Conseguences of soil crude oil pollution on some wood properties of olive trees https://doi.org/10.30526/31.2.1960 Chemistry | 86 2018( عام 2العدد ) 13المجلد مجلة إبن الهيثم للعلوم الصرفة والتطبيقية Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 31 (2) 2018 Two Derivative Spectrophotometric Methods for the Simultaneous Determination of 4-AminoAntipyrine in Presence of Its Acidic Products Ruba Fahmi Abbas Dept. of Chemistry/ Collage of Science/ Al-Mustansiryiah University rubaf1983@uomustansiriyah.edu.iq Received in:10/October/2017, Accepted in: 6/December/2017 Abstract Simple, economic and sensitive mathematical spectrophotometric methods were developed for the estimation 4-aminoantipyrine in presence of its acidic product. The estimation of binary mixture 4-aminoantipyrine and its acidic product was achieved by first derivative and second derivative spectrophotometric methods by applying zero-crossing at (valley 255.9nm and 234.5nm) for 4-aminoantipyrine and (peak 243.3 nm and 227.3nm) for acidic product. The value of coefficient of determination for the liner graphs were not less than 0.996 and the recovery percentage were found to be in the range from 96.555 to 102.160. Normal ratio spectrophotometric method 0DD was used 50 mg/l acidic product as a divisor and then measured at 299.9 nm with correlation coefficient 0.998 and limit of detection 0.04098. ratio derivative methods 1DD and 2DD; are based on measuring the first derivative and second derivative for normal ratio spectrum at (peak 290.7 nm and valley 310 nm) for 1DD and (peak 286, valley 301 and peak 316nm) for 2DD the correlation coefficient for linearity graph not less than 0.997 and the recovery percentage were found to be in the range from 99.64 to 100.11. Keyword: 4-Aminoantipyrine; zero-crossing; spectrophotometric; ratio derivative; 1DD and 2DD. https://doi.org/10.30526/31.2.1960 mailto:rubaf1983@uomustansiriyah.edu.iq https://doi.org/10.30526/31.2.1960 Chemistry | 87 2018( عام 2العدد ) 13لمجلد ا مجلة إبن الهيثم للعلوم الصرفة والتطبيقية Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 31 (2) 2018 Introduction 4-Aminoantipyrine(4AAP) is an antipyretic, analgesic and anti-inflammatory properties [1]. It is used as a reagent for biochemical reactions producing phenol or peroxides [2], and used for the estimation of drugs via oxidative coupling reaction forming coloured products [3- 5]. There are many methods for the determination of 4-Aminoantipyrine including electrochemical method based on fabrication of multi walled carbon nanotube electrodes for the estimation toxic drugs 4-Aminoantipyrine [6], solid-phase spectrophotometry [7], electrochemical method by using graphite pencil electrode [8], capillary electrophoresis [9] and LC/Mass spectrometry [10]. On the other hand, spectrophotometric methods such as zero-crossing [11-12] and ratio derivative [13-14] methods are still favorite studies because of the simplicity, accuracy and availability of the instrumentation [15-16]. Therefore, the aim of this study is to develop rapid, simple and inexpensive spectrophotometric methods for the analysis of 4- Aminoantipyrine in the presence of its acidic product without chemical process separation. Furthermore, the zero-crossing and ratio derivative spectrophotometric methods could be used for the estimation of 4-Aminoantipyrine without any interference from its acidic product. Experimental Instruments 1. Uv-Visble spectrophotometer (model 1650 PC, SHEMADZU, Japan) with software program. 2. FTIR spectrophotometer (SHEMADZU, Japan) Materials Standard pure powder of 4-Aminoantipyrine (Sigma-Aldrich) (C11H13N3O) (M.wt= 203.24 gm/mol) and hydrochloric acid(BHD) prepared by 2N aqueous solution. a. Preparation of acidic product for IR- spectral 0.01 gm of pure 4-Aminoantipyrine was refluxed with 100 ml 2N HCl for 60 min. after cooling, the solution was evaporated to dryness by using oven at 700C, the residue was extracted with ethanol, filtered and then dried in air. The separated acidic product was subjected to IR spectral analysis [17-18]. b. Preparation of standard solutions 1. 