06Jan 2018

KINETICS AND MECHANISM OF HYDROLYSIS OF UREA AND N, N′-DIACETYL UREA IN PRESENCE OF COBALT(II), COPPER(II), ZINC(II)-SCHIFF BASE COMPLEXES.

  • Department of Chemistry, University of Rajshahi, Rajshahi-6205, Bangladesh.
  • Department of Environmental Science, Independent University, Dhaka, Bangladesh.
  • Abstract
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Solid aquo CoII, CuII and ZnII complexes of Schiff bases derived from amino acids and salicylaldehyde had been prepared, characterized and used as model enzymes of Urease. Using a pH-stat method, the kinetics of acid hydrolysis of urea and its derivative N,N′-diacetyl urea in the presence of the complexes had been studied in pH range of 4.91?6.19 at 300C and I = 0.10 mol dm-3 (KNO3). It was found that the hydrolytic reactions followed first order kinetics (pseudo-unimolecular) with respect to urea or N,N′-diacetyl urea concentration. The complexes enhanced the rate of hydrolysis markedly; the values of the second-order rate constants (kH) being 106 times greater than those found in the absence of the catalysts. Comparison showed that the complexes acted as better catalysts for urea [kH = (0.79?2.34)?102 dm3 mol-1 s-1] than N,N′-diacetyl urea [kH = (0.36?1.19)?102 dm3 mol-1 s-1] towards the hydrolysis reactions. The catalytic performance of the complexes was 30-100% greater in urea than in N,N′-diacetyl urea. The proposed mechanism involved the formation of mixed ligand chelate complex by replacement of two coordinated labile water molecules by NHR′ (R′= H or COCH3) and carbonyl group of urea or N,N′-diacetyl urea followed by nucleophilic and electrohilic attacks by H2O and H+ respectively. The average half-life period (t?) ranges for urea and N,N′-diacetyl urea hydrolysis were 450?676 and 529?807 seconds respectively. [CoII(Gly)(Sal)(H2O)3] was found as the most efficient catalyst towards urea hydrolysis reactions. This investigation would establish the potential catalytic role of the complexes in hydrolyzing urea and its derivative, and thereby would throw more light on hydrolytic mechanism of urease enzyme.


