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. 2024 Feb 22;9(9):10190–10200. doi: 10.1021/acsomega.3c07074

Effective Treatment Methodology for Environmental Safeguard Catalytic Degradation of Fluconazole by Permanganate Ions in Different Acidic Environments: Kinetics, Mechanistics, RSM, and DFT Modeling

Arafat Toghan †,‡,*, Ahmed Fawzy §,*, Nada Alqarni ∥, Ahmed M Eldesoky ⊥, Omar K Alduaij †, Ahmed A Farag #,*
PMCID: PMC10918786  PMID: 38463285

Abstract

graphic file with name ao3c07074_0013.jpg

In this paper, the degradation of fluconazole drug (Flz) was explored kinetically utilizing permanganate ion [MnO–4] as an oxidant in different acidic environments, namely sulfuric and perchloric acids at various temperatures. Stoichiometry of the reactions between Flz and [MnO–4] in both acidic environments was attained to be 1.2 ± 0.07 mol. The kinetics of the degradation reactions in both cases were the same, being unit order regarding [MnO–4], fewer than unit orders in [Flz], and fractional second orders in acid concentrations. The rate of oxidative degradation of fluconazole in H2SO4 was higher than that in HClO4 at the same investigational circumstances. The addition of small amounts of Mg2+ and Zn2+ enhanced the degradation rates. The activation quantities were evaluated and debated. The gained oxidation products were characterized using spot tests. A mechanistic approach for the fluconazole degradation was suggested. Finally, the rate law expressions were derived which were agreed with the acquired outcomes. The rates of degradation for various [Flz] were mathematically modeled using the response surface methodology (RSM). The RSM model’s conclusions and the experimental findings are in agreement. The oxidative degradation mechanism of Flz using density functional theory (DFT) was performed. The fluconazole drug degrades in acidic settings, protecting both the environment and human health, according to a method that is easy to use, powerful, inexpensive, practical, affordable, and safe.

1. Introduction

The safe disposal of waste that is harmful to the environment is one of the most prominent challenges at the present time, especially with the technological and industrial development.1−6 Medications or medical drugs are chemical substances used to detect, remedy, or avoid diseases in human, animals, and plants.7−10 While medical drugs are fundamentally essential, they are foreign substances to the human body and must be eliminated after showing their medical role via the drug metabolism process in which drugs undergo a certain chemical reaction such as oxidation, reduction, hydrolysis, and so forth. Drug metabolism may transform drugs to medically effective, ineffective, or toxic materials that are excreted into the ecosystem and water sites.11−13 Since the structures of these metabolites comprise complex organic compounds which can also stay in the environment for a long time without removal, these metabolites can be deliberated as dangerous pollutants.14−16 Consequently, there is a huge interest to recognize efficient green treating methods or techniques for the removal or degradation of these materials to protect the ecosystem and human health.17−20

In various media, medical drugs are generally subjected to a variety of oxidation processes resulting in their decomposition or degradation.21−25 Throughout these oxidation processes, oxidizers convert harmful or toxic materials to lower toxic ones which can be discharged safely to the environment.26−30 Thus, oxidation of medical drugs has been considered as one of the supreme substantial methods for drug degradation and water-treating processes.31 Fluconazole is a significant antifungal drug utilized for a wide number of fungal infections. Literature review illuminated very few reports that have been published on the oxidative degradation of fluconazole.32 In these few reports, the employed strategies or chemicals may be relatively expensive or not widely available. In the light of these arguments, the existing investigation has been performed which is concerned with the study of kinetic and mechanistic features of oxidative degradation of the antibiotic fluconazole using the permanganate ion [MnO–4], which is one of the furthermost significant, available, powerful, inexpensive, and eco-friendly oxidants,33,34 in a variety of acidic environments. The topmost aims of our investigation were to illuminate the capability of permanganate for the decomposition or degradation of fluconazole, to examine the impact of the acid type on the degradation kinetics as well as the influence of numerous effects. The catalytic impacts of certain metal cations, mainly Mg2+ and Zn2+, were examined.35 Also, the activation quantities were evaluated, and a reasonable degradation mechanism was suggested. Furthermore, this study is also extended to apply the RSM-CCD method to find the best answer through a sequence of well-planned tests. The individual and interaction effects of numerous conventional features were evaluated using CCD based on RSM in order to produce a more precise model for the sensitivity of the degradation rate of Flz. Additionally, the oxidative degradation mechanism of Flz using density functional theory (DFT) was performed. Accordingly, the present study aims to present a promising, simple, convenient, low-cost, and safe method for fluconazole disposal to protect the human health and ecosystem.

