Skip to main content
SpringerLink
Log in

Hydrolysis of Tetraglycine by a Zr(IV)-Substituted Wells–Dawson Polyoxotungstate Studied by Diffusion Ordered NMR Spectroscopy

  • Original Paper
  • Published:
Journal of Cluster Science Aims and scope Submit manuscript

Abstract

The use of diffusion ordered NMR spectroscopy (DOSY) for the analysis of complex reaction mixtures involving polyoxometalates (POMs) was demonstrated for the hydrolysis of the peptide tetraglycine by the K15H[Zr(α2-P2W17O61)2]·25H2O Wells–Dawson type cluster. 1H DOSY NMR studies have shown that severe signal overlap observed in the one-dimensional 1H NMR spectrum of reaction mixtures containing a POM and peptides could be overcome by the two-dimensional character of a DOSY NMR measurement. A clear distinction between the 1H NMR signals of the products formed during the hydrolysis of 5.0 mM of tetraglycine catalyzed by 1.0 mM of K15H[Zr(α2-P2W17O61)2]·25H2O was observed based on the extra dimension containing information about diffusion coefficients that distinguishes a typical DOSY measurement from conventionally used 1D 1H NMR. The spectrum clearly shows the presence of 5 species with diffusion coefficients of 3.71 × 10−10 m2/s (3.91; 3.84; 3.82 and 3.62 ppm), 4.39 × 10−10 m2/s (3.87; 3.76 and 3.61 ppm), 5.26 × 10−10 m2/s (3.67 and 3.63 ppm), and 7.46 × 10−10 m2/s (3.37 ppm) that are assigned to the non-hydrolyzed tetraglycine, the hydrolysis intermediate products triglycine and glycylglycine, and the end product of hydrolysis glycine, respectively. In addition, a signal assigned to cyclic glycylglycine, with a diffusion coefficient practically identical to the diffusion coefficient of glycylglycine was observed at 3.86 ppm. In addition, 1H and 31P NMR spectroscopy were further used to study the binding of tetraglycine to K15H[Zr(α2-P2W17O61)2]·25H2O and the solution speciation of K15H[Zr(α2-P2W17O61)2]·25H2O.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7

Similar content being viewed by others

References

  1. G. Absillis and T. N. Parac-Vogt (2012). Inorg. Chem. 51, 9902.

    Article  CAS  Google Scholar 

  2. A. Proust, R. Thouvenot, and P. Gouzerh (2008) Chem. Commun 1837.

  3. H. N. Miras, J. Yan, D.-L. Long, and L. Cronin (2012). Chem. Soc. Rev. 41, 7403.

    Article  CAS  Google Scholar 

  4. B. Hasenknopf (2005). Frontiers Biosci 10, 275.

    Article  CAS  Google Scholar 

  5. H. Yanagie, A. Ogata, S. Mitsui, T. Hisa, T. Yamase, and M. Eriguchi (2006). Biomed. Pharmacother. 60, 349.

    Article  CAS  Google Scholar 

  6. H. Stephan, M. Kubeil, F. Emmerling, and C. E. Mueller (2013) Eur. J. Inorg. Chem. 1585.

  7. P. H. Ho, E. Breynaert, C. E. A. Kirschhock, and T. N. Parac-Vogt (2011). Dalton Trans. 40, 295.

    Article  CAS  Google Scholar 

  8. G. Absillis, E. Cartuyvels, R. Van Deun, and T. N. Parac-Vogt (2008). J. Am. Chem. Soc. 130, 17400.

    Article  CAS  Google Scholar 

  9. N. Steens, A. M. Ramadan, G. Absillis, and T. N. Parac-Vogt (2010). Dalton Trans. 39, 585.

    Article  CAS  Google Scholar 

  10. H. Phuong Hien, K. Stroobants, and T. N. Parac-Vogt (2011). Inorg. Chem. 50, 12025.

    Article  CAS  Google Scholar 

  11. S. Vanhaecht, G. Absillis, and T. N. Parac-Vogt (2012). Dalton Trans. 41, 10028.

    Article  CAS  Google Scholar 

  12. G. Zhang, B. Keita, C. T. Craescu, S. Miron, P. de Oliveira, and L. Nadjo (2007). J. Phys. Chem. B 111, 11253.

    Article  CAS  Google Scholar 

  13. G. J. Zhang, B. Keita, C. T. Craescu, S. Miron, P. de Oliveira, and L. Nadjo (2008). Biomacromolecules 9, 812.

    Article  CAS  Google Scholar 

  14. I. Kozhevnikov Catalysis by polyoxometalates, vol. 2 (Wiley, Chisester, 2002).

    Google Scholar 

  15. S. Vanhaecht, G. Absillis, and T. N. Parac-Vogt (2013). Dalton Trans. 42, 15437.

    Article  CAS  Google Scholar 

  16. H. G. T. Ly, G. Absillis, and T. N. Parac-Vogt (2013). Dalton Trans. 42, 10929.

    Article  CAS  Google Scholar 

  17. K. Stroobants, E. Moelants, H. G. T. Ly, P. Proost, K. Bartik, and T. N. Parac-Vogt (2013). Chem. Eur. J. 19, 2848.

    Article  CAS  Google Scholar 

  18. V. Goovaerts, K. Stroobants, G. Absillis, and T. N. Parac-Vogt (2013). Phys. Chem. Chem. Phys. 15, 18378.

    Article  CAS  Google Scholar 

  19. A. Radzicka and R. Wolfenden (1996). J. Am. Chem. Soc. 118, 6105.

    Article  CAS  Google Scholar 

  20. C. Boglio, K. Micoine, P. Rémy, B. Hasenknopf, S. Thorimbert, E. Lacôte, M. Malacria, C. Afonso, and J.-C. Tabet (2007). Chem. Eur. J. 13, 5426.

    Article  CAS  Google Scholar 

  21. G. Al-Kadamany, S. S. Mal, B. Milev, B. G. Donoeva, R. I. Maksimovskaya, O. A. Kholdeeva, and U. Kortz