  1. Raman N, Dhaveethu RJ, Sakthivel A, Synthesis, Spectral Characterization of Schiff base Transition Metal Complexes: DNA Cleavage and Antimicrobial Activity Studies, J Chemical Sciences, 119(4), 2007, 303310.
  2. Nassr LAE, Dief AMA, Kinetic Screening for the Acid-Catalyzed Hydrolysis of Some Hydrophobic Fe(II) Schiff Base Amino Acid Chelates and Reactivity Trends in the Presence of Alkali Halide and Surfactant, Int. J. Chem. Kinetics, 47(8), 2015, 501-508.
  3. Mohamad ADM, Abualreish MJA, Adam MSS, Kinetics of the base hydrolysis of iron (II) complexes with pyridyl?quinolyl Schiff base ligands in aqueous and aqueous/methanol binary mixtures, Journal of the Iranian Chemical Society, 12(9), 2015, 1521-1528.
  4. Donde KJ, Synthesis and characterization of transition metal complexes of 2-(salicylimino)-3-hydroxypyridine, J. Chem. Pharm. Res., 2015, 7(6), 798-803.
  5. Maret W, Wedd A, Binding, Transport and Storage of Metal Ions in Biological Cells, Royal Society of Chemistry, Cambridge, UK, 2014. RSC Metallobiology Series No. 2.
  6. Fidaleo M, Lavecchia R, Kinetic Study of Enzymatic Urea Hydrolysis in the pH Range 4?9, Chem. Biochem. Eng. Q., 2003, 17(4), 311?318.
  7. Dixon M, Webb EC, Enzymes, 3rd edition, Academic Press Inc., London, 1981.
  8. Khan M, Javed MM, Zahoor S, Haq IU, Kinetics and Thermodynamic Study of Urease Extracted from Soybeans,Biologia, 2013, 59(1), 7-14.
  9. Cartes P, Jara AA, Demanet R, Mora ML, Urease activity and nitrogen mineralization kinetics as affected by temperature and urea input rate in southern chileanandisols, J. Soil Sc. Plant Nutr., 2009, 9(1), 69-82.
  10. Blakeley RL, Treston A, Andrews RK, Zerner B, Nickel(II) promoted ethanolysis of N-(2-Pyridylmethyl)urea: A model for urease, J. Am. Chem. Soc, 1982, 104, 612.
  11. Banu S, Catalytic activities of Zn(II), Co(II), Ni(II), Cu(II), Ru(II), Pd(II) and Mn(II) towards the hydrolysis of urea, M.Sc Thesis, 1988, Department of Chemistry, University of Rajshai, Bangladesh.
  12. Furniss BS, Hannaford AJ, Smith PWG, Tatchell AR, Vogel?s Textbook of Practical Organic Chemistry, 5th edition (eighth impression), 2011, Dorling Kindersley Pvt. Ltd., New Delhi, India.
  13. Azzouz ASP, Synthesis of Schiff bases derived from benzaldehyde and salicylaldehyde with some amino acids by a new develop method, National Journal of Chemistry, 2010, 37, 158-168.
  14. Salama MM, Ahmed SG, Hassan SS, Synthesis, characterizations, biological, and molecular docking studies of some amino acid Schiff bases with their cobalt(II) complexes, Advances in Biological Chemistry, 2017, 7(5), 182-194.
  15. Chakraborty H, Rahman ML, Kinetics of hydrolysis of amino acid esters in presence of aquocomplexes involving ethylenediamine, diethylenetriamine and triethylenetetramine ligands. Part 1 - copper(II) and nickel(II), Transition Met. Chem., 1993, 18, 545-547.
  16. Laidler KJ, Reaction Kinetics: Reactions in Solution, Volume 2, Literary Licensing LLC, Whitefish, MT, USA, ISBN: 9781258820725.
  17. Zheng H, Du X, Reduced steric hindrance and optimized spatial arrangement of carbohydrate ligands in imprinted monolayers for enhanced protein binding, Biochimica et BiophysicaActa, 2013, 1828, 792?800.
  18. Knobloch B, Linert W, Sigel H,Metal ion-binding properties of (N3) deprotonated uridine, thymidine, and related pyrimidine nucleosides in aqueous solution, PNAS, 2005, 102(21), 7459?7464.
  19. Chakraborty H, Paul N, Rahman ML, Catalytic activities of Schiff base aquocomplexes of copper(II) towards hydrolysis of amino acid esters, Transition Met. Chem., 1994, 19, 524-526.
  20. Lee JD, Concise Inorganic Chemistry, 5th edition, Wiley (India) Pvt. Limited, New Delhi, India, 2008. ISBN: 8126515546.
  21. Alvarez S, Distortion Pathways of Transition Metal Coordination Polyhedra Induced by Chelating Topology, Chem. Rev., 2015, 115, 13447−
  22. Khalil MMH, Ismail EH, Mohamed GG, Zayed EM, Badr, A, Synthesis and characterization of a novel schiff base metal complexes and their application in determination of iron in different types of natural water, Open Journal of Inorganic Chemistry, 2012, 2, 13-21.
  23. Arish D, Nair MS, Synthesis of some Schiff base metal complexes involving para substituted aromatic aldehydes and glycylglycine: Spectral, electrochemical, thermal and surface morphology studies, Journal of Molecular Structure, 2010, 983, 112?121.
  24. DePauw University. Kinetic of the Hydrolysis of Urea: Part II. DePauw University, Greencastle, Indiana, USA. Available: http://dpuadweb.depauw.edu/harvey_web/Chem260/Chem260pdfs/WorksheetKeys/ureaPart2_ Key.pdf (accessed: January 02, 2018)

[Nazmul Islam, Habibur Rahman and M. Lutfor Rahman. (2018); KINETICS AND MECHANISM OF HYDROLYSIS OF UREA AND N, N′-DIACETYL UREA IN PRESENCE OF COBALT(II), COPPER(II), ZINC(II)-SCHIFF BASE COMPLEXES. Int. J. of Adv. Res. 6 (Jan). 521-529] (ISSN 2320-5407). www.journalijar.com


Md. Nazmul Islam
Department of Chemistry, University of Rajshahi, Rajshahi-6205, Bangladesh

DOI:


Article DOI: 10.21474/IJAR01/6252      
DOI URL: https://dx.doi.org/10.21474/IJAR01/6252