2. Experimental Section

2.1. Chemicals and Solutions

Fluconazole drug (Sigma-Aldrich, 98%) stock solution was made with DMSO solvent. A fresh potassium permanganate solution was made with bidistilled water. Stock solutions of H2SO4 and HClO4 (Merck) were made by dilution of 99% H2SO4 and 70% HClO4, respectively, with bidistilled water.36 Solutions of sodium sulfate and sodium perchlorate (BDH, British Drug Houses) were prepared to fix the ionic strengths (I) in H2SO4 and HClO4 environments, individually. Solutions of sulfate salts of magnesium and zinc (BDH) were utilized to catalyze the degradation rates.

2.2. Kinetic Measurements

The oxidative degradation reactions in both acidic environments were performed under pseudo-first-order circumstances ([Flz] ≫ [MnO–4]). The degradation reactions were tracked by recording the reduction of [MnO–4] absorbance at λ = 525 nm with time. The recorded UV–vis absorption readings were made on a thermostat Shimadzu UV–vis–NIR-3600 double-beam spectrophotometer. Most runs were performed three times to check the reproducibility (±4%).

2.3. Theoretical Calculation Analysis

The programs Gaussian View 06 and Gaussian 09W were used for all computations. The Lee–Yang–Parr (B3LYP) concept and the 6-31+G(d,p) base established were used to optimize the geometrical parameters of Flz, and also to calculate the Mulliken charge distribution.

2.4. Response Surface Methodology (RSM)

Analyzing statistical information can help uncover hidden data and create models for prediction and estimation. Box and Wilson established the response surface methodology (RSM), a potent technique for analyzing and optimizing a phenomenon’s interaction impacts.37 In this case, the temperature (K), concentration of acid [H+], and fluconazole dosage (mol dm–3) are selected as independent factors, and the rate at which the drug degrades with the concentration of H2SO4 or HClO4 is selected as the response variable to be optimized via RSM. This decreased quantity of runs as well as the effectiveness of the modeling means that the face-centered composite design, or CCD for short, is used.38 Thirty-six designs of experiment matrices and their outcomes are shown in Table 1.

Table 1. Experimental Designs Using Central Composite Design (CCD) for Degradation Rate.

run operating conditions response (103 kobs (s–1))
102 [Flz] (mol dm–3) [H+] (mol dm–3) T (K) in sulfuric acid in perchloric acid
1 2 0.5 288 15.6 9.0
2 2 0.5 298 19.8 15.1
3 2 0.5 308 26.3 21.8
4 2 0.5 318 33.0 24.6
5 4 0.5 288 28.1 20.7
6 4 0.5 298 39.1 24.9
7 4 0.5 308 49.0 37.9
8 4 0.5 318 64.4 47.8
9 6 0.5 288 36.2 29.4
10 6 0.5 298 53.9 40.6
11 6 0.5 308 72.3 50.1
12 6 0.5 318 94.8 74.8
13 8 0.5 288 50.8 34.1
14 8 0.5 298 66.8 50.4
15 8 0.5 308 92.7 66.4
16 8 0.5 318 120.9 89.9
17 10 0.5 288 61.3 42.3
18 10 0.5 298 80.2 58.1
19 10 0.5 308 110.1 85.0
20 10 0.5 318 140.8 115.3
21 6 0.1 288 2.7 1.8
22 6 0.1 298 3.2 2.3
23 6 0.1 308 4.5 2.9
24 6 0.1 318 5.6 7.2
25 6 0.3 288 14.0 12.0
26 6 0.3 298 20.2 15.0
27 6 0.3 308 27.1 20.8
28 6 0.3 318 37.5 29.8
29 6 0.7 288 58.8 53.8
30 6 0.7 298 93.0 69.9
31 6 0.7 308 127.0 97.7
32 6 0.7 318 163.0 119.7
33 6 0.9 288 99.1 78.2
34 6 0.9 298 133.4 112.5
35 6 0.9 308 196.9 138.5
36 6 0.9 318 241.8 201.3
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3. Results and Discussion

