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Oxidative Degradation of Atropine Drug by Permanganate Ion in Perchloric and Sulfuric Acid Solutions: A Comparative Kinetic Study

Received: 28 August 2016     Accepted: 5 September 2016     Published: 18 October 2016
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Abstract

The kinetics of oxidations of atropine (ATR) by permanganate ion in both perchloric and sulfuric acid solutions was studied using spectrophotometric technique at a constant ionic strength of 1.2 moldm-3 and at 25°C. In both acids, the reactions showed a first order dependence with respect to [permanganate], whereas the orders with respect to [ATR] and [H+] were found to be less than unity. The effect of acid concentration suggests that the reactions were acid-catalyzed. Variation of either ionic strength or dielectric constant of the medium had no effect significantly on the oxidation rates. The reactions mechanism adequately describing the kinetic results was proposed. In both acids, the main oxidation products of atropine were identified by spectral and chemical analyses as tropine and phenylmalonic acid. Under comparable experimental conditions, the oxidation rate of atropine in sulfuric acid was approximately three times higher than that in perchloric acid. The reactions constants involved in the different steps of the reactions mechanism have been evaluated. With admiration to the rate-limiting step of these reactions, the activation parameters have been evaluated and discussed.

Published in Advances in Biochemistry (Volume 4, Issue 5)
DOI 10.11648/j.ab.20160405.12
Page(s) 58-65
Creative Commons

This is an Open Access article, distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution and reproduction in any medium or format, provided the original work is properly cited.

