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Advancement and Validation of New Derivative Spectrophotometric Method for Individual and Simultaneous Estimation of Diclofenac sodium and Nicotinamide

Samar Ahmed Darweesh, Husam Saleem Khalaf, Rokayia Samir Al-Khalisy, Hamsa Muneam Yaseenand Ruaa Muayed Mahmood

Department of Chemistry, College of Education for Pure Science-Ibn Al-Haitham, University of Baghdad, Baghdad, Iraq.

Corresponding Author E-mail: husam250@yahoo.com

DOI : http://dx.doi.org/10.13005/ojc/340357

Article Publishing History
Article Received on : February 27, 2018
Article Accepted on : April 03, 2018
Article Published : 06 May 2018
Article Metrics
ABSTRACT:

Derivative spectrophotometry, which is primarily based on the first and second derivative spectra of absorption, was applied for individual and simultaneous spectrophotometric determination of Diclofenac sodium (DS) and nicotinamide (NAM) in the ultraviolet region. The method depends on 1st and 2nd derivative UV spectrophotometry, with the amplitude of peak-to-base line, peak to peak, the area under peak at selected spectrum intervals and zero-crossing at certain wavelengths for each compound measurement. Under optimal conditions, a linear working range of 5-80 μg.ml-1 and 10-140 μg.ml-1 for (DS) and (NAM) with correlation coefficient R2 between 0.9938-0.9998. The mean % recoveries were found to be in the range of 97.95-102.50 % for two drugs. The proposed technique has been effectively applied to the estimation of (DS) and (NAM) in pharmaceutical formulations.

KEYWORDS:

UV-Visible Spectrophotometer; Derivative Spectrophotometric Method; Simultaneous Determination; Diclofenac Sodium; Nicotinamide

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Darweesh S. A, Khalaf H. S, Al-Khalisy R. S, Yaseen H. M, Mahmood R. M. Advancement and Validation of New Derivative Spectrophotometric Method for Individual and Simultaneous Estimation of Diclofenac sodium and Nicotinamide. Orient J Chem 2018;34(3).


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Darweesh S. A, Khalaf H. S, Al-Khalisy R. S, Yaseen H. M, Mahmood R. M. Advancement and Validation of New Derivative Spectrophotometric Method for Individual and Simultaneous Estimation of Diclofenac sodium and Nicotinamide. Orient J Chem 2018;34(3). Available from: http://www.orientjchem.org/?p=45434


Introduction

Derivative spectrophotometry is a technique of incredible usefulness for separating both qualitative and quantitative information from spectra made of uncertain bands by utilizing the first or higher derivatives of absorbance concerning wavelength[1]. This technique offers different advantages over the customary absorbance methods, for example: the separation of the sharp spectral features over the huge bands and the improvement of the resolution of overlapping spectra[2] what’s more, allow the assay of certain analyses from complex mixtures or matrices via mathematical interpretation of the absorption signal [3]. UV-Vis spectroscopic approach for analysis is broadly utilized within the determination of drug in pharmaceutical preparations and for separation studies, which disposes interference from the formulation of matrix by utilizing zero-crossing techniques[4].

Many reports were found for the analysis in individual form particularly for (DS) and (NAM) including spectrophotometric method [5-8], chromatographic method [9,10], flow injection [11], voltammetry [12], potentiometric [13], electrochemical method [14], capillary electrophoresis [15,16].

Experimental

Instruments           

[UV]-Visible double beam spectrophotometer with 10 mm quartz cell shimadzu 1800, a personal computer.

Chemicals and reagents

Pharmaceutical grade (DS) and (NAM) powder received in pure form (99.99 %) was provided as an endowment from the State Company for Drug manufacture and Medical Appliances Samara-Iraq (SDI), methanol (99.7 %) provide by (SCR). All chemical substance utilized were of analytical grade.

Preparation of standard stock solution (200 µg. mL-1), Diclofenac sodium and nicotinamide

The standard solution of (DS) and (NAM) were prepared by dissolving accurate weighted 20.0 mg of pure drug in 10.0 ml of methanol and further diluted to 100 ml with distilled water.

Preparation both Diclofenac sodium and nicotinamide from dosage form

The content of 10 tablets and capsules was grinded and blended well. Take accurately weighted from a specific quantity of the fine powder to give an equivalent to 50 mg for (DS) tablets and 20 mg for (NAM) capsules and dissolve in ten mL of methanol then diluted to the mark with distilled water in a volumetric flask 100 ml. The solution was filtered by utilizing filter paper (Whatman No.41) to evade any undissolved or suspended components before use; also the first part of the solution filtrate was rejected.

