| Peer-Reviewed

A Comparative Kinetic Study of Silver(I)-Catalyzed Oxidations of Alanine and Valine by Platinum (IV) in Perchloric and Sulfuric Acids Solutions

Received: 17 April 2016     Accepted: 25 April 2016     Published: 10 May 2016
Views:       Downloads:
Abstract

The kinetics of oxidations of two aliphatic α-amino acids (AA), namely, alanine and valine by platinum (IV) has been investigated spectrophotometrically in perchloric and sulfuric acids solutions in the presence of silver (I) catalyst at a constant ionic strength of 1.0 mol dm-3 and at 25°C. The reactions were very slow to be measured in the absence of the catalyst. The reactions in both acids showed a first order dependence on both [PtIV] and [AgI], and less than unit order dependences with respect to both [AA] and [H+]. Increasing ionic strength was found to decrease the oxidation rates. Under comparable experimental conditions, the oxidation rates of alanine and valine in perchloric acid solutions were found to be about five times higher than those obtained in sulfuric acid solutions and the oxidation rates of alanine in both acids were found to be higher than those recorded with respect to valine. A plausible oxidations mechanism has been proposed and the rate law expression has been derived. Both spectral and kinetic evidences revealed formation of 1:1 intermediate complexes between AA and AgI in both acids before the rate-controlling step. Then the formed complexes react with the oxidant (PtIV) by an inner-sphere mechanism to give rise to the oxidation products of the amino acids which were identified as the corresponding aldehyde, ammonium ion and carbon dioxide. The activation parameters of the second order rate constants were evaluated and discussed.

Published in American Journal of Physical Chemistry (Volume 5, Issue 3)
DOI 10.11648/j.ajpc.20160503.13
Page(s) 65-73
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

α-Amino Acids, Platinum (IV), Kinetics, Mechanism, Oxidation, Silver (I) Catalyst