3.1. Reaction Stoichiometry and Product Description

Sets of reaction mixtures with various ratios of [MnO–4]/[Flz] at fixed [H+] = 0.5 M and I = 1.0 M at 298 K were reacted for 24 h until the completion of degradation reactions. The unconsumed [MnO–4] was determined by spectrophotometry. The results designated that 4 mol of [MnO–4] was consumed to oxidize 5 mol of Flz to give the degradation products. The observed stoichiometry may be represented by the subsequent stoichiometric eq 1:

3.1. 1

In eq 1, the compounds (I), (II), and (III) are Flz and its degradation products, individually. The products of fluconazole oxidation were separated by chromatography.39 Then, the separated products were recognized by spot tests via 2,4-dinitrophenylhydrazine, Schiff’s, Tollen’s and sodium nitroprusside reagents. It is widely known that the derivatives of 1,2,4-triazoles have a variety of biological functions. Based on earlier studies, most 1,2,4-triazole compounds appear to be relatively nontoxic. For example, Zhiyong Liu et al. estimated the toxicity of derivatives of 1,2,4-triazoles which demonstrated low toxicity and low environmental hazards.40

3.2. Spectroscopic Changes

Figure 1 shows the absorbance versus wavelength curves during the permanganate ion oxidation of fluconazole (Flz) in (a) sulfuric and (b) perchloric acid environments at 298 K. The figure illuminates the regular vanishing of permanganate ion band at λ = 525 nm. Figure 1 also shows no other features between 400 and 650 nm in which MnIV intermediate absorbs,36 designating that manganese dioxide is not an oxidation product. Also, no increase in absorption at 418 nm was manifested, signifying that MnIV ions did not contribute to the oxidation process.

Figure 1.

Figure 1

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Spectroscopic changes during the permanganate oxidation of fluconazole (Flz) in (a) sulfuric acid and (b) perchloric acid environments. [MnO–4] = 4.5 × 10–4, [Flz] = 1.0 × 10–3, [H+] = 0.1, and I = 0.2 mol dm–3 at 298 K. Scan time intervals = 1 min.

3.3. Order of Degradation Reactions Regarding their Constituents

The pseudo-first-order rate constants (kobs) were estimated as the gradients of ln(absorbance) versus time plots (first-order plots). The orders of reactions with regard to [reactants] in both acidic environments were assessed from the gradients of log kobs versus log(concentration) by varying [Flz] and [H+] in turn, whereas other constituents were retained fixed.

To investigate the dependence of the rates of oxidative degradation reactions on [MnO–4] and hence the reaction order with regard to it, the preliminary [MnO–4] was altered from 1 × 10–4 to 8 × 10–4 M at firm [Flz] = 3.0 × 10–2, [H+] = 0.5, and I = 1.0 M at 298 K. It was noticed that the first-order graphs were approximately linear for the examined initial concentrations of [MnO–4] (Figure S1 in the Supporting Information), signifying that the oxidative degradation reactions were of unit order in [MnO–4]. This result was indicated by the fixed values of kobs in both acidic environments for various [MnO–4] concentrations, as given in Table 1.

Also, in order to help in the elucidation of the degradation mechanism, the rates of degradation of fluconazole by [MnO–4] was evaluated at various concentrations of the examined acidic environments (H2SO4 and HClO4) at different temperatures. The gained outcomes signified increasing rates of antibiotic degradation with rising [H+], as shown from the values of kobs listed in Table 1 (at 298 K) and in Table S1 in the Supporting Information at all temperatures. Plots of kobs against [H+],2 at different temperatures, were linear with + ve intercepts, as illustrated in Figure 2. In addition, the plots of log kobs against log [H+] gave straight lines with gradients of 1.75 and 1.78, as shown in Figure S2 in the Supporting Information, signifying that these reactions were fractional second orders in [H+]. On the other hand, the values of kobs in both acidic environments were determined at several concentrations of fluconazole, [Flz], at stable [MnO–4], [H+], I, and T. The acquired values of kobs (presented in Tables 1 and S1) designated that the degradation rates were enhanced with rising [Flz]. In addition, the plots of kobs versus [Flz] at different temperatures were straight with +ve intercepts (Figure 3). Furthermore, the plots of log [Flz] against log kobs at 298 K gave straight lines with gradients of 0.86 and 0.88 in H2SO4 and HClO4, correspondingly (Figure S3 in the Supporting Information), indicating that such degradation reactions were fractional first orders in fluconazole concentration.