Copyright

Copyright © The Author(s), 2016. Published by Science Publishing Group

Keywords

Atropine, Permanganate, Oxidation, Kinetics, Mechanism

References
[1] Kittakoop P, Mahidol C, Ruchirawat S (2014) Alkaloids as important scaffolds in therapeutic drugs for the treatments of cancer, tuberculosis, and smoking cessation. Curr. Top Med. Chem. 14: 239-252.
[2] Cushnie TP, Cushnie B, Lamb AJ (2014) Alkaloids: an overview of their antibacterial, antibiotic-enhancing and antivirulence activities. Int. J. Antimicrob. Agents, 44: 377-386.
[3] Qiu S, Sun H, Zhang AH, Xu HY, Yan GL, Han Y, Wang XJ (2014) Natural alkaloids: basic aspects, biological roles, and future perspectives. Chin. J. Nat. Med. 12: 401-6.
[4] Bartholomew BA, Smith MJ, Trudgill PW, Hopper DJ (1996) Atropine metabolism by pseudomonas sp. Strain AT3: Evidence for nortropine as an intermediate in tropine breakdown and reactions leading to succinate. Appl. Environ. Microbiol. 62: 3245-3250.
[5] Brust J C M (2004) InNeurological aspects of substance aabuse, 2nd (ed.) (Philadelphia: Elsevier) p. 310.
[6] Rörsch A, Berends FA, Bartlema CH, Stevens WF, Winsinck F (1971) The isolation and properties of Pseudomonas strains growing on atropine and producing an atropine esterase, Proc. K. Ned. Akad. Wet. Ser. C 74: 132-147.
[7] Stewart R (1965) Oxidation in Organic Chemistry, Part A (ed.) Wiberg KB, New York, Academic Press.
[8] Jose TP, Nandibewoor ST, Tuwar SM (2005) Mechanism of oxidation of L-histidine by heptavalent manganese in alkaline medium. E-J. Chem. 2: 75 -85.
[9] Fawzy A, Ashour SS, Musleh MA, (2014) Base-catalyzed oxidation of L-asparagine by alkaline permanganate and the effect of alkali-metal ion catalysts: kinetics and mechanistic approach, React. Kinet. Mech. Catal. 111: 443-460.
[10] Fawzy A, Shaaban MR (2014) Kinetic and mechanistic investigations on the oxidation of N’-heteroaryl unsymmetrical formamidines by permanganate in aqueous alkaline medium. Transition Met. Chem. 39: 379-386.
[11] Fawzy A, Zaafarany IA, Alfahemi J, Tirkistani FA (2015) Base-catalyzed oxidation of aminotriazole derivative by permanganate ion in aqueous alkaline medium: a kinetic study. Int. J. Inn. Res. Sci. Eng. Tech. 4: 6802-6814.
[12] AsgharBH, Fawzy A (2014) Kinetic, mechanistic, and spectroscopic studies of permanganate oxidation of azinylformamidines in acidic medium, with autocatalytic behavior of manganese (II). J. Saudi Chem. Soc., in press.
[13] Fawzy A, Ashour SS, Musleh MA (2014) Kinetics and mechanism of oxidation of L-histidine by permanganate ions in sulfuric acid medium. Int. J. Chem. Kinet. 46: 370-381.
[14] Ahmed GA, Fawzy A, Hassan RM (2007) Spectrophotometric evidence for the formation of short-lived hypomanganate (V) and manganite (VI) transient species during the oxidation of K-carrageenan by alkaline permanganate. Carbohydr. Res. 342: 1382-1386.
[15] Zaafarany IA, Fawzy A, Ahmed GA, Ibrahim SA, Hassan RM, Takagi HD (2010) Further evidence for detection of short-lived transient hypomanganate (V) and manganite (VI) intermediates during oxidation of some sulfated polysaccharides by alkaline permanganate using conventional spectrophotometeric techniques. Carbohydr. Res. 345: 1588-1593.
[16] Hassan RM, Fawzy A, Alarifi A, Ahmed GA, Zaafarany IA, Takagi HD (2011) Base-catalyzed oxidation of some sulfated macromolecules: kinetics and mechanism of formation of intermediate complexes of short-lived manganate (VI) and/or hypomanganate (V) during oxidation of iota- and lambda-carrageenan polysaccharides by alkaline permanganate. J. Mol. Catal. A, 335: 38-45.
[17] Hassan RM, Dahy A, Ibrahim S, Zaafarany IA, Fawzy A (2012) Oxidation of some macromolecules. Kinetics and mechanism of oxidation of methyl cellulose polysaccharide by permanganate ion in acid perchlorate solutions. Ind. Eng. Chem. Res. 51: 5424–5432.
[18] Gardner KA, Kuehnert LL, Mayer JM (1997) Hydrogen atom abstraction by permanganate:  oxidations of arylalkanes in organic solvents. Inorg. Chem. 36: 2069-2078.
[19] Perez-Benito JF (2009) Permanganate oxidation of α-amino acids: kinetic correlations for the non-autocatalytic and autocatalytic reaction pathways. J. Phys. Chem. 113: 15982-5989.
[20] Babatunde OAA (2008) study of the kinetics and mechanism of oxidation L-ascorbic acid by permanganate ion in acidic medium. World J. Chem. 3: 27-35.
[21] Day MC, Selbin J (1985) Theoretical Inorganic Chemistry, Reinhold Publishing Corporation, New York, p. 344.
[22] Byadagi KS, Hosahalli RV, Nandibewoor ST, Chimatadar SA (2012) Oxidation of a anticholinergic drug atropine sulfate monohydrate by alkaline copper (III) periodate complex: a kinetic and mechanistic study. Z. Phys. Chem. 226: 233–249.
[23] Byadagi KS, Nandibewoor ST, Chimatadar SA (2013) Catalytic activity of ruthenium (III) on the oxidation of an anticholinergic drug-atropine sulfate monohydrate by copper (III) periodate complex in aqueous alkaline medium - decarboxylation and free radical mechanism. ActaChim. Slov., 60: 617-627.
[24] Meti M, Nandibewoor ST, Chimatadar S (2014) Spectroscopic investigation and oxidation of the anticholinergic drug atropine sulfate monohydrate by hexacyanoferrate (III) in aqueous alkaline media: a mechanistic approach, Turk. J. Chem. 38: 477-487.
[25] Abdullah S, Al-Ghreizat S K, Abdel-Halim HM (2015) Kinetics of oxidation of atropine by alkaline KMnO4 in aqueous solutions. Asian J. Chem. 27: 3877-3882.
[26] Do Pham D D, Kelso G F, Yang Y, Hearn M T W (2014) Studies on the oxidative N-demethylation of atropine, the baine and oxycodone using a FeIII-TAML catalyst, Green Chem. 16: 1399-1405.
[27] Vogel IAA (1978) Text Book of Quantitative Inorganic Analysis. 4th Ed. ELBS and Longman, New York, p. 352.
[28] Furniss BS, Hannaford AJ, Smith WG, Tatchell AR (2004) In Vogel’s textbook of practical organic chemistry, 5th (ed.) (Pearson Education Ltd).
[29] Vogel AI (1973) In Text book of practical organic chemistry, 3rd (ed.) (London: Longman) p. 332.
[30] Feigl F (1975) Spot tests in organic analysis, p. 195, Elsevier, New York.
[31] Bailey N, Carrington A, Lott T, Symons MCRJ (1960) Structure and reactivity of the oxyanions of transition metals. PartVIII. Acidities and spectra of protonated oxyanions. J. Chem. Soc. 290-297.
[32] Carrington A, Symons MCRJ (1963) Structure and reactivity of the oxyanions of transition metals. Chem. Rev. 63: 443-460.
[33] Michaelis L, Menten ML (1913) The kinetics of invertase action. Biochem. Z., 49: 333–369.
[34] Frost AA, Person RG (1973) Kinetics and mechanism, p. 147, Wiley Eastern, New Delhi.
[35] Amis ES (1966) Solvent effect on reaction rates and mechanism, p. 28, Academic Press, New York.
[36] Weissberger A (1974) In Investigation of rates and mechanism of reactions in techniques of chemistry,(New York: John Wiley & Sons), p. 421.
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    Ahmed Fawzy, Ishaq A. Zaafarany, Fahd A. Tirkistani, Basim H. Asghar. (2016). Oxidative Degradation of Atropine Drug by Permanganate Ion in Perchloric and Sulfuric Acid Solutions: A Comparative Kinetic Study. Advances in Biochemistry, 4(5), 58-65. https://doi.org/10.11648/j.ab.20160405.12