Procedures

Individual determination of Diclofenac sodium and nicotinamide

In 10 mL calibrated flask transfer aliquots of (DS) standard solutions containing 50-800 μg (or NAM standard solutions containing 100-1400 μg), and dilute with 10 % methanol solution to the mark. The spectrum for each solution was recorded against a 10 % methanol solution as blank. Zero order spectrums were then manipulated for each to get its first derivative (D1) and second derivative (D2).

Simultaneous determination of Diclofenac sodium and nicotinamide

The content of a series of 10 mL calibrated flasks containing different amounts (50-800) μg of (DS) standard solutions and 50 μg of (NAM) solution the mixture was then diluted with 10 % methanol solution to the mark. Record the spectrum for each solution against a 10 % methanol solution as a blank. The recorded spectra were then manipulated to get D1 and D2.(II) The content of a series of 10 mL calibrated flasks containing different amounts (100-1400) μg of (NAM) standard solutions and 100 μgof (DS) solution the mixture was then diluted with 10 % methanol solution to the mark. The spectrum for each solution was recorded against a 10 % methanol solution as a blank. The recorded spectra were then manipulated to get D1 and D2.

Result and Discussion

Absorption spectra

The absorption spectra were record of each compounds (DS), (NAM) then their mixture against 10 % methanol solution as a blank. Figure 1 (a) demonstrates the absorption spectrum of (DS) 10 μg. mL-1 with maximum wavelength at 276 nm, (b) demonstrates the absorption spectrum of (NAM) 50 μg. mL-1 with two maxima wavelength of absorption at 214 nm and 262 nm. The aggregate spectrum to the mixture is demonstrating in (c) with two λmax 212 and 266 nm.

Figure 1: Absorption spectra of: (A) 10 μg. mL-1 (DS), (B) 50 μg. mL-1 (NAM) and (C) a mixture of 10 μg. mL-1 Diclofenac sodium and 50 μg. mL-1 nicotinamide.

Figure 1: Absorption spectra of: (A) 10 μg. mL-1 (DS), (B) 50 μg. mL-1 (NAM) and (C) a mixture of 10 μg. mL-1 Diclofenac sodium and 50 μg. mL-1 nicotinamide.


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First derivative mode and 2nd derivative mode    

The derivative spectra 1st, 2nd order of (DS) and (NAM) and for their blend are appeared within Figure 2, Figure 3 respectively. Clearly there is a large overlap in spectra of Diclofenac sodium and nicotinamide hence, their determination, making use of the zero order absorption measurements, at the point when present in the same solution it is very difficult when utilizing customary two wavelengths of λmax or the tangential base-line approach strategies [17]. Then again, derivative technique is of a specific utility in finding the concentration of single component in a blends, with a large overlapping in spectrum. Consequently, both first, second order derivative spectrophotometric methods have been applied.

In the existing work, graphically peak-to-baseline, peak to peak, zero-crossing technique in addition to peak area were utilized to deal with derivatives spectra to complete the data. Truth be told, the any one of these techniques in the 1st and 2nd derivative modes indicate good proportion to Diclofenac sodium and nicotinamide amounts in their blends.

Figure 2: 1st derivative spectra of (A) 10 μg. mL-1 Diclofenac sodium, (B) 50 μg. mL-1 nicotinamide and (C) a mixture of 10 μg. mL-1 Diclofenac sodium and 50 μg. mL-1 nicotinamide.

Figure 2: 1st derivative spectra of (A) 10 μg. mL-1 Diclofenac sodium, (B) 50 μg. mL-1 nicotinamide and (C) a mixture of 10 μg. mL-1 Diclofenac sodium and 50 μg. mL-1 nicotinamide.



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Figure 3: 2nd derivative spectra of (A) 10 μg. mL-1 Diclofenac sodium, (B) 50 μg. mL-1 nicotinamide and (C) a mixture of 10 μg. mL-1 Diclofenac sodium and 50 μg. mL-1 nicotinamide.

Figure 3: 2nd derivative spectra of (A) 10 μg. mL-1 Diclofenac sodium, (B) 50 μg. mL-1 nicotinamide and (C) a mixture of 10 μg. mL-1 Diclofenac sodium and 50 μg. mL-1 nicotinamide.