4-Aminoantipyrine stock standard solution 100mg/l was prepared by dissolving 0.01 gm of pure 4-Aminoantipyrine with distilled water and then complete to the 100ml with the same solvent. After then different volumes of 4-Aminoantipyrine stock standard solution (100mg/l) ranging from (2.5 ml to 17.5 ml) were transferred into a series of 25 ml volumetric flasks and completed to the mark with distilled water to obtain a range of concentrations from (10 to 70 mg/l). https://doi.org/10.30526/31.2.1960 https://doi.org/10.30526/31.2.1960 Chemistry | 88 2018( عام 2العدد ) 13لمجلد ا مجلة إبن الهيثم للعلوم الصرفة والتطبيقية Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 31 (2) 2018 2. 4-Aminoantipyrine acidic product stock standard solution was prepared by refluxing 0.01 gm of pure 4-Aminoantipyrine with 100ml 2N HCl for 60 min. after cooling, were transferred into a series of (2.5, 5, 7.5, 10, 12.5, 15, 17.5 ml) of this solution to 25 ml volumetric flasks and complete to the mark with distilled water to obtain the acidic product solutions in the concentration range of (10 to 70 mg/l). Procedure a. Zero-crossing method 1. The first derivative 1D and second derivative 2D of the uv spectrum of pure 4- Aminoantipyrine standard solutions were measured. Two calibration graphs were obtained by plotting the valley of 1D spectra at 255.9nm and the valley of 2D spectra at 234.5nm (corresponding to zero-crossing of its acidic product) of 1D and 2D spectra against the corresponding concentrations. In the same way, the 1Dand 2D of 4-Aminoantipyrine acidic product standard solution were recorded. Two calibration graphs were obtained by plotting the values of 1D spectra at 243.3 nm and peak of 2D spectra at 227.3nm (corresponding to zero-crossing of pure 4-Aminoantipyrine) of 1D and 2D spectra against the corresponding concentrations. 2. To series of binary mixtures solutions of pure 4-Aminantipyrine standard and its acidic product were prepared; the first series was prepared by using a concentration of 20 mg/l of acidic product with different concentrations of pure 4-aminoantipyrine, while the second series of mixture was prepared by using a concentration 20 mg/l of pure 4-aminoantipyrine with difference concentrations of the acidic product. b. Ratio spectra method Standard solutions of 4-Aminoantipyrine ranging from 10 to 70 mg/l were scanned in the range (from 200 to 400nm), and then divided by a spectrum of standard solution (50 mg/l) of its acidic product (as a divisor). The value of peak 299.9nm of the resultant spectra were plotted against the corresponding concentrations to obtain a calibration graph. The first derivative of ratio spectra(1DD) at peak 291 nm and valley 310 nm was selected, the value of the resultant at these pair of wavelength was measured and plotted against the concentrations to obtain two calibration graphs for 1DD method. The second derivative of ratio spectra (2DD) at peak 286nm, valley 299.9 nm and peak 316nm were selected, three calibration graphs were constructed for 2DD method to the corresponding 4-Aminoantipyrine concentration and the regression validation parameters were calculated. Results and discussion The derivative spectrophotometric methods for the estimation of organic and pharmaceuticals compounds in presence of its acidic degradation products without chemical separation are always of interest. In this study, the acidic product of 4-Aminoantipyrine was carried out by dissolving the pure organic compound 4-Aminoantipyrine in 2M HCl and reflux at 1000C for 60 min. the suggested scheme of acidic product might be written as follows: https://doi.org/10.30526/31.2.1960 https://doi.org/10.30526/31.2.1960 Chemistry | 89 2018( عام 2العدد ) 13لمجلد ا مجلة إبن الهيثم للعلوم الصرفة والتطبيقية Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 31 (2) 2018 The acidic product was subjected to IR spectrophotometry analysis, the comparison of IR- spectra of 4-Aminoantipyrine with that the acidic product, the characteristic band at 3433.41- 3331.18 corresponding to the NH2 of the amine groups shown in (Figure1a) , has been disappeared in the IR- spectra of the acidic products (Figure1b)[19]. Figure (1): IR- spectra of (a) pure 