| Peer-Reviewed

Thermodynamic Parameters of Complexation Calixpyrrole Derivative with Lanthanides Cations (Lu3, Ho3, Eu3+ and Pr3+) in Nonaquoeus Media

Received: 12 January 2015     Accepted: 23 January 2015     Published: 21 March 2015
Views:       Downloads:
Abstract

Calix [4] pyrrole derivative was used to target lanthanide cations. Meso tetramethyl-tetrakis-[(4-N, N-diethylacetamide) phenoxymethyl] calix [4] pyrrole, L2 was synthesised. This receptor constituted of hard donor atoms at the lower rim which interact with lanthanide cations being hard cations. 1H NMR investigations showed that both, the pyrrolic N and the acetamide arm group provide sites for interaction with lanthanide metal cations. These findings are verified by conductance measurements in acetonitrile, plots of molar conductance against the ligand/metal cation ratio reveal the formation of 1:2 complexes between this ligand with lanthanide metal cations. Standard thermodynamics parameters of complexation (log Ks, ΔHᵒc, ΔSᵒc, ΔGᵒc) of L2 with lanthanide cations in acetonitrile were determined using the Nano ITC (isothermal titration calorimetry). The complexation process between these metal cations and the receptor L2 was enthalpically controlled.

Published in American Journal of Physical Chemistry (Volume 4, Issue 1)
DOI 10.11648/j.ajpc.20150401.12
Page(s) 6-15
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), 2015. Published by Science Publishing Group

Keywords

Calixpyrrole Receptor, Lanthanide Metal Cations, 1H NMR Investigations, Conductance Measurements, Thermodynamic Studies

References
[1] J.W. Steed, J. L. Atwood, “Supramolecular Chemistry”; John Wiley & Sons: New York, pp. 2–9, 2000.
[2] D. S. Flett. “Resin impregnated: the current position”. Chem. Ind. Vol.6, pp., 1977.
[3] L. L. Tavlarides, J.H. Bae, C. K. Lee. “Solvent extraction, membranes and ion exchange in hydrometallurgical dilute metals sepration”. Separation Science and Technology. Vol.22, no. 2-3, pp.581-617, 1987.
[4] A. Warshawsky. “Extraction with solvent-impregnated resins”. Ion Exch. Solvent Extr. Vol. 8, pp. 229-310, 1981.
[5] K. D. Bhatt, D. J. Vyas, H. S. Gupte, B. A. Makwana, S. M. Darjee, V. K. Jain. “Solid phase extraction, pre concentration and sequential separation of U(VI), Th(IV), La(III) and Ce(III) by Octa- O- methoxy resorcin [4] arene based Amberlite XAD-4 Chelating Resin”. World J. Anal. Chem. Vol. 2, pp. 31-41, 2014.
[6] T. P. Rao, V. Biju. “Trace determination of lanthanides in metallurgical, environmental, and geological samples”. Crit. Rev. Anal. Chem. Vol. 30, no. 2–3, pp. 179–220, 2000.
[7] K. Greinacher. “Industrial application of rare earth elements”, in ACS Symposium Series; American Chemical Society: Washington, DC, 1981.
[8] E. El-Sofany. “Removal of lanthanum and gadolinium from nitrate medium using Aliquat-336 impregnated onto Amberlite XAD-4”. J. Hazard. Mater. Vol. 153, no. 3, pp. 948–954, 2008.
[9] C. Stem, F. Franceschi, E. Solari, C. Floriani, R. Nazzareno, R. Scopelliti. “The use of macrocyclic and polydentate ligands in ruthenium organometallic chemistry”. J. Organomet. Chem. Vol. 86, pp. 593, 2000.
[10] H. L. Handl, R. J. Gillies. “Lanthanide-based luminescent assays for ligand-receptor interactions”. Life Sciences. Vol. 77, pp. 361–371, 2005.
[11] B. S. Furniss, A. J. Hannford, P. W. G. Smith, A. R. Tatchell, “Vogel s Textbook of Practical Organic Chemistry”, 5th Eds.; Logman Scientific and Technical, London, 1989.
[12] L. E.Briggner, I.Wadso. “Test and calibration processes for microcalorimeters, with special reference to heat conduction instruments used with aqueous systems” . J. Biochem. Biophys. Methods. Vol. 22, pp. 101, 1991.
[13] P. Anzenbacher , K. Jursı´kova´ , V. M. Lynch, P. A. Gale and J. L. Sessler. “Calix[4]pyrroles Containing Deep Cavities and Fixed Walls. “Synthesis Structural Studies and Anion Binding Properties of the Isomeric Products Derived from the Condensation of p-Hydroxyacetophenone and Pyrrole”. J. Am. Chem. Soc. Vol. 121, pp. 11020–11021, 1999.
Cite This Article
  • APA Style