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Figure 4 and Figure 5 illustrate sets of 1st order spectra of medley containing (5-80) μg.ml-1 of Diclofenac sodium in the existence of (5 μg.ml-1) nicotinamide and (10-140) μg.ml-1 of nicotinamide in the existence of    (10 μg.ml-1) Diclofenac sodium respectively. Figure 4 indicate that when the amount of nicotinamide is kept constant and varied the concentration of Diclofenac sodium, the peak-to-base line, peak to peak, peak areas and zero crossing of nicotinamide were proportional to the concentration of Diclofenac sodium. Moreover, the same features were found for the determination of nicotinamide in Figure 5, i.e. area under peak, peak-to-baseline, peak to peak and zero crossing of Diclofenac sodium were in proportion to the concentration of nicotinamide (Table 1 and 2).

Figure 4: First derivative spectra of mixture contain (5, 10, 20, 40, 60 and 80 μg. mL-1); Diclofenac sodium with (5 μg. mL-1) nicotinamide. Figure 4: First derivative spectra of mixture contain (5, 10, 20, 40, 60 and 80 μg. mL-1); Diclofenac sodium with (5 μg. mL-1) nicotinamide. 

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Figure 5: First derivative spectra of mixture contain (10, 20, 50, 70, 100 and 140 μg. mL-1); nicotinamide with (10 μg. mL-1) diclofenac sodium.

Figure 5: First derivative spectra of mixture contain (10, 20, 50, 70, 100 and 140 μg. mL-1); nicotinamide with (10 μg. mL-1) diclofenac sodium.



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In the further sets of 2nd derivative of the same above blend, as illustrated in Figure 6 and Figure 7. By applying the same mentioned approached in account peak amplitudes (in millimeter) at peak-to-baseline, peak to peak and at zero crossing point of the other compound, and peak areas at selected wavelengths intervals enable the measurement of Diclofenac sodium and nicotinamide respectively (Table 1 and 2).

Figure 6: Second derivative spectra of mixture contain (5, 10, 20, 40, 60 and 80 μg. mL-1); Diclofenac sodium in existence of (5 μg. mL-1) nicotinamide.

Figure 6: Second derivative spectra of mixture contain (5, 10, 20, 40, 60 and 80 μg. mL-1); Diclofenac sodium in existence of (5 μg. mL-1) nicotinamide.



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Figure 7: Second derivative spectra of mixture contain (10, 20, 50, 70, 100 and 140 μg. mL-1); nicotinamide in existence of (10 μg. mL-1) Diclofenac sodium.

Figure 7: Second derivative spectra of mixture contain (10, 20, 50, 70, 100 and 140 μg. mL-1); nicotinamide in existence of (10 μg. mL-1) Diclofenac sodium.



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Table 1: Statistical analysis for the determination of Diclofenac sodium.

Drug Order of derivative Mode of calculations λ  (nm) Regression equation Slope
Diclofenac sodium First Peak to baseline 259 y = 0.0011x + 0.0014 0.9955 0.0011
Peak to baseline 295 y = -0.0013x + 0.0002 0.9955 -0.0013
Peak to peak 259-295 y = 0.0024x + 0.0012 0.9955 0.0024
Area under peak 248.5-276 y = 0.0188x – 0.0095 0.9961 0.0188
Area under peak 276-334 y = -0.0367x + 0.1702 0.9944 -0.0367
Zero cross 260 y = 0.0011x + 0.0008 0.9948 0.0011
Zero cross 296 y = -0.0013x + 0.0001 0.9955 -0.0013
Second Peak to baseline 247 y = 0.0002x + 0.0004 0.9965 0.0002
Peak to baseline 310 y = 7E-05x – 3E-05 0.9961 7.00E-05
Area under peak 239-260 y = 0.0017x + 0.0011 0.9988 0.0017
Area under peak 260-294 y = -0.0027x + 0.0154 0.9961 -0.0027
Area under peak 294-340 y = 0.0013x – 0.0005 0.9988 0.0013
Zero cross 252 y = 0.0001x + 0.0002 0.9955 0.0001
Zero cross 272 y = -0.0001x – 0.0002 0.9938 -0.0001
Zero cross 310 y = 7E-05x – 3E-05 0.9961 7.00E-05


Table 2: Statistical analysis for the determination of nicotinamide.

