1. INTRODUCTION:

More and more pharmaceuticals products are being discharged and consumed by people and domestic animals as industry and agriculture have grown. In many countries, the danger of pollution increased due to massive industrial growth,a number of pharmaceutical have attracted considerable interest in surface in land, drinking water and the The world's biggest concern is water contamination^1,23,4.They are as emerging contaminants that have not yet being monitored and because of the possible harm to animals and humans, their appearance a traces in water source is of great concern^5,6because the biologically active nature and the physico chemical properties of lipophilic and persistent⁷. Therefore pharmaceuticals must be degraded and excluded from the sources of water.

Heterocyclic compounds are very widely distributed in nature⁸.Pyrazolone is five membered heterocyclic containing two adjacent nitrogen atoms⁹. Many Derivatives of pyrazolone such as antipyrine, 4-aminoantipyrineare commonly prescribed as analgesics and anti-inflammatory drugs particularly dipyrone (metamizole). Up to four dipyrone metabolites mainly 4-aminoantipyrine (4-AAP) with contents range from 20ngL^-1 to 27ngL^-1 ^10,11,12. 4-AAP has biologically activity¹³, is used in viral disorder therapy¹⁴ and form stable hemoglobin complexes to decrease blood flow (i.e. agranulocytosis). Because of health risk of 4-AAP, its determination is important¹⁵.Since 4-AAP has been identified toxic to laboratory animals¹⁶.

4-AAP could be effectively determined by some expensive instrumental methods like LC-QTRAP-MS ¹⁷ and LC-electrospary tandem MA (LC-ES-MS-MS)¹⁸ liquid and gas chromatography, spectrophotometry ^19,20,21 and solid-phase spectrophotometry²². The challenges with these approaches are time consuming process of extraction and separation.

Electroanalytical methods are superior among the various methods and voltammetry is the right choice.^23,24 Voltammetry is an environmentally safe technique²⁵ gives quick information of reduction-oxidation process of an electroactive species by measuring the resulting current as function of the applied potential ^26,27. The redox properties of drugs can give us insight to their metabolite fate in in vivo redox process or pharmacological activity ^28,29. It is widely used to determine kinetic parameters, mechanism and potential of electrode reactions.^30,31,32.In this present work we find out electrochemical and kinetic behaviour of 4-AAP in BR buffer .

2. EXPERIMENTAL SECTION:

2.1. Reagents and Chemicals:

4-Aminoantipyrine (99%) was purchased from Merck and used without any more purification. Double-distilled water was used to prepare a stock solution of 4-aminoantipyrine (2mM). Britton-Robinson buffer (BR buffer) 0.2 M of pH=2.0 was also prepared in double-distilled water and pH was adjusted by 0.2 M NaOH. Other chemicals used were of analytical grade.

2.2. Instrumentation and Analytical Procedure:

An Autolab model PGATAT 101 potentiostat/galvanostat 663VA stand (Metrohm AG, Netherland) was used for the all electrochemical measurments. Voltammetric measurements has been taken by three-electrode glass cell with a platinum electrode (0.031cm2) as working electrode, a platinum wire as the counter electrode, and Ag/AgCl (3.0 M KCl) as the reference electrode. Working electrode was polished by alumina powder before each experiment. All measurements were taken at the temperature of 25-26 ˚C.

3. RESULTS AND DISCUSSION:

3.1. Cyclic voltammetric experiments for platinum electrode:

Electro-oxidation of 4-AAP at a platinum electrode was studied by CV in 0.2M BR buffer at pH=2.0, at different scan rates and potential window range from +0.3 to +1.0 V. As on reverse scan no cathodic peak was seen, it suggests that process was irreversible. First cyclic voltammogram at the scan rate v=0.025Vs^-1 shows an anodic peak with the peak potential (Ep) = + 0.55V (Figure 1 b). CV explored the effect of different scan rates on the electro-oxidation of 4-AAP as shown in (figure 2).

Figure 1: Cyclic voltammogram for 2mM 4-AAP on Pt electrode in 0.2M BR buffer (A) Blank (B) 4-aminoantipyrine at scan rate (v) = 0.025 V s^-1

Figure 2: Cyclic voltammograms on Pt electrode for 2mM 4-AAP at different scan rates0.025,0.050,0.100,0.150,0.200,0.250,0.300 and 0.350 Vs^-1

3.2. Effect of Scan Rate:

The effect of the square root of the scan rate on the peak current was found to be linear from 0.025, 0.050 - 0.350 V s^-1, if there is a linear change in Ip with v1/2, the origin of the co-ordinates intercepted, it is believed that the process would not have kinetic interference. However, if Ip has an intercept value that is not zero for the linear coefficient, then the process is accompained by homogeneous chemical reaction³³. By this linear fit origin of the coordinates is not intercepted (figure 3), the electrode process is diffusion-control in nature and can be expressed as:

Ipa (µA) = 14.4 v^1/2(V^1/2s^-1/2) + 0.069 (r=0.9925) (1)

Figure 3: Ipa vs v^1/2

Figure 4: log Ipa vs log v

A linear relationship between log Ipa and log v has been observed (Figure 4), corresponding to the equation

log Ipa (µA) = 0.464 log v (V s^-1) + 1.136 (r=0.9933) (2)

As the theoretical value for diffusion controlled current process is 0.5,In our system the slope value is 0.46 which is close to theoretically value ³⁴. So the electro-oxidation of 4-AAP is diffusion controlled, and with an increase the scan rate range of 0.025 vs-1 to 0.350 Vs-1,Ep shifted to more positive value, a linear relationship between Ep and log v has shown in (figure 5).

Ep (V) = 0.019 log v (V s^-1) + 0.5854 (r=0.9906) (3)

Figure 5: Ep vs log v

According to Laviron,³⁵ Ep is defined as for an irreversible electrode process

(4)

Where E⁰ is the formal standard redox potential, α is the transfer coefficient, k⁰ is the standard heterogeneous rate constant of the reaction, n is the number of electrons transferred, v is the scan rate, other symbols have their usual meanings. Thus, the value of αn can be easily calculated from the slope of a plot of Ep versus log v. The αn value was calculated to be 3.11.

According to Bard and Faulkner ³⁰ α can be expressed as:

(5)

Where Ep is peak potential, Ep_1/2is the potential when peak current is half.

The average value of electron transfer coefficient ( a) was evaluted to be 1.38 and number of electrons (n) transferred in 4-AAP was calculated to be 2.25»2. Additionaly, the standard heterogeneous rate constant (k⁰) can be calculated by knowing the value of the formal potential (E⁰), as E⁰ can be obtained from the intercept of the peak potential versus scan rate curve by extrapolating to the vertical axis at v=0 ³⁶. E⁰ and k⁰was calculated to be 0.5562 V and 2.145 x10³ s^-1respectively. The electron transfer rate constant (k_0x) is a function of the applied potential can be calculated from the equation ³⁷

So, the value of K_ox was calculated to 2.316 x 10³ s^-1.

CONCLUSION:

The electrochemical oxidation process of 4-Aminoantipyrine was found to be purely diffusion controlled and the nature of reaction is irreversible at the platinum electrode. There are two electrons are transferred during the process with fast electron transfer rate constant. Therefore, this toxic compound can be degraded with help of cyclic voltammetry easily and eco-friendly.

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Received on 24.12.2020 Modified on 25.02.2021

Research J. Pharm.and Tech 2022; 15(2):551-554.

DOI: 10.52711/0974-360X.2022.00089