Figure 2.

Figure 2

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Plots of kobs vs [H+]2 in the oxidative degradation of fluconazole in (a) sulfuric acid and (b) perchloric acid. [MnO–4] = 4.5 × 10–4, [Flz] = 3.0 × 10–2, and I = 1.0 mol dm–3 at 298 K.

Figure 3.

Figure 3

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Plots of kobs vs [Flz] in the oxidative degradation of fluconazole in (a) sulfuric acid and (b) perchloric acid. [MnO–4] = 4.5 × 10–4, [H+] = 0.5, and I = 1.0 mol dm–3 at 298 K.

3.4. Influences of the Ionic Strengths and Dielectric Constants of the Reaction Media

The kinetic runs were performed at numerous concentrations of sodium sulfate (in the case of H2SO4) and sodium perchlorate (in the case of HClO4), while other ingredients persisted stable. The acquired results showed that the degradation rates were approximately unchanged as the value of I increased (Table 1). The influence of dielectric constants was examined by varying the acetic acid–water ratios in the reaction media, with all other circumstances being fixed. The experimental outcomes signified that the values of kobs were altered unimportantly by increasing the acetic acid content in the reaction media (decreasing the dielectric constants).

3.5. Influence of Temperature on the Oxidative Degradation of Fluconazole

To investigate the impact of rising temperature on the degradation rates as well as to evaluate the activation parameters, kinetic experiments were carried out at various temperatures, namely 288, 298, 308, and 318 K, at numerous concentrations of fluconazole and acidic environments, but other variables remained constant. The experimental results (Figures 2, 3 and Tables 1, S1) showed that the degradation rates were set to improve by rising temperatures.

3.6. Influence of [Mg2+] and [Zn2+] on the Oxidative Degradation of Fluconazole

The catalytic impacts of certain environmentally friendly metal cations, namely Mg2+ and Zn2+, on the degradation rates of fluconazole were studied in both acidic environments, and such rates were recorded after adding different concentrations of such cations at other fixed reaction ingredients. The obtained results (shown in Figure 4) indicated that the rates were improved by increasing the doses of the supplemented metal ions.

Figure 4.

Figure 4

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Influence of (a) [Mg2+] and [Zn2+] on the rates of the oxidative degradation of fluconazole by permanganate ion in sulfuric and perchloric acid environments. [MnO–4] = 4.0 × 10–4, [Flz] = 3.0 × 10–2, [H+] = 0.5, and I = 1.0 mol dm–3 at 298 K.

3.7. Acrylonitrile Test

To explore whether free radicals were formed throughout the examined degradation reactions or not, the acrylonitrile tests in both acidic environments were implemented. Acrylonitrile test was done by adding a certain volume of acrylonitrile to the reaction mixtures for 4 h. The investigational findings manifested that there were white precipitates formed, i.e., polymerization occurred in the reaction mixtures proposing the intervention of free radicals during such reactions.

3.8. Proposed Degradation Mechanism

The enhancement of the degradation rates by rising [H+] in addition to permanganate chemistry41 recommends the construction of a more forceful oxidizing agent,

3.8. 2

The protonated permanganate ion (HMnO4) is stronger than [MnO–4] itself. Also, the fractional second-order reliance of the degradation rates regarding [H+] was an evidence of fluconazole protonation:

3.8. 3

Thus, the protonated forms of both the oxidant and antibiotic were regarded as the reactive species in the rate-limiting stage of the degradation reactions.

On the other hand, the lower-than unit order reliance on fluconazole concentration consists with complex formation (1/kobs vs 1/[Flz] plot) (Figure 5). Furthermore, enhancing the rates with [Mg2+] and [Zn2+] signifies complexation between Flz and such cations.

Figure 5.

