Autocatalyzed oxidation of amino acid, L-Citrulline by diperiodatocuprate(III) complex in aqueous alkaline medium: a kinetics and mechanistic approach

Journal of Chemical Sciences volume 132, Article number: 17 (2020) Cite this article

Abstract

Autocatalysed oxidation of important amino acid, L-Citrulline(L-Cit) by coordination complex, diperiodatocuprate(III) in aqueous alkaline medium at a constant ionic strength of 0.05 mol dm−3 was studied spectrophotometrically. Autocatalysis was observed by one of the products formed, i.e., Cu (II). 1:4 stoichiometry (L-Cit:DPC) exhibited between the reaction of L-Cit and DPC in aqueous alkaline medium. The path is of first-order in [DPC], less than unit order in [L-Cit] and independent in [OH-]. Periodate has a retarding effect on the rate of reaction. Ionic strength has a negligible effect on the reaction rate. The main reaction products were identified by spot tests and spectroscopic analysis. A composite mechanism involving uncatalysed and an autocatalysed reaction path (via free radical) was proposed. The activation parameters for the slow step of the mechanism and also the thermodynamic quantities for different steps of the mechanism were determined and discussed.

Graphic abstract

SYNOPSIS The oxidation of L-Citrulline by diperiodatocuprate(III) complex has been studied. Autocatalysis was observed by one of the products formed, i.e., Cu (II). 1:4 stoichiometry (L-Cit:DPC) exhibited between the reaction of L-Cit and DPC. A composite mechanism involving uncatalysed and an autocatalysed reaction path (via free radical) was proposed.

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References

  1. 1.

    Frank F C 1953 On spontaneous asymmetric synthesis Biochem. Biophys. Acta 11 459

    CAS  Article  Google Scholar 

  2. 2.

    Plasson R, Kondepudi D K, Bersini H, Commeyras A and Asakura K 2007 Emergence of homochirality in far-from-equilibrium systems: mechanisms and role in prebiotic chemistry Chirality 19 589

    CAS  Article  Google Scholar 

  3. 3.

    Kondepudi D K, Kaufman R J and Singh N 1990 Symmetry breaking in sodium chlorate crystallization Science 250 975

    CAS  Article  Google Scholar 

  4. 4.

    Soai K, Shibata T, Morioka H and Choji K 1995 Asymmetric autocatalysis and amplification of enantiomeric excess of a chiral molecule Nature 378 767

    CAS  Article  Google Scholar 

  5. 5.

    Fawzy A 2016 Kinetics and mechanism of uncatalyzed and ruthenium(III)-catalyzed oxidation of formamidine derivative by hexacyanoferrate(III) in aqueous alkaline medium J. Chem. Sci. 128 733

    CAS  Article  Google Scholar 

  6. 6.

    Malodi S J, Abbar J C and Nandibewoor S T 2010 Mechanistic aspects of uncatalyzed and ruthenium(III) catalyzed oxidation of DL-ornithine monohydrochloride by silver(III) periodate complex in aqueous alkaline medium Inorg. Chim. Acta 363 2430

    Article  Google Scholar 

  7. 7.

    Yatsimirskii K B, Strizhak P E and Zakrevskaya L N 1990 Space-time chaos in reactions of NADH with atmospheric oxygen in the presence of copper(II) complexes Teor. Eksp. Khim. 27 175

    Google Scholar 

  8. 8.

    Yatsimirskii K B, Zakrevskaya L N, Strizhak P E and Rybak-Akimova E V 1991 New oscillation reactions and pattern formation in dioxygen systems Chem. Phys. Lett. 186 15

    CAS  Article  Google Scholar 

  9. 9.

    Movius W G 1973 Oxidation of alcohols by diperiodatocuprate(III) Inorg. Chem. 12 31

    CAS  Article  Google Scholar 

  10. 10.

    Levason W and Spicer M D 1987 The chemistry of copper and silver in their higher oxidation states Coord. Chem. Rev. 76 45

    CAS  Article  Google Scholar 

  11. 11.

