Mechanistic aspects of oxidation on L-tyrosine by diperiodatocuprate(III) complex in alkali media: a kinetic model

• Authors: Nagaraj Shetti , Rajesh Hegde , Sharanappa. Nandibewoor
• Languages of publication: EN

Abstracts

EN

Oxidation of an amino acid, L-tyrosine (L-Tyr) by diperiodatocuprate(III) (DPC) in alkaline medium at a constant ionic strength of 0.1 mol dm−3 was studied spectrophotometrically at different temperatures (288.1–313.1 K). The reaction between DPC and L-Tyr in alkaline medium exhibits 1:4 stoichiometry (L-Tyr:DPC). Intervention of free radicals was observed in the reaction. Based on the observed orders and experimental evidence, a mechanism involving monoperiodatocuprate(III) (MPC) as the reactive oxidant species has been proposed. A suitable mechanism is proposed through the formation of a complex and free radical intermediate. The products were identified by spot test and characterized by spectral studies. The reaction constants involved in the different steps of the mechanism were calculated. The activation parameters with respect to slow step of the mechanism were computed and are discussed. The thermodynamic quantities were determined for different equilibrium steps. Isokinetic temperature was also calculated and found to be 252.3 K. [...]

Keywords

EN

Kinetics; Mechanism; L-tyrosine; Diperiodatocuprate(III)

• Publisher: De Gruyter Open
• Journal: Open Chemistry
• Year: 2009
• Volume: 7
• Issue: 4
• Pages: 929-937

Dates

published

1 - 12 - 2009

online

6 - 10 - 2009

Contributors

author

Nagaraj Shetti

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

author

Rajesh Hegde

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

author

Sharanappa. Nandibewoor

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

References

• [1] G.C. Barrett, J.S. Davies, Amino acids, Peptides and Proteins vol. 33 (The Royal Society of Chemistry, 2002)
• [2] D.S. Mahadevappa, K.S. Rangappa, N.M. Gouda, B. Thimmegowda, Int. J. Chem. Kinet. 14, 1183 (1982) http://dx.doi.org/10.1002/kin.550141103[Crossref]
• [3] M.K. Mahanti, D. Laloo, J. Chem. Soc. Dalton Trans. 311 (1990)
• [4] R.M. Kulkarni, D.C. Bilehal, S.T. Nandibewoor, Transition Met. Chem. 28, 199 (2003) http://dx.doi.org/10.1023/A:1022924400513[Crossref]
• [5] W. Niu, Y. Zhu, K. Hu, C. Tong, H. Yang, Int. J. Chem. Kinet. 28, 899 (1996) http://dx.doi.org/10.1002/(SICI)1097-4601(1996)28:12<899::AID-KIN6>3.0.CO;2-I[Crossref]
• [6] K.D. Karlin, Y. Gultneh, In: J. Lipard (Ed.), Progress in Inorganic Chemistry (Wiley, New York, 1997) Vol. 35
• [7] W.B Tolman, Acc. Chem. Res. 30, 227 (1997) http://dx.doi.org/10.1021/ar960052m[Crossref]
• [8] J.L. Piere, Chem. Soc. Rev. 29, 251 (2000) http://dx.doi.org/10.1039/a909719h[Crossref]
• [9] T.S. Kiran, D.C. Hiremath, S.T. Nandibewoor, Z. Phys. Chem. 221, 501 (2007)
• [10] C.P. Murthy, B. Sethuram, T. Navaneeth Rao, Z. Phys. Chem. 262, 252 (1981)
• [11] G.H. Jeffery, J. Bassett, J. Mendham, R.C. Denney, Vogel’s Text Book of Quantitative Chemical Analysis, 5th edition (ELBS, U.K., 1996)
• [12] K. Randrerath, Thin Layer Chromatography (Academic Press, New York, 1968)
• [13] D.R. Lide, Hand book of Chemistry and Physics, 73rd edition (CRC, London, 1992)
• [14] S. Bhattacharya, P. Banerjee, Bull. Chem. Soc. Japan 69, 3475 (1996) http://dx.doi.org/10.1246/bcsj.69.3475[Crossref]
• [15] K. Sharanabasamma, M.S. Salunke, S.M. Tuwar, J. Solution Chem. 37, 1217 (2008) http://dx.doi.org/10.1007/s10953-008-9307-x[Crossref]
• [16] J.C. Bailar, H.J. Emeleus, S.R. Nyholm, A.F. Trotman-Dikenson, Comprehensive Inorganic Chemistry (Pergamon press, Oxford, 1975) Vol. 2
• [17] R. Chang, Physical Chemistry with Applications to Biological Systems (Mcmillan, New York, 1981)
• [18] P. Atkins, J.D. Paula, Atkin’s Physical Chemistry, 7th edition (Oxford University Press, New York, 2002)
• [19] K.S. Rangappa, M.P. Raghavendra, D.S. Mahadevappa, D. Channegouda, J. Org. Chem. 63, 531 (1998) http://dx.doi.org/10.1021/jo971398t[Crossref]
• [20] L. Pauling, The Nature of the Chemical Bond, 3rd edition (Oxford&IBH publishers, New Delhi, 1969)
• [21] C. Walling, Free Radicals in Solution (Academic Press, New York, 1957)
• [22] S.A. Farokhi, S.T. Nandibewoor, Tetrahedron 59, 7595 (2003) http://dx.doi.org/10.1016/S0040-4020(03)01148-7[Crossref]
• [23] E.S. Lewis, Investigations of Rates and Mechanisms of Reactions, 3rd edition (Wiley, New York, 1974)
• [24] O. Exner, Chem. Commun. 17, 1655 (2000) [and ref. therein] http://dx.doi.org/10.1039/b002758h[Crossref]
• [25] J.E. Leffler, J. Org. Chem. 20, 1202 (1955) http://dx.doi.org/10.1021/jo01126a009[Crossref]
• [26] B.A. Deganatti, N.P. Shetti, S.T. Nandibewoor, Transition Met. Chem. 34, 143 (2009) http://dx.doi.org/10.1007/s11243-008-9170-z[Crossref]

Identifiers

DOI

10.2478/s11532-009-0085-0