Figure 5

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Plots of 1/kobs vs 1/[Flz] in the oxidative degradation of fluconazole by permanganate ion in (a) sulfuric, and (b) perchloric acid environments at different temperatures. [MnO4—] = 4 × 10–4, [H+] = 0.5, and I = 1.0 mol dm–3.

In the light of these aspects, the plausible degradation mechanism involves the attack of the powerful acidic permanganate (produced through the reaction represented by eq 2) on the protonated fluconazole (produced through the reaction represented by eq 3) to construct a complex (C), as denoted by the succeeding equation,

3.8. 4

The negligible impacts of both ionic strengths and dielectric constants of the reaction media propose that these reactions were among two neutral molecules or between an ion (Flz-H+) and a neutral molecule (HMnVIIO4).

The complex (C) is rapidly decomposed in the rate-limiting (slow) stage, leading to the formation of fluconazole free radical (Flz.+) and MnVI intermediate, as illustrated by eq 5,

3.8. 5

The next step involves the attack of the formed Flz.+ by the MnVI intermediate to produce the final degradation products of fluconazole, eq 6,

3.8. 6

The formed MnV species is very unstable in strong acidic environments, and it converted rapidly into MnII and MnVII by the disproportionation process as follows,

3.8. 7

This was followed by other fast steps between the permanganate ion and fluconazole, leading to the formation of the degradation products, as illuminated in the overall stoichiometric reaction 1.

3.9. Rate Law Equations

According to the proposed oxidative degradation mechanism and the rate-determining stage expressed by eq 5, the rate of vanishing of [MnO–4] or construction of the complex (C) can be written by the succeeding rate equation,

3.9. 8

From reaction 2

3.9. 9

and from the reaction expressed by eq 3,

3.9. 10
3.9. 11

Exchanging eqs 9 and 10 into eq 11 gives,

3.9. 12

Also exchanging eq 12 into eq 8 leads to,

3.9. 13

The total [MnO4—] is given by (where “T’ and ‘F” stand for total and free):

3.9. 14

Exchanging eqs 9 and 11 into eq 14 results in,

3.9. 15
3.9. 16

Consequently,

3.9. 17

As a result of high [H+], we can propose that,

3.9. 18

Correspondingly,

3.9. 19

Replacement of eqs 17–19 into eq 13 (and excluding “T’ and ‘F” subscripts) results in,

3.9. 20

Under pseudo-first-order circumstance, the rate law can be stated by the equation,

3.9. 21

Comparing eqs 20 and 21,

3.9. 22

and

3.9. 23

Rendering to eq 23, the graphs of 1/kobs versus 1/[Flz] at fixed [H+] should be linear with +ve intercepts, as were manifested from Figure 5 at different temperatures. The values of the rate constant of the rate-limiting stage, k1, at various temperatures are evaluated and presented in Table 2.

Table 2. Dependence of the Values of kobs on [MnO–4], [Flz], [H+], and Ionic Strength (I) in the Oxidative Degradation of Fluconazole by Permanganate Ion in Sulfuric and Perchloric Acid Environments at 298 K.

104 [MnO–4] (mol dm–3) 102 [Flz] (mol dm–3) [H+] (mol dm–3) I (mol dm–3) 103kobs (s–1) 104 [MnO–4] (mol dm–3)
sulfuric acid perchloric acid
1.0 6.0 0.5 1.0 52.1 40.9
2.0 6.0 0.5 1.0 53.7 42.1
4.0 6.0 0.5 1.0 53.9 40.6
6.0 6.0 0.5 1.0 52.4 41.0
8.0 6.0 0.5 1.0 54.2 39.8
4.0 2.0 0.5 1.0 19.8 15.1
4.0 4.0 0.5 1.0 39.1 24.9
4.0 6.0 0.5 1.0 53.9 40.6
4.0 8.0 0.5 1.0 67.0 50.4
4.0 10.0 0.5 1.0 79.9 58.0
4.0 6.0 0.1 1.0 3.2 2.3
4.0 6.0 0.3 1.0 20.2 15.0
4.0 6.0 0.5 1.0 53.9 40.6
4.0 6.0 0.7 1.0 93.0 69.9
4.0 6.0 0.9 1.0 133.4 112.5
4.0 6.0 0.5 1.0 53.9 40.6
4.0 6.0 0.5 1.5 52.4 41.2
4.0 6.0 0.5 2.0 53.1 40.5
4.0 6.0 0.5 2.5 52.7 41.6
4.0 6.0 0.5 3.0 54.2 40.1
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The acquired insignificant intercepts (in Figure 5) may lead to shorten eq 23 to 24:

3.9. 24

According to eq 24, when the graphs were made between [Flz]/kobs and 1/[H+], good straight lines with + ve intercepts would be obtained, as illustrated in Figure 6, which approve the legality of the proposed mechanism.

Figure 6.

Figure 6

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Plots of [H+]/kobs vs 1/[H+] in the oxidative degradation of fluconazole by permanganate ion in (a) sulfuric acid and (b) perchloric acid environments at different temperatures. [MnO4—] = 4 × 10–4, [Flz] = 6.0 × 10–2, and I = 1.0 mol dm–3.

3.10. Activation Parameters

The activation quantities related to the rate-limiting stage, k1, were evaluated via Arrhenius and Eyring equations (illustrated in Figures 7a,b, correspondingly). The acquired values of activation quantities, namely, entropy (ΔS‡), enthalpy (ΔH‡), free energy (ΔG‡), and activation energy (Ea‡) are listed in Table 3. The acquired great negative ΔS‡ values verify the compression of the constructed intermediate complex (C). Also, the positive ΔH‡ and ΔG‡ values designated the endothermic construction of the complex and its nonspontaneity, individually.42

Figure 7.

Figure 7

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(a) Arrhenius, and (b) Eyring plots of k1 in the oxidative degradation of fluconazole (Flz) by permanganate ion in (a) sulfuric and (b) perchloric acid environments. [MnO4—] = 5.0 × 10–4, [Flz] = 5.0 × 10–2, [H+] = 0.5, and I = 1.0 mol dm–3.

Table 3. Activation Parameters of k1 in the Oxidative Degradation of Fluconazole by Permanganate Ion in Sulfuric and Perchloric Acid Environmentsa.

acidic medium ΔS‡ (J mol–1 K–1) ΔH‡ (kJ mol–1) ΔG‡ (kJ mol–1) Ea‡ (kJ mol–1)
Sulfuric –118.89 39.82 75.25 39.57
Perchloric –174.59 24.11 76.14 24.61
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a

[MnO4—] = 4 × 10–4 and I = 1.0 mol dm–3.

3.11. Mechanism of Oxidative Degradation with Assistance from DFT Calculations

The electrostatic potential (ESP) is a useful descriptor for distinguishing the locations of electrophilic (areas with low electron density) and nucleophilic (areas with high electron density) reactions because of its link to electron density. Blue is connected with the electrophilic region, while red is related with the nucleophilic region (which is quickly damaged by oxidants).43−46 The carbons at the linker between the benzene and the two triazole rings were related with the electrophilic blue region in Figure 8a, while the nitrogen atoms of the two triazole rings were the site of the nucleophilic red region. The frontier-orbital theory states that nucleophilic interaction more likely occurs at particles with higher values of the lowest unoccupied molecular orbital (LUMO), and electrophilic interaction is more likely to happen at particles with higher values of the highest occupied molecular orbital (HOMO).47−49 According to certain experts, atoms with higher frontier electron density HOMO values are more susceptible to oxidation.50−52Figure 8b gives the Mulliken charge distributions for each atom. C1 in the benzene ring of the Flz structure had the highest HOMO value, which was 0.408, followed by C3 in the benzene ring and C17 and C22 in the triazole ring, which had HOMO values of 0.354 and 0.0322, respectively. C19 was one of the positions, with the HOMO value greater than 0.2. According to Figure 8c,d, the border electron densities of HOMO and LUMO for Flz were individually estimated.

Figure 8.

Figure 8

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Theoretical calculation of the Flz structure; (a) electrostatic potential (ESP), (b) Mulliken charge distributions, and (c,d) HOMO and LUMO.