4-Aminoantipyrine and (b) its acidic product 4-Aminoantipyrine and its acidic product UV-spectra are shown in (Figure2); direct estimation of 4-Aminoantipyrine in presence of its acidic products is impossible, zero- crossing and ratio spectrophotometric methods can be resolved and estimation of 4- Aminoantipyrine in presence of its acidic products. https://doi.org/10.30526/31.2.1960 https://doi.org/10.30526/31.2.1960 Chemistry | 90 2018( عام 2العدد ) 13لمجلد ا مجلة إبن الهيثم للعلوم الصرفة والتطبيقية Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 31 (2) 2018 Figure (2): zero order spectra of 4-Aminoantipyrine 30 mg/l(red) and acidic product 30 mg/l (black). Zero-crossing method Zero-crossing method used individual determination of 4-Aminoantipyrine and its acidic product in binary mixture at the selected wavelengths as shown in (Figure3) and (Figure4) respectively. Figure (3):Zero-crossing measurements for (10-70 mg/l) 4-Aminoantipyrine (red) and 40 mg/l acidic product(black) a- 1D at valley 255.9nm, b- 2D at valley 234.5nm for determination of 4-Aminoantipyrine. https://doi.org/10.30526/31.2.1960 https://doi.org/10.30526/31.2.1960 Chemistry | 91 2018( عام 2العدد ) 13لمجلد ا مجلة إبن الهيثم للعلوم الصرفة والتطبيقية Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 31 (2) 2018 Figure (4): Zero-crossing measurements for (10-70 mg/l) acidic product(blue) and 40 mg/l 4- Aminoantipyrine(black) a- 1D at peak 243.3nm, b- 2D at peak 227.3nmfor determination of acidic product. Linearity graphs for 1D and 2D at zero-crossing measurements of standard solutions of (10- 70mg/l) for each of 4-Aminoantipyrine and its acidic product were obtained. linear equation, limit of detections and other validation parameters are listed in Table 1. Table ( 1 ): Validation parameters for the obtained calibration graphs for the determination of 4AAP and its acidic product using zero-crossing measurements. Validation parameters 1D 2D 4AAP at valley 255.9nm Acidic product at peak 243.3 nm 4AAP at valley 234.5nm Acidic product at peak 227.3 nm Linearity range (mg/L) 10-70 10-70 10-70 10-70 equation Y= -0.026x -0.0041 Y=0.0095x +0.0012 Y=-0.0037x -0.018 Y=0.0093x +0.0135 R2 0.9960 0.9980 0.9970 0.9970 Slope -0. 026 0. 0095 -0.0037 0.0093 Intercept -0.0041 0.0012 -0.018 0.0135 LOD 0.495 1.354 3.478 1.383 LQD 1.5 4.105 1.054 4.193 R2= Coefficient of determination, 4AAP=4-Aminoantipyrine and LOD= limit of detection = 3.3×SDb/S , LQD=10×SDb/S. where, SDb= is the standard deviation of the solvent (n=3) and S= is the slop of the corresponding linearity graph. https://doi.org/10.30526/31.2.1960 https://doi.org/10.30526/31.2.1960 Chemistry | 92 2018( عام 2العدد ) 13لمجلد ا مجلة إبن الهيثم للعلوم الصرفة والتطبيقية Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 31 (2) 2018 1D and 2D methods used for the estimation 4-Aminoantipyrine in presence of its acidic product by using zero-order measurements at valley 255.9nm and 234.5nm respectively. In the same way, 1D and 2D methods were used for estimation of the acidic product of 4- Aminoantipyrine in presence of 4-Aminoantipyrine by using zero-crossing measurements at peak values at 243.3 nm and 227.3 nm respectively. The relative error and recovery percents for the estimation of 4AAP and in presence of its acidic product in synthetic mixtures were calculated for triplicate measurements for the suggested zero-crossing spectrophotometric method. The values of recovery percentage were found in the range between 96.555 and 102.160 indicating that the recommended zero-crossing method is accurate as shown in Table 2. Table (2): The relative error and recovery percentage for estimation of 4AAP and its acidic product using zero-crossing method Taken Mixture of 4AAP +acidic product Found mg/l 4AAP 1D at valley 255.9nm E% Rec% Found mg/l 4AAP 2D at valley 234.5nm E% Rec% 20 mg/l+0 mg/l 19.397 -3.015 96.985 19.781 -1.095 98.905 20 mg/l+20 mg/l 19.718 -1.41 98.590 19.920 -0.400 99.600 40 mg/l+20 mg/l 39.511 -1.222 98.777 39.130 -2.175 97.825 30 mg/l+5 mg/l 30.219 0.730 100.730 30.424 1.413 101.413 30 mg/l+10 mg/l 29.624 -1.253 98.746 29.110 -2.966 97.033 Taken Mixture of 4AAP +acidic