    Balikungeri A, Pelletier M and Monnier D 1977 Contribution to the study of the complexes bis(dihydrogen tellurato)cuprate(III) and argentate(III), bis(hydrogen periodato)cuprate(III) and argentate(III) Inorg. Chim. Acta 22 7

    CAS  Article  Google Scholar 

  12. 12.

    Weijun N, Yan Z, Kecheng H, Changlun T and Hangsheng Y 1996 Kinetics of oxidation of SCN− by diperiodato cuprate(III) (DPC) in alkaline medium Int. J. Chem. Kinet. 28 899

    Article  Google Scholar 

  13. 13.

    Karlin K D and Gultneh Y 1997 Progress in Inorganic Chemistry Vol. 35 S J Lippard (Ed.) (New York: Wiley) p. 220

  14. 14.

    Kitajima N and Moro-oka Y 1994 Copper-dioxygen complexes. Inorganic and bioinorganic perspectives Chem. Rev. 94 737

    CAS  Google Scholar 

  15. 15.

    RamReddy M G, Sethuram B and Rao T 1978 Effect of copper(I) catalysed oxidation of some amino acids by peroxydisulphate ion in aqueous alkaline medium Indian J. Chem. 16A 313

    Google Scholar 

  16. 16.

    “NOS2 - Nitric Oxide Synthase” 2015 Uniprot.org. uniprot consortium.

  17. 17.

    Jayaprakash Rao P, Sethuram B and Navaneeth Rao T 1985 Kinetics of oxidative deamination of some amino acids by diperiodatoargentate(III) in alkaline medium React. Kinet. Catal. Lett. 29 289

    Article  Google Scholar 

  18. 18.

    Laloo D and Mahanti M K 1990 Kinetics of oxidation of amino acids by alkaline hexacyanoferrate(III) J. Chem. Soc. Dalton Trans. 1 311

    Article  Google Scholar 

  19. 19.

    Bal Reddy K, Sethuram B and Navaneeth Rao T 1981 Kinetics of oxidative deamination and decarboxylation of some amino-acids by diperiodatocuprate (III) in alkaline-medium Indian J. Chem. 20A 395

    Google Scholar 

  20. 20.

    Althagafi I I and Fawzy A 2016 Kinetics and mechanistic study of permanganate oxidation of L-Citrulline in acidic and basic media Amer. J. Phys. Chem. 5 99

    CAS  Article  Google Scholar 

  21. 21.

    Murthy C P, Sethuram B and Navaneeth Rao T 1981 Kinetics of oxidation of some alcohols by diperiodatocuprate(III) in alkaline medium Z. Phys. Chem. 262 336

    CAS  Article  Google Scholar 

  22. 22.

    Jeffery G H, Bassett J, Mendham J and Denney R C 1996 Vogel’s Textbook of Quantitative Chemical Analysis (Essex: ELBS, Longman) (a) p. 455; (b) p. 371

  23. 23.

    Panigrahi G P and Misro P K 1978 Kinetics and mechanism of oxidation of aliphatic ketones by sodium metaperiodate: a comparative study of uncatalysed versus osmium tetraoxide-catalysed oxidation Indian J. Chem. 16A 762

    CAS  Google Scholar 

  24. 24.

    Gouda J I, Hanabaratti R M, Pattanshetti N A and Nandibewoor S T 2013 Oxidation of glycine by a (III) in aqueous alkaline medium Indian J. Chem. 52A 200

    Google Scholar 

  25. 25.

    Feigl F 1957 Spot Tests in Organic Analysis (New York: Elsevier) p. 195

  26. 26.

    Das A K and Das M 1994 Kinetics and mechanism of ruthenium(III) catalysed oxidation of formic acid by cerium(IV) in aqueous sulfuric acid media J. Chem. Soc. Dalton Trans. 4 589

    Article  Google Scholar 

  27. 27.

    Magdum P A, Bagoji A M and Nandibewoor S T 2015 Ruthenium(III) catalysed and uncatalysed oxidative mechanisms of methylxanthine drug theophylline by copper(III) periodate complex in alkali media: a comparative approach J. Phys. Org. Chem. 28 743

    CAS  Article  Google Scholar 

  28. 28.

