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Catalytic Effect of Cationic Gemini Micelles on the Rate of Condensation between Glycyl-dl-Aspartic Acid and Ninhydrin in the Absence and Presence of Organic Solvents

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Abstract

The reaction between glycyl-dl-aspartic acid (Gly-dl-Asp) and ninhydrin has been investigated in cationic gemini surfactants [alkanediyl-α,ω-bis (dimethyltetradecylammonium bromide)] (14-m-14). The study was carried out as functions of [Gly-dl-Asp], [ninhydrin], solvent (v/v %) and [surfactant] at pH = 5.0 and 70 °C. The reaction followed first-order kinetics in [Gly-dl-Asp] and fractional-order kinetics in [ninhydrin]. The reaction is catalyzed by TTABr/14-m-14. Addition of an organic solvent at fixed [surfactant] increases the absorbance as well as the rate of formation of Ruhemann’s purple. The results obtained in micellar media are treated quantitatively in terms of pseudophase and Piszkiewicz kinetic models. The Eyring equation is valid for the reaction over the range of temperatures used and different activation parameters have been evaluated. The kinetic data have been used to calculate the micellar binding constants K S for Gly-dl-Asp and K N for ninhydrin.

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References

  1. Ruhemann, S.: CCXII.—triketohydrindene hydrate. J. Chem. Soc., Trans. 97, 2025–2031 (1910)

    Article  Google Scholar 

  2. Joullie, M.M., Thompson, T.R., Nemeroff, N.H.: Ninhydrin and ninhydrin analogs. Syntheses and applications. Tetrahedron 47, 8791–8830 (1991)

    Article  CAS  Google Scholar 

  3. Oden, S., Von Hofsten, B.: Detection of fingerprints by the ninhydrin reaction. Nature 173, 449–450 (1954)

    Article  CAS  Google Scholar 

  4. Stoilovie, M., Kobus, H.J., Margot, P.A., Warrener, R.N.: Improved enhancement of ninhydrin developed fingerprints by cadmium complexation using low temperature photoluminescence technique. J. Forensic Sci. 31, 432–445 (1986)

    Google Scholar 

  5. Almog, J., Hirshfeld, A.: 5-methoxyninhydrin: a reagent for the chemical development of latent fingerprints that is compatible with the copper-vapor laser. J. Forensic Sci. 33, 1027–1030 (1988)

    CAS  Google Scholar 

  6. Liberti, A., Calabro, G., Chiarotti, M.: Storage effects on ninhydrin-developed fingerprints enhanced by zinc complexation. Forensic Sci. Int. 72, 161–169 (1995)

    Article  CAS  Google Scholar 

  7. Thomas, J.K.: Radiation-induced reactions in organized assemblies. Chem. Rev. 80, 283–299 (1980)

    Article  CAS  Google Scholar 

  8. Fendler, J.H.: Membrane Mimetic Chemistry. Wiley-Interscience, New York (1982)

    Google Scholar 

  9. Grätzel, M., Kalyansundaram, K.: Kinetics and Catalysis in Microheterogeneous Systems. Surfactant Science Series, vol. 38. Marcel Dekker, New York (1992)

    Google Scholar 

  10. Tanford, C.: The Hydrophobic Effect: Formation of Micelles and Biological Membranes. Wiley, New York (1973)

    Google Scholar 

  11. Patist, A., Kanicky, J.R., Shukla, P.K., Shah, D.O.: Importance of micellar kinetics in relation to technological processes. J. Colloid Interface Sci. 245, 1–15 (2002)

    Article  CAS  Google Scholar 

  12. Rosen, M.J.: Surfactants and Interfacial Phenomena. Wiley-Interscience, New York (2004)

    Book  Google Scholar 

  13. Kabir-ud-Din, Kumar: S., Aswal, V.K., Goyal, P.S.: Effect of the addition of n-alkylamines on the growth of sodium decyl sulfate micelles. J. Chem. Soc. Faraday Trans. 92, 2413–2415 (1996)

    Article  CAS  Google Scholar 

  14. Menger, F.M., Keiper, J.S.: Gemini surfactants. Angew. Chem. Int. Ed. 39, 1906–1920 (2000)

    Article  Google Scholar 

  15. Cerichelli, G., Mancini, G., Luchetti, L., Savelli, G., Bunton, C.A.: Specific micellar rate effects on unimolecular decarboxylation and cyclization. J. Phys. Org. Chem. 4, 71–76 (1991)