References
[1] Sumathi T, Sundaram PS, Chandramohan G (2011) A kinetic and mechanistic study on the silver (I)-catalyzed oxidation of L-alanine by cerium (IV) in sulfuric acid medium. Arab J. Chem. 4: 427–435.
[2] Hassan RM (1991) Kinetics and mechanism of oxidation of DL-a-alanine by permanganate ion in acid perchlorate media. J. Chem. 69: 2018-2023.
[3] Singh R, Tamta DK, Joshi SK, Chandra N, Kandpal ND (2011) Oxidation of amino acids by manganese (III) in aqueous sulphuric acid. J. Chem. Pharm. Res. 3: 529-535.
[4] Devra V, Jain S, Sharma PD (1994) Kinetics and mechanism of oxidation of glycine, alanine, and threonine by fluoride coordinated bismuth (V) in aqueous HclO4–HF medium. Int. J. Chem. Kinet. 26: 577–585.
[5] Pérez‐benito JF, Rodriguez RM, De Andrés G, Brillas E, Garrido JA (2012) Kinetics and mechanisms of the permanganate oxidation of L‐valine in neutral aqueous solutions. Int. J. Chemi. Kinet. 21:71–81.
[6] Sharanabasamma K, Angadi MA, Salunke MS, Tuwar S (2012) Kinetics of oxidation of L-valine by a copper (III) periodate complex in alkaline medium. J. Solution Chem. 41: 187-199.
[7] Chidan Kumar CS, Chandraju S, Made Gowda NM (2012) Oxidation of L-valine by manganese (III) in pyrophosphate medium: kinetics and mechanism. Am. J. Org. Chem. 2: 21-25.
[8] Criado S, Marioli JM, Allegretti PE, Furlong J, Rodríguez Nieto FJ, Mártire DO, García NA (2001) Oxidation of di- and tripeptides of tyrosine and valine mediated by singlet molecular oxygen, phosphate radicals and sulfate radicals. J Photochem Photobiol B. 65: 74-84.
[9] Fawzy A, Ashour SS, Musleh MA, Hassan RM, Asghar BH (2015) Kinetics and mechanistic approach to the chromic acid oxidation of L-tryptophan with a spectral detection of chromium (III) product. J. Saudi Chem. Soc. in press.
[10] Sanjeevagowda TP, Mahantesh AA, Abdulazizkhan LH (2008) Oxidative deamination and decarboxylation of L-asparagine by the aqueous alkaline diperiodato-nickelate (IV) complex. J. Solution Chem. 37: 1795–180.
[11] Khalid MAA (2007) Oxidative kinetics of amino acids by peroxydisulfate: Effect of dielectric constant, Arabian J. Sci. Eng. 33: 199-210.
[12] Senagar SKS, Yadav BS (1988) Kinetics and mechanism of copper (II)–catalyzed oxidation of asparagine by sodium N-chloro-p-toluene sulphonamide in alkaline media. J. Indian Chem. Soc. 65: 88–90.
[13] Asghar BH, Altass HM, Fawzy A (2015) Copper (II) catalysis for oxidation of L-tryptophan by hexacyanoferrate (III) in alkaline medium: a kinetic and mechanistic approach. J. Saudi. Chem. Soc. in press.
[14] Fawzy A (2015) Palladium (II)-catalyzed oxidation of L-tryptophan by hexacyanoferrate (III) in perchloric acid medium: a kinetic and mechanistic approach. J. Chem. Sci. In press.
[15] Fawzy A (2014) Influence of copper (II) catalyst on the oxidation of L-histidine by platinum (IV) in alkaline medium: a kinetic and mechanistic study. Transition Met. Chem. 39: 567-576.
[16] Fawzy A (2015) Kinetics and mechanistic approach to the oxidative behavior of biological anticancer platinum (IV) complex towards L-asparagine in acid medium and the effect of copper (II) catalyst. Int. J. Chem. Kinet. 47: 1-12.
[17] Fawzy A, Asghar BH (2015) Kinetics and mechanism of uncatalyzed and silver (I)-catalyzed oxidation of L-histidine by hexachloroplatinate (IV) in acid medium. Transition Met. Chem. 40: 287-295.
[18] Asghar BH, Altass HM, Fawzy A (2015) Transition metal ions-catalyzed oxidation of L-asparagine by platinum (IV) in acid medium: a kinetic and mechanistic study. Transition Met. Chem. 40: 587–594.
[19] Fawzy A, Zaafarany IA (2015) Kinetic and mechanistic investigation on the zirconium (IV)-catalyzed oxidation of L-histidine by hexachloroplatinate (IV) in acid medium. Chem. Sci. Rev. Lett. 4: 608-618.
[20] Fawzy A, Zaafarany IA (2015) Mechanistic investigation of copper (II)-catalyzed oxidation of L-asparagine by hexachloroplatinate (IV) in aqueous alkaline medium: a kinetic approach. J. Multidisc. Eng. Sci. Technol. 2: 1038-1045.
[21] Asghar BH, Altass HM, Fawzy A (2016) Silver (I)-catalysis of oxidative deamination and decarboxylation of L-asparagine and L-histidine by platinum (IV) in perchloric acid solutions: a comparative kinetics study. J. Env. Chem. Eng. 4: 617-623.
[22] 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.
[23] 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.
[24] Keage MC, Kelland MJ, Neidles LR, Warning MJ, ed. (1993) Molecular Aspects of Anticover Drug DNA Interactions, vol. 1, CRC Press, New York, NY, USA.
[25] Lemma K, Sargeson A, Elding LI (2000) Kinetics and mechanism for reduction of oral anticancer platinum (IV) dicarboxylate compounds by L-ascorbate ions. J. Chem. Soc. Dalton Trans. 7: 1167-1172.
[26] Lemma K, Shi T, Elding LI (2000) Kinetics and mechanism for reduction of the anticancer prodrug trans, trans, trans-[PtCl2 (OH)2 (c-C6H11NH2) (NH3)] (JM335) by thiols. Inorg. Chem. 39: 1728–1734.
[27] Weiss RP, Christian MC (1993) New cisplatin analogues in development. A review. Drugs 46: 360-377.
[28] Beattie K, Basolo F (1967) Reduction of some platinum (IV) complexes with tris (bipyridine) chromium (II) ion. Inorg. Chem. 6: 2069-2073.
[29] Beattie K, Basolo F (1971) Two-electron inner-sphere reduction of chloropentaammine-platinum (IV) ion by aquochromium (II) ion. Inorg. Chem. 10: 486-491.
[30] Moodley KG, Nicol MJ (1977) Kinetics of the reduction of platinum (IV) by tin (II) and copper (I) in aqueous chloride solutions. J. Chem. Soc., Dalton Trans. 239-243.
[31] Pal B, Sen Gupta KK (2000) Kinetics and mechanism of hexachloroplatinate (IV) reduction by some neutralized alpha-hydroxy acids in a carbonate-hydrogencarbonate buffer medium, Bull. Chem. Soc. Jpn. 73: 553-560.
[32] Shukla R, Upadhyay SK (2008) Non-ionic micellar inhibition on the rate of oxidation of L-histidine by alkaline hexacyanoferrate (III). Indian J. Chem. 47A: 551-555.
[33] Georgieva M, Andonovski B (2003) Determination of platinum (IV) by UV spectrophotometry. Anal. Bioanal. Chem. 375: 836-839.
[34] Vogel AI (1973) Text book of practical organic chemistry, third ed., ELBS Longman, London, 1973, pp. 332 and 679.
[35] Feigl F (1975) Spot tests in organic analysis, 195 pp. Elsevier, New York.
[36] Kramer J, Koch KR (2006) 195Pt NMR Study of the speciation and preferential extraction of Pt (IV)−mixed halide complexes by diethylenetriamine-modified silica-based anion exchangers. Inorg. Chem. 45: 7843-7855.
[37] Mason WR (1972) Platinum (II)-catalyzed substitutions of platinum (IV) complexes. Coord. Chem. Rev.7: 241-255.
[38] Hassan RM, Kojima T, Fukutomi T (1982) Kinetics of the oxidation of uranium (IV) by hexachloroplatinate (IV) in aqueous solution. VI International symposium on solute-solute-solvent interactions. Japan, pp. 113.
[39] Martell AE, Smith RM (1974) In: Critical Stability Constants. vol. I. Plenum Press, New York, pp. 321.
[40] Amis ES (1966) Solvent Effect on Reaction Rates and Mechanism, Academic Press, New York, pp. 28.
[41] Frost AA, Person RG (1970) Kinetics and mechanism, Wiley Eastern, New Delhi, pp. 147.
[42] Laidler K (1965) Chemical Kinetics. McGraw-Hill, New York.
[43] Weissberger A (1974) In Investigation of rates and mechanism of reactions in techniques of chemistry, John Wiley & Sons (New York: Interscience Publication) pp. 421.
Cite This Article
  • APA Style