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    Ahmed Fawzy; Ishaq A. Zaafarany; Fahd A. Tirkistani; Basim H. Asghar. Oxidative Degradation of Atropine Drug by Permanganate Ion in Perchloric and Sulfuric Acid Solutions: A Comparative Kinetic Study. Adv. Biochem. 2016, 4(5), 58-65. doi: 10.11648/j.ab.20160405.12

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    AMA Style

    Ahmed Fawzy, Ishaq A. Zaafarany, Fahd A. Tirkistani, Basim H. Asghar. Oxidative Degradation of Atropine Drug by Permanganate Ion in Perchloric and Sulfuric Acid Solutions: A Comparative Kinetic Study. Adv Biochem. 2016;4(5):58-65. doi: 10.11648/j.ab.20160405.12

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  • @article{10.11648/j.ab.20160405.12,
      author = {Ahmed Fawzy and Ishaq A. Zaafarany and Fahd A. Tirkistani and Basim H. Asghar},
      title = {Oxidative Degradation of Atropine Drug by Permanganate Ion in Perchloric and Sulfuric Acid Solutions: A Comparative Kinetic Study},
      journal = {Advances in Biochemistry},
      volume = {4},
      number = {5},
      pages = {58-65},
      doi = {10.11648/j.ab.20160405.12},
      url = {https://doi.org/10.11648/j.ab.20160405.12},
      eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ab.20160405.12},
      abstract = {The kinetics of oxidations of atropine (ATR) by permanganate ion in both perchloric and sulfuric acid solutions was studied using spectrophotometric technique at a constant ionic strength of 1.2 moldm-3 and at 25°C. In both acids, the reactions showed a first order dependence with respect to [permanganate], whereas the orders with respect to [ATR] and [H+] were found to be less than unity. The effect of acid concentration suggests that the reactions were acid-catalyzed. Variation of either ionic strength or dielectric constant of the medium had no effect significantly on the oxidation rates. The reactions mechanism adequately describing the kinetic results was proposed. In both acids, the main oxidation products of atropine were identified by spectral and chemical analyses as tropine and phenylmalonic acid. Under comparable experimental conditions, the oxidation rate of atropine in sulfuric acid was approximately three times higher than that in perchloric acid. The reactions constants involved in the different steps of the reactions mechanism have been evaluated. With admiration to the rate-limiting step of these reactions, the activation parameters have been evaluated and discussed.},
     year = {2016}
    }
    

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  • TY  - JOUR
    T1  - Oxidative Degradation of Atropine Drug by Permanganate Ion in Perchloric and Sulfuric Acid Solutions: A Comparative Kinetic Study
    AU  - Ahmed Fawzy
    AU  - Ishaq A. Zaafarany
    AU  - Fahd A. Tirkistani
    AU  - Basim H. Asghar
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    N1  - https://doi.org/10.11648/j.ab.20160405.12
    DO  - 10.11648/j.ab.20160405.12
    T2  - Advances in Biochemistry
    JF  - Advances in Biochemistry
    JO  - Advances in Biochemistry
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    EP  - 65
    PB  - Science Publishing Group
    SN  - 2329-0862
    UR  - https://doi.org/10.11648/j.ab.20160405.12
    AB  - The kinetics of oxidations of atropine (ATR) by permanganate ion in both perchloric and sulfuric acid solutions was studied using spectrophotometric technique at a constant ionic strength of 1.2 moldm-3 and at 25°C. In both acids, the reactions showed a first order dependence with respect to [permanganate], whereas the orders with respect to [ATR] and [H+] were found to be less than unity. The effect of acid concentration suggests that the reactions were acid-catalyzed. Variation of either ionic strength or dielectric constant of the medium had no effect significantly on the oxidation rates. The reactions mechanism adequately describing the kinetic results was proposed. In both acids, the main oxidation products of atropine were identified by spectral and chemical analyses as tropine and phenylmalonic acid. Under comparable experimental conditions, the oxidation rate of atropine in sulfuric acid was approximately three times higher than that in perchloric acid. The reactions constants involved in the different steps of the reactions mechanism have been evaluated. With admiration to the rate-limiting step of these reactions, the activation parameters have been evaluated and discussed.
    VL  - 4
    IS  - 5
    ER  - 

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Author Information
  • Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia

  • Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia

  • Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia

  • Chemistry Department, Faculty of Applied Science, Umm Al-Qura University, Makkah, Saudi Arabia

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