    Reddy K B, Sethuram B and Navaneeth Rao T 1987 Oxidation of 1,2 ethane diol, 1,2 propane diol and 1,2 butane diol by diperiodatocuprate(III) in aqueous alkaline medium: a kinetic study Z. Phys. Chem. 268 706

    CAS  Google Scholar 

  29. 29.

    Valkai L, Peintler G and Horvath A K 2017 clarifying the equilibrium speciation of periodate ions in aqueous medium Inorg. Chem. 56 11417

    CAS  Article  Google Scholar 

  30. 30.

    Sethuram B 2003 Some Aspects of Electron Transfer Reactions Involving Organic Molecules (New Delhi: Allied Publishers (P) Ltd.) p. 73

  31. 31.

    Pattar V P, Magdum P A, Patil D G and Nandibewoor S T 2016 Thermodynamic, kinetic and mechanistic investigations of Piperazine oxidation by Diperiodatocuprate(III) complex in aqueous alkaline medium J. Chem. Sci. 128 477

    CAS  Article  Google Scholar 

  32. 32.

    Timy P J and Suresh M T 2007 Oxidation of threonine by the analytical reagent diperiodatocuprate(III) – An autocatalysed reaction J. Mol. Struct. 827 137

    Article  Google Scholar 

  33. 33.

    Kumar A, Kumar P and Ramamurthy P 1999 Kinetics of oxidation of glycine and related substrates by diperiodatoargentate (III) Polyhedron 18 773

  34. 34.

    Haines R I and McAuley A 1981 Synthesis and reactions of nickel(III) complexes Coord. Chem. Rev. 39 77

    CAS  Article  Google Scholar 

  35. 35.

    Chang R 1981 Physical Chemistry with Applications to Biological Systems (New York: McMillan) p. 326

  36. 36.

    Bagoji A M, Magdum P A and Nandibewoor S T 2016 Oxidation of acebutolol by copper(III) periodate complex in aqueous alkaline medium: a kinetic and mechanistic approach J. Sol. Chem. 45 1715

    CAS  Article  Google Scholar 

  37. 37.

    Munavalli D S, Naik P N, Ariga G G, Nandibewoor S T and Chimatadar S A 2015 Kinetics and mechanistic studies of oxidation of fluoroquionoline antibacterial agent norfloxacin by diperiodatocuprate(III) in aqueous alkaline medium Cogent Chem. 1 Article ID 1068510, 1

  38. 38.

    Weissberger A 1974 In: Investigation of rates and mechanism of reactions in techniques of chemistry Vol. 4 E S Lewis (Ed.) (New York: Wiley) p. 421

  39. 39.

    Farokhi S A and Nandibewoor S T 2003 Kinetic, mechanistic and spectral studies for the oxidation of sulfanilic acid by alkaline hexacyanoferrate(III) Tetrahedron 59 7595

    CAS  Article  Google Scholar 

  40. 40.

    Jaky M, Szeverenyi Z and Simandi L I 1991 Formation of manganate(V) in oxidations by permanganate ion in strongly alkaline solution Inorg. Chim. Acta 186 33

    CAS  Article  Google Scholar 

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Acknowledgements

The corresponding author thanks the UGC, New Dehli for the award of UGC-BSR faculty fellowship to Dr. S. T. Nandibewoor. Research scholar, Mr. S. B. Konnur thanks Department of Chemistry Karnatak University, Dharwad, providing necessary laboratory facilities.

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  1. P. G. Department of Studies in Chemistry, Karnatak University, Dharwad, Karnataka, 580 003, India

    Santosh B Konnur & Sharanappa T Nandibewoor

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  1. Santosh B Konnur
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  2. Sharanappa T Nandibewoor
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Correspondence to Sharanappa T Nandibewoor.

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Konnur, S.B., Nandibewoor, S.T. Autocatalyzed oxidation of amino acid, L-Citrulline by diperiodatocuprate(III) complex in aqueous alkaline medium: a kinetics and mechanistic approach. J Chem Sci 132, 17 (2020). https://doi.org/10.1007/s12039-019-1718-2

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Keywords

  • Kinetics
  • mechanism
  • diperiodatocuprate(III)
  • L-citrulline
  • autocatalysis