3.12. RSM Model Optimization

From the investigational data in Table 1, a semiempirical appearance equation that comprised 10 statistically substantial factors was obtained and stated as follows:

3.12. 25
3.12. 26

where Y1 and Y2 are the response variables of kobs in the presence of H2SO4 and HClO4, respectively. A, B, and C represent three experimental factors, the fluconazole drug concentration (mol dm–3), acid concentration [H+], and temperature (K), respectively. With a good correlation (R2 = 0.994 376 and 0.991 for Y1 and Y2, respectively), the comparison of experimental values (Yexp) in 374 that are consistent with the responses predicted by the typical (Ycal) 375 for the deterioration rate indicates that this is generally 377. As shown in Figure 9, this makes the investigative series very clear.

Figure 9.

Figure 9

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Experimental and calculated values for the degradation rate of Flz in (a) H2SO4 and (b) HClO4.

Afterward, the variance among the values of the results from experimentation and estimates (residuals) could be pragmatic to assess the perfect suitability. The externally estimated residual design is specified in Figure 10. All residuals may be shown to be uniformly distributed within a line that is straight, suggesting there is is no serious non-normality. Based on these findings, the residuals appeared to be caused by random scatter, and the model developed is appropriate for describing the link between the deterioration rate and the three aforementioned factors.

Figure 10.

Figure 10

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Externally studentized residual plot in the presence of (a) H2SO4 and (b) HClO4.

The values of P (significant probability values) on the other hand confirm that the model terms are highly significant53−56 if they are smaller than 0.05. In addition, Figure 11 demonstrates that, regardless of how the expected value varies, in addition, the residuals lack any discernible pattern or systematic organization and are distributed between −4 and +4.

Figure 11.

Figure 11

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Residuals vs predicted in (a) H2SO4 and (b) HClO4.

These results lead to the conclusion that the created model is enough to describe the link between the deteriorating efficiency and the previously indicated parameters, and the residuals approximate an arbitrary scatter.57 The results are shown in Figure 12, which shows that the degradation rate of Flz increases by rising the temperature and increasing the acid concentration [H+] of both sulfuric and perchloric acids. The closeness of the two results suggests that the semiempirical expression is sufficient to maximize Flz degradation.

Figure 12.

Figure 12

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Three-dimensonal surface plots: effect of [H+] × temperature (T) on the degradation of Flz in (a) H2SO4 and (b) HClO4.

4. Conclusions

Oxidative degradation of Flz was discovered kinetically using permanganate ion in H2SO4 and HClO4 electrolytes at various temperatures. The degradation reactions were found to be acid-catalyzed. The rate of oxidative degradation of fluconazole in H2SO4 electrolyte was higher than that in HClO4 electrolyte at the same investigational circumstances. Addition of little amounts of Mg2+ and Zn2+ enhanced the degradation rates. The activation quantities of the mechanism at slow stage were calculated and debated. The obtained oxidation products were characterized using spot tests. A mechanistic approach for the fluconazole degradation was suggested. The rate law expressions were derived which agreed with the acquired outcomes. Mulliken charge distributions indicated that C1 in the benzene ring of the Flz structure had the highest HOMO value, which was 0.408, followed by C3 in the benzene ring and C17 and C22 in the triazole ring, which had HOMO values of 0.354 and 0.0322, respectively. The present research work may introduce a promising, modest, opportune, low-priced, and harmless tool to be employed for dilapidation of fluconazole in acid atmospheres to defend the humanoid healthiness and ecosystems.

Acknowledgments

The authors extend their appreciation to the Deanship of Scientific Research at Imam Mohammad Ibn Saud Islamic University (IMSIU) for funding and supporting this work through Research Partnership Program no.RP-21-09-74.

Supporting Information Available

The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsomega.3c07074.

  • Identified separated products of degradation reactions; effect of temperature on kobs (× 10–3 s–1) in the oxidative degradation of fluconazole by permanganate ion in sulfuric and perchloric acid environments; plots of ln absorbance vs time in the oxidative degradation of fluconazole by permanganate ion; plots of log kobs vs log [H+] in the oxidative degradation of fluconazole by permanganate ion; and plots of log kobs vs log [Flz] in the oxidative degradation of fluconazole by permanganate ion (PDF)

The authors declare no competing financial interest.

Supplementary Material

ao3c07074_si_001.pdf (131.3KB, pdf)

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