Drug Order of derivative Mode of calculations λ  (nm) Regression equation Slope
Nicotinamide First Peak to baseline 253 y = 0.0007x + 0.0057 0.9994 0.0007
Peak to baseline 272 y = -0.0021x + 0.0068 0.9998 -0.0021
Peak to peak 253-272 y = 0.0028x – 0.0011 0.9998 0.0028
Area under peak 244.5-261 y = 0.0074x + 0.0393 0.9995 0.0074
Area under peak 261-334 y = -0.0256x – 0.5788 0.999 -0.0256
Zero cross 248 y = 0.0005x – 0.0009 0.9998 0.0005
Zero cross 276 y = -0.0014x + 0.0017 0.9997 -0.0014
Second Peak to baseline 244 y = 0.0002x + 0.0013 0.9995 0.0002
Peak to baseline 262 y = -0.0004x + 6E-05 0.9998 -0.0004
Peak to baseline 270 y = -0.0003x – 0.0006 0.9995 -0.0003
Peak to baseline 275 y = 0.0003x – 0.0013 0.9996 0.0003
Peak to peak 270-275 y = 0.0006x – 0.0003 0.9992 0.0006
Area under peak 272-329 y = 0.0039x + 0.0235 0.9995 0.0039

 

Accuracy and Precision

Under the optimum conditions, the accuracy and precision of the proposed method (peak to baseline, zero cross and area under the peak for each of first and second order derivative modes) were checked. Table 3 shows the values of relative error percent and relative standard deviation percent for two different level of concentration of Diclofenac sodium and nicotinamide with three replicate.

Table 3: Accuracy and precision of the methods.

Drug

Approach of analysis

Wavelengths

λ  (nm)

Taken (μg.ml-1)

Found *

(μg.ml-1)

RE%

*RSD%

Diclofenac sodium

First order

(area under peak)

248.5-276

30.00

30.34

1.133

2.130

60.00

59.57

-0.717

0.499

Second order

(area under peak)

239-260

30.00

29.62

-1.267

0.668

60.00

60.55

0.917

0.365

nicotinamide

First order

(zero cross)

248

50.00

49.70

-0.600

0.748

100.00

99.45

-0.550

0.235

Second order

(peak to base line)

262

50.00

50.38

0.760

0.878

100.00

99.67

-0.330

0.277

 

*Average of three determinations.

Application in dosage form

The proposed method first and second procedures were successfully applied for direct determination of Diclofenac sodium in tablets and nicotinamide in capsules. The results obtained are presented in Table 4, and are in quite agreement with the spiked values. Good recovery 97.95-102.50 % and RSD % values 0.667-2.005 % indicated the suitability of these methods for routine analysis of Diclofenac sodium and nicotinamide.

Table 4: Results for analysis of Diclofenac sodium and nicotinamide in four pharmaceutical formulation samples.

Pharmaceutical preparation

Method of analysis

λ(nm)

amount (mg)

 Rec.%  *RSD %

Taken

Found*

Olfen-50

Acion

switzerland

First order

(area under peak)

248.5-276.0

50.00

50.41

100.82

0.778

Second order

(area under peak)

239.0-260.0

50.00

49.68

99.36

0.702

Optifenac-50

M. H. drugs

India

First order

(area under peak)

248.5-276.0

50.00

49.54

99.08

0.667

First order

(area under peak)

239.0-260.0

50.00

49.25

98.50

0.806

Modoplex Caps

M. V. C.

India

First order

(zero cross)

248.0

20.00

19.70

98.50

2.005

Second order

(peak to base line)

262.0

20.00

20.28

101.40

1.482

P-blex Caps

S. D. I.

Iraq

First order

(zero cross)

248.0

20.00

20.50

102.50

0.959

Second order

(peak to base line)

262.0

20.00

19.59

97.95

1.244

 

*Average of three determinations.

Conclusion

Derivative Spectrophotometric technique was found to be sensitive, simple, rapid, economical, the results indicates that a good accuracy and precision of the proposed method, good recovery from the results applications in dosage form and it can be used in routine analysis of Diclofenac sodium and nicotinamide in their pure forms, dosage form without prior separation or treatment.

In this work, 1st and 2nd derivative modes indicate good proportion to Diclofenac sodium and nicotinamide amounts in pure form and in their blends, by graphically peak-to-baseline, peak to peak, zero-crossing technique in addition to peak area were utilized to deal with derivatives spectra to complete the data.

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