    Ahmed Yahya Issa Rubaye. (2015). Thermodynamic Parameters of Complexation Calixpyrrole Derivative with Lanthanides Cations (Lu3, Ho3, Eu3+ and Pr3+) in Nonaquoeus Media. American Journal of Physical Chemistry, 4(1), 6-15. https://doi.org/10.11648/j.ajpc.20150401.12

    Copy | Download

    ACS Style

    Ahmed Yahya Issa Rubaye. Thermodynamic Parameters of Complexation Calixpyrrole Derivative with Lanthanides Cations (Lu3, Ho3, Eu3+ and Pr3+) in Nonaquoeus Media. Am. J. Phys. Chem. 2015, 4(1), 6-15. doi: 10.11648/j.ajpc.20150401.12

    Copy | Download

    AMA Style

    Ahmed Yahya Issa Rubaye. Thermodynamic Parameters of Complexation Calixpyrrole Derivative with Lanthanides Cations (Lu3, Ho3, Eu3+ and Pr3+) in Nonaquoeus Media. Am J Phys Chem. 2015;4(1):6-15. doi: 10.11648/j.ajpc.20150401.12

    Copy | Download

  • @article{10.11648/j.ajpc.20150401.12,
      author = {Ahmed Yahya Issa Rubaye},
      title = {Thermodynamic Parameters of Complexation Calixpyrrole Derivative with Lanthanides Cations (Lu3, Ho3, Eu3+ and Pr3+) in Nonaquoeus Media},
      journal = {American Journal of Physical Chemistry},
      volume = {4},
      number = {1},
      pages = {6-15},
      doi = {10.11648/j.ajpc.20150401.12},
      url = {https://doi.org/10.11648/j.ajpc.20150401.12},
      eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.ajpc.20150401.12},
      abstract = {Calix [4] pyrrole derivative was used to target lanthanide cations. Meso tetramethyl-tetrakis-[(4-N, N-diethylacetamide) phenoxymethyl] calix [4] pyrrole, L2 was synthesised. This receptor constituted of hard donor atoms at the lower rim which interact with lanthanide cations being hard cations. 1H NMR investigations showed that both, the pyrrolic N and the acetamide arm group provide sites for interaction with lanthanide metal cations. These findings are verified by conductance measurements in acetonitrile, plots of molar conductance against the ligand/metal cation ratio reveal the formation of 1:2 complexes between this ligand with lanthanide metal cations. Standard thermodynamics parameters of complexation (log Ks, ΔHᵒc, ΔSᵒc, ΔGᵒc) of L2 with lanthanide cations in acetonitrile were determined using the Nano ITC (isothermal titration calorimetry). The complexation process between these metal cations and the receptor L2 was enthalpically controlled.},
     year = {2015}
    }
    

    Copy | Download

  • TY  - JOUR
    T1  - Thermodynamic Parameters of Complexation Calixpyrrole Derivative with Lanthanides Cations (Lu3, Ho3, Eu3+ and Pr3+) in Nonaquoeus Media
    AU  - Ahmed Yahya Issa Rubaye
    Y1  - 2015/03/21
    PY  - 2015
    N1  - https://doi.org/10.11648/j.ajpc.20150401.12
    DO  - 10.11648/j.ajpc.20150401.12
    T2  - American Journal of Physical Chemistry
    JF  - American Journal of Physical Chemistry
    JO  - American Journal of Physical Chemistry
    SP  - 6
    EP  - 15
    PB  - Science Publishing Group
    SN  - 2327-2449
    UR  - https://doi.org/10.11648/j.ajpc.20150401.12
    AB  - Calix [4] pyrrole derivative was used to target lanthanide cations. Meso tetramethyl-tetrakis-[(4-N, N-diethylacetamide) phenoxymethyl] calix [4] pyrrole, L2 was synthesised. This receptor constituted of hard donor atoms at the lower rim which interact with lanthanide cations being hard cations. 1H NMR investigations showed that both, the pyrrolic N and the acetamide arm group provide sites for interaction with lanthanide metal cations. These findings are verified by conductance measurements in acetonitrile, plots of molar conductance against the ligand/metal cation ratio reveal the formation of 1:2 complexes between this ligand with lanthanide metal cations. Standard thermodynamics parameters of complexation (log Ks, ΔHᵒc, ΔSᵒc, ΔGᵒc) of L2 with lanthanide cations in acetonitrile were determined using the Nano ITC (isothermal titration calorimetry). The complexation process between these metal cations and the receptor L2 was enthalpically controlled.
    VL  - 4
    IS  - 1
    ER  - 

    Copy | Download

Author Information
  • Department of Chemistry, College of Science, University of Basrah, Basrah, Iraq

  • Sections