product Found mg/l Acidic product 1D at peak 243.3nm E% Rec% Found mg/l Acidic product 2D at peak 227.3nm E% Rec% 0mg/l+30mg/l 29.676 -1.08 98.920 29.522 -1.593 98.406 20mg/l+10mg/l 9.732 -2.68 97.320 9.866 -1.340 98.660 20mg/l+20mg/l 19.995 -0.025 99.975 19.311 -3.445 96.555 10mg/l+10mg/l 10.054 0.54 100.540 10.216 2.160 102.160 30mg/l+10mg/l 10.124 1.24 101.240 10.098 0.980 100.980 4AAP=4-Aminoantipyrine, E% = relative error = = 𝑓𝑜𝑢𝑛𝑑−𝑡𝑎𝑘𝑒𝑛 𝑡𝑎𝑘𝑒𝑛 ×100 and Rec% =recovery= E%+100 https://doi.org/10.30526/31.2.1960 https://doi.org/10.30526/31.2.1960 Chemistry | 93 2018( عام 2العدد ) 13لمجلد ا مجلة إبن الهيثم للعلوم الصرفة والتطبيقية Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 31 (2) 2018 Ratio spectrophotometric method In the ratio spectrophotometric methodthe obtained absorption spectra of the mixtures of 4-Aminoantipyrine and its acidic product were divided then by the absorption spectrum of the acidic product standard solution (as divisor) as shown in (Figure5). The first derivative 1DD and the second derivative 2DD spectra in each case was then obtained, as shown in (Figure6). Figure (5): Normal ratio spectra (0DD) of 4-Aminoantipyrine (10-70 mg/l) using 50 mg/l of acidic product as a divisor Figure (6): Derivative ratio spectra of 4-Aminoantipyrine (10-70 mg/l) using 50 mg/l of acidic product as a divisor: (a) first derivative ratio spectra (1DD) and (b) second derivative ratio spectra (2DD) In order to optimize the Ratio spectrophotometric method, various concentrations divisor solution (10, 30, 50, 70 mg/l) were tried of acidic product; the best results were obtained when a 50 mg/l of acidic product was used as a divisor. Dividing the absorption spectrum of 4-Aminoantipyrine in the range(10-70mg/l) by absorption spectrum of 50 mg/l of acidic product (as a divisor). The validation parameters of the obtained linear graphs are summarized in Table 3. https://doi.org/10.30526/31.2.1960 https://doi.org/10.30526/31.2.1960 Chemistry | 94 2018( عام 2العدد ) 13لمجلد ا مجلة إبن الهيثم للعلوم الصرفة والتطبيقية Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 31 (2) 2018 Table (3): Validation parameters for the linear graphs for the determination of 4AAP and its acidic product using 0DD, 1DD and 2DD methods. Validation parameters 0DD at peak 299.9nm 1DD at peak 290.7 nm 1DD at valley 310.nm 2DD at peak 286 nm 2DD at valley 301 nm 2DD at peak 316 nm Linearity range (mg/L) 10-70 10-70 10-70 10-70 10-70 10-70 Equation Y=0.314x +1.338 Y=0.014x +0.093 Y=-0.014x -0.078 Y=0.01x +0.06 Y=-0.02x -0. 02 Y=0.01x +0.05 R2 0.9980 0.9980 0.9970 0.9980 0.9970 0.9990 Slope 0.314 0.014 -0.014 0.01 -0.02 0.01 Intercept 1.338 0.093 -0.078 0.006 -0.02 0.05 LOD 0.040 0.919 0.919 1.287 0.643 1.287 LQD 0.124 2.785 2.785 3.9 1.950 3.9 R2= coefficient of determination The relative error and recovery percentage were calculated and presented in Table 4. The obtained values correspond to triplicate analysis of 4-Amionantipyrine solution in the concentration range 25 -45 mg.l-1 using the ratio derivative method. The values of recovery percentage were found to be in the range between 99.64 and 100.11, indicating that the ratio derivative method is reliable and accurate. Table (4): The relative error and recovery percentage for estimation of 4AAP and its acidic product using 0DD, 1DD and 2DD methods parameters 0DD at 299.9 nm 1DD at 290.7 nm 1DD at 310 nm 2DD at 286 nm 2DD at 301 nm 2DD at 316 nm Taken mg/l 25 25 25 25 25 25 Found mg/l 24.92 24.96 24.93 24.96 24.91 24.93 E% -0.32 -0.16 -0.28 -0.16 -0.36 -0.28 Rec% 99.68 99.84 99.72 99.84 99.64 99.73 Taken mg/l 45 45 45 45 45 45 Found mg/l 44.95 44.98 45.08 44.93 44.96 45.02 E% -0.11 -0.044 0.111 -0.155 -0.088 0.044 Rec% 99.88 99.95 100.11 99.84 99.91 100.04 https://doi.org/10.30526/31.2.1960 https://doi.org/10.30526/31.2.1960 Chemistry | 95 2018( عام 2العدد ) 13لمجلد ا مجلة إبن الهيثم للعلوم الصرفة والتطبيقية Ibn Al-Haitham Jour. for Pure & Appl. Sci. Vol. 31 (2) 2018 Conclusion The proposed methods are simple and accurate making them easily for estimation of 4- aminoantipyrine in presence its acidic product. 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