    Ahmed Fawzy, Ishaq A. Zaafarany, Fahd A. Tirkistani, Ismail Althagafi, Jabir Alfahemi. (2016). A Comparative Kinetic Study of Silver(I)-Catalyzed Oxidations of Alanine and Valine by Platinum (IV) in Perchloric and Sulfuric Acids Solutions. American Journal of Physical Chemistry, 5(3), 65-73. https://doi.org/10.11648/j.ajpc.20160503.13

    Copy | Download

    ACS Style

    Ahmed Fawzy; Ishaq A. Zaafarany; Fahd A. Tirkistani; Ismail Althagafi; Jabir Alfahemi. A Comparative Kinetic Study of Silver(I)-Catalyzed Oxidations of Alanine and Valine by Platinum (IV) in Perchloric and Sulfuric Acids Solutions. Am. J. Phys. Chem. 2016, 5(3), 65-73. doi: 10.11648/j.ajpc.20160503.13

    Copy | Download

    AMA Style

    Ahmed Fawzy, Ishaq A. Zaafarany, Fahd A. Tirkistani, Ismail Althagafi, Jabir Alfahemi. A Comparative Kinetic Study of Silver(I)-Catalyzed Oxidations of Alanine and Valine by Platinum (IV) in Perchloric and Sulfuric Acids Solutions. Am J Phys Chem. 2016;5(3):65-73. doi: 10.11648/j.ajpc.20160503.13

    Copy | Download

  • @article{10.11648/j.ajpc.20160503.13,
      author = {Ahmed Fawzy and Ishaq A. Zaafarany and Fahd A. Tirkistani and Ismail Althagafi and Jabir Alfahemi},
      title = {A Comparative Kinetic Study of Silver(I)-Catalyzed Oxidations of Alanine and Valine by Platinum (IV) in Perchloric and Sulfuric Acids Solutions},
      journal = {American Journal of Physical Chemistry},
      volume = {5},
      number = {3},
      pages = {65-73},
      doi = {10.11648/j.ajpc.20160503.13},
      url = {https://doi.org/10.11648/j.ajpc.20160503.13},
      eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ajpc.20160503.13},
      abstract = {The kinetics of oxidations of two aliphatic α-amino acids (AA), namely, alanine and valine by platinum (IV) has been investigated spectrophotometrically in perchloric and sulfuric acids solutions in the presence of silver (I) catalyst at a constant ionic strength of 1.0 mol dm-3 and at 25°C. The reactions were very slow to be measured in the absence of the catalyst. The reactions in both acids showed a first order dependence on both [PtIV] and [AgI], and less than unit order dependences with respect to both [AA] and [H+]. Increasing ionic strength was found to decrease the oxidation rates. Under comparable experimental conditions, the oxidation rates of alanine and valine in perchloric acid solutions were found to be about five times higher than those obtained in sulfuric acid solutions and the oxidation rates of alanine in both acids were found to be higher than those recorded with respect to valine. A plausible oxidations mechanism has been proposed and the rate law expression has been derived. Both spectral and kinetic evidences revealed formation of 1:1 intermediate complexes between AA and AgI in both acids before the rate-controlling step. Then the formed complexes react with the oxidant (PtIV) by an inner-sphere mechanism to give rise to the oxidation products of the amino acids which were identified as the corresponding aldehyde, ammonium ion and carbon dioxide. The activation parameters of the second order rate constants were evaluated and discussed.},
     year = {2016}
    }
    

    Copy | Download

  • TY  - JOUR
    T1  - A Comparative Kinetic Study of Silver(I)-Catalyzed Oxidations of Alanine and Valine by Platinum (IV) in Perchloric and Sulfuric Acids Solutions
    AU  - Ahmed Fawzy
    AU  - Ishaq A. Zaafarany
    AU  - Fahd A. Tirkistani
    AU  - Ismail Althagafi
    AU  - Jabir Alfahemi
    Y1  - 2016/05/10
    PY  - 2016
    N1  - https://doi.org/10.11648/j.ajpc.20160503.13
    DO  - 10.11648/j.ajpc.20160503.13
    T2  - American Journal of Physical Chemistry
    JF  - American Journal of Physical Chemistry
    JO  - American Journal of Physical Chemistry
    SP  - 65
    EP  - 73
    PB  - Science Publishing Group
    SN  - 2327-2449
    UR  - https://doi.org/10.11648/j.ajpc.20160503.13
    AB  - The kinetics of oxidations of two aliphatic α-amino acids (AA), namely, alanine and valine by platinum (IV) has been investigated spectrophotometrically in perchloric and sulfuric acids solutions in the presence of silver (I) catalyst at a constant ionic strength of 1.0 mol dm-3 and at 25°C. The reactions were very slow to be measured in the absence of the catalyst. The reactions in both acids showed a first order dependence on both [PtIV] and [AgI], and less than unit order dependences with respect to both [AA] and [H+]. Increasing ionic strength was found to decrease the oxidation rates. Under comparable experimental conditions, the oxidation rates of alanine and valine in perchloric acid solutions were found to be about five times higher than those obtained in sulfuric acid solutions and the oxidation rates of alanine in both acids were found to be higher than those recorded with respect to valine. A plausible oxidations mechanism has been proposed and the rate law expression has been derived. Both spectral and kinetic evidences revealed formation of 1:1 intermediate complexes between AA and AgI in both acids before the rate-controlling step. Then the formed complexes react with the oxidant (PtIV) by an inner-sphere mechanism to give rise to the oxidation products of the amino acids which were identified as the corresponding aldehyde, ammonium ion and carbon dioxide. The activation parameters of the second order rate constants were evaluated and discussed.
    VL  - 5
    IS  - 3
    ER  - 

    Copy | Download

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

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

  • Sections