3PPAN) and its Ni (II) complex with their probable assignment are given in Table. 4. The IR spectrum of ligand shows a broad band at 3387 cm^-1 corresponding to O-H. This band is shifted to lower with low intensity at 3157 cm^-1 frequency value upon complexation suggesting chelation via the (M-O)³¹ However, the υ(N=N) stretching band in the free ligand is weak because of the non-polar nature of the bond observed at 1575 cm^-1.This band is shifted to lower with low intensity at 1544 cm^-1 frequency value upon complexation suggesting chelation via the (M-N)³². Fig 9, 10.

 

 

Figure 7: mole-ratio method for Ni [(3PPAN)2] complex

 

 

Figure 8: Job s method for Ni [(3PPAN)2] complex

 

Fig. 9 FT.IR for the reagent

 

Fig. 10 FT.IR for the Ni[(3PPAN)₂] complex

On the basis of the FT.IR, stoichiometric, and molar conductivity data the structure of complex can be suggested as the following:

 

 

Structure of Ni[(3PPAN)₂]

 

Applications:

Estimation of Ni(II) in the nails sample taken from male and female in (20-40) years old:

The sample was prepared for determination by two steps:

Step one:

washing prosses, after collecting the nails from human, washed by Triton X-100 v/v, 1% solution three times, after that, sample kept in deionized water for 3 minutes. Then, sample transform into 100 ml baker and 25 ml of acetone is added to remove the trash for 20 minutes. The sample washed by distelled water three times and get dried for 1 hour in oven at (110 ^оC).

 

Step two:

sample preparing for determination. (0.7019 gm)from sample has been taken and burn at (300^оC) for 15 minutes, 10 ml of HNO₃:HClO₄ 6:1 added to the sample, after that, sample kept at room temperature for 24 hour. Finally, sample kept in oven at (160 – 180^оC) until its concentrated to 2 ml, and moved into 50 ml volumetric flask, the volume completed by 0.1 M HNO₃.

 

Sample is ready for UV-Visible and atomic absorption spectrometric analysis³³. The results are shown in Table 4, indicate that satisfactory precision and accuracy could be attained with proposed method.

 

Table 4: Determination of Ni(II) in human beings nails.

*Amount found by our spectrophotometric method (ppm)	*Amount found by atomic absorption (ppm)
0.4833	0.612

*For five determinations

 

ACKNOWLEDGEMENT:

The authors grateful to the department of chemistry college of Science university of kufa to complete the requirements of research

 

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Accepted on 24.11.2017        © RJPT All right reserved

Research J. Pharm. and Tech 2018; 11(4): 1355-1360.