    Article  CAS  Google Scholar 

  16. Parker, A.J.: Protic-dipolar aprotic solvent effects on rates of biomolecular reactions. Chem. Rev. 69, 1–32 (1969)

    Article  CAS  Google Scholar 

  17. Azum, N., Naqvi, A.Z., Akram, M., Kabir-ud-Din: Studies of mixed micelle formation between cationic gemini and cationic conventional surfactants. J. Chem. Eng. Data 54, 1518–1523 (2009)

    Article  CAS  Google Scholar 

  18. Koya, P.A., Kabir-ud-Din, Ismail, K.: Micellization and thermodynamic parameters of butanediyl-1,4-bis(tetradecyldimethylammonium bromide) gemini surfactant at different temperatures: Effect of the addition of 2-methoxyethanol. J. Solution Chem. 41, 1271–1281 (2012)

    Article  Google Scholar 

  19. Pine, S.H.: Organic Chemistry. McGraw Hill International Editions, New York (1987)

    Google Scholar 

  20. Farme, S., Reusch, W.: Reaction with Primary Amines to form Imines. STEMWiki Hyperlibrary. http://chemwiki.ucdavis.edu (2014). Accessed 20 April 2014

  21. Bunton, C.A., Robinson, L.: Micellar effects upon nucleophilic aromatic and aliphatic substitution. J. Am. Chem. Soc. 90, 5972–5979 (1968)

    Article  CAS  Google Scholar 

  22. Vera, S., Rodenas, E.: Inhibiton effect of cationic micelles on the basic hydrolysis of aromatic esters. Tetrahedron 42, 143–149 (1986)

    Article  CAS  Google Scholar 

  23. Cerichelli, G., Mancini, G., Luchetti, L., Savelli, G., Bunton, C.A.: Surfactant effects upon cyclization of o-(.omega.-haloalkoxy)phenoxide ions. The role of premicellar assemblies. Langmuir 10, 3982–3987 (1994)

    Article  CAS  Google Scholar 

  24. Brinchi, L., Germani, R., Gorracci, L., Savelli, G., Bunton, C.A.: Decarboxylation and dephosphorylation in new gemini surfactants. changes in aggregate structures. Langmuir 18, 7821–7825 (2002)

    Article  CAS  Google Scholar 

  25. Kabir-ud-Din, Fatma, W.: Role of cationic gemini surfactants toward enhanced ninhydrin–tryptophan reaction. J. Phys. Org. Chem. 20, 440–447 (2007)

    Article  Google Scholar 

  26. Akram, M., Kumar, D., Kabir-ud-Din: Effect of dicationic gemini surfactants 16-s-16 (s = 4, 5, 6) on the ninhydrin–dipeptide (glycyl–tyrosine) reaction. Int. J. Chem. Kinet. 44, 800–809 (2012)

    Article  CAS  Google Scholar 

  27. Karaborni, S., Esselink, K., Hilbers, P.A., Smit, B., Karthauser, J., van Os, N.M., Zana, R.: Simulating the self-assembly of gemini (dimeric) surfactants. Science 266, 254–256 (1994)

    Article  CAS  Google Scholar 

  28. Menger, F.M., Portnoy, C.E.: Chemistry of reactions proceeding inside molecular aggregates. J. Am. Chem. Soc. 89, 4698–4703 (1967)

    Article  CAS  Google Scholar 

  29. Bunton, C.A.: Reactivity in aqueous association colloids. Descriptive utility of the pseudophase model. J. Mol. Liq. 72, 231–249 (1997)

    Article  CAS  Google Scholar 

  30. Piszkiewicz, D.: Positive cooperativity in micelle-catalyzed reactions. J. Am. Chem. Soc. 99, 1550–1557 (1977)

    Article  CAS  Google Scholar 

  31. Hill, A.V.: A new mathematical treatment of changes of ionic concentration in muscle and nerve under the action of electric currents, with a theory as to their mode of excitation. J. Physiol. 40, 190–224 (1910)

    Article  CAS  Google Scholar 

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Author notes

  1. Kabir-ud-Din

    Present address: Department of Chemistry, Faculty of Natural Sciences, Arba Munch University, Arba Munch, Ethiopia

Authors and Affiliations

  1. Department of Chemistry, Aligarh Muslim University, Aligarh, 202 002, India

    Mohd. Akram, Adel A. M. Saeed &  Kabir-ud-Din

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  1. Mohd. Akram
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  2. Adel A. M. Saeed
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  3. Kabir-ud-Din
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Akram, M., Saeed, A.A.M. & Kabir-ud-Din Catalytic Effect of Cationic Gemini Micelles on the Rate of Condensation between Glycyl-dl-Aspartic Acid and Ninhydrin in the Absence and Presence of Organic Solvents. J Solution Chem 44, 1529–1544 (2015). https://doi.org/10.1007/s10953-015-0360-y

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