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Kinetics and Mechanism of Silver(I)-Catalyzed Oxidation of Tryptophan by Platinum(IV) in Perchlorate Solutions

Received: 15 January 2016     Accepted: 26 January 2016     Published: 25 February 2016
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Abstract

The kinetics of oxidation of tryptophan by platinum(IV) was investigated in aqueous perchlorate solutions in the presence of silver(I) catalyst at a constant ionic strength of 2.0 mol dm-3 and at 25°C. The progress of the reaction was followed spectrophotometrically. The reaction did not proceed in the absence of the catalyst. The catalyzed reaction exhibited a first order dependence on both [PtIV] and [AgI] whereas the order with respect to tryptophan concentration was found to be less than unity. Increasing ionic strength and dielectric constant was found to decrease the oxidation rate. The suggested oxidation mechanism involves formation of a silver(I)-tryptophan intermediate complex in a pre-equilibrium step, which confirmed by both spectral and kinetic evidences. The complex reacts with the oxidant by an inner-sphere mechanism leading to decomposition of the complex in the rate-determining step. The final oxidation products of tryptophan were identified as the corresponding aldehyde (indole-3-acetaldehyde), ammonium ion and carbon dioxide.

Published in American Journal of Chemical Engineering (Volume 4, Issue 1)
DOI 10.11648/j.ajche.20160401.14
Page(s) 23-29
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

Tryptophan, Catalyzed-Oxidation, Silver(I), Platinum(IV), Kinetics, Mechanism

References
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  • APA Style

    Ahmed Fawzy, Ismail Althagafi. (2016). Kinetics and Mechanism of Silver(I)-Catalyzed Oxidation of Tryptophan by Platinum(IV) in Perchlorate Solutions. American Journal of Chemical Engineering, 4(1), 23-29. https://doi.org/10.11648/j.ajche.20160401.14

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    ACS Style

    Ahmed Fawzy; Ismail Althagafi. Kinetics and Mechanism of Silver(I)-Catalyzed Oxidation of Tryptophan by Platinum(IV) in Perchlorate Solutions. Am. J. Chem. Eng. 2016, 4(1), 23-29. doi: 10.11648/j.ajche.20160401.14

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    AMA Style

    Ahmed Fawzy, Ismail Althagafi. Kinetics and Mechanism of Silver(I)-Catalyzed Oxidation of Tryptophan by Platinum(IV) in Perchlorate Solutions. Am J Chem Eng. 2016;4(1):23-29. doi: 10.11648/j.ajche.20160401.14

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  • @article{10.11648/j.ajche.20160401.14,
      author = {Ahmed Fawzy and Ismail Althagafi},
      title = {Kinetics and Mechanism of Silver(I)-Catalyzed Oxidation of Tryptophan by Platinum(IV) in Perchlorate Solutions},
      journal = {American Journal of Chemical Engineering},
      volume = {4},
      number = {1},
      pages = {23-29},
      doi = {10.11648/j.ajche.20160401.14},
      url = {https://doi.org/10.11648/j.ajche.20160401.14},
      eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ajche.20160401.14},
      abstract = {The kinetics of oxidation of tryptophan by platinum(IV) was investigated in aqueous perchlorate solutions in the presence of silver(I) catalyst at a constant ionic strength of 2.0 mol dm-3 and at 25°C. The progress of the reaction was followed spectrophotometrically. The reaction did not proceed in the absence of the catalyst. The catalyzed reaction exhibited a first order dependence on both [PtIV] and [AgI] whereas the order with respect to tryptophan concentration was found to be less than unity. Increasing ionic strength and dielectric constant was found to decrease the oxidation rate. The suggested oxidation mechanism involves formation of a silver(I)-tryptophan intermediate complex in a pre-equilibrium step, which confirmed by both spectral and kinetic evidences. The complex reacts with the oxidant by an inner-sphere mechanism leading to decomposition of the complex in the rate-determining step. The final oxidation products of tryptophan were identified as the corresponding aldehyde (indole-3-acetaldehyde), ammonium ion and carbon dioxide.},
     year = {2016}
    }
    

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  • TY  - JOUR
    T1  - Kinetics and Mechanism of Silver(I)-Catalyzed Oxidation of Tryptophan by Platinum(IV) in Perchlorate Solutions
    AU  - Ahmed Fawzy
    AU  - Ismail Althagafi
    Y1  - 2016/02/25
    PY  - 2016
    N1  - https://doi.org/10.11648/j.ajche.20160401.14
    DO  - 10.11648/j.ajche.20160401.14
    T2  - American Journal of Chemical Engineering
    JF  - American Journal of Chemical Engineering
    JO  - American Journal of Chemical Engineering
    SP  - 23
    EP  - 29
    PB  - Science Publishing Group
    SN  - 2330-8613
    UR  - https://doi.org/10.11648/j.ajche.20160401.14
    AB  - The kinetics of oxidation of tryptophan by platinum(IV) was investigated in aqueous perchlorate solutions in the presence of silver(I) catalyst at a constant ionic strength of 2.0 mol dm-3 and at 25°C. The progress of the reaction was followed spectrophotometrically. The reaction did not proceed in the absence of the catalyst. The catalyzed reaction exhibited a first order dependence on both [PtIV] and [AgI] whereas the order with respect to tryptophan concentration was found to be less than unity. Increasing ionic strength and dielectric constant was found to decrease the oxidation rate. The suggested oxidation mechanism involves formation of a silver(I)-tryptophan intermediate complex in a pre-equilibrium step, which confirmed by both spectral and kinetic evidences. The complex reacts with the oxidant by an inner-sphere mechanism leading to decomposition of the complex in the rate-determining step. The final oxidation products of tryptophan were identified as the corresponding aldehyde (indole-3-acetaldehyde), ammonium ion and carbon dioxide.
    VL  - 4
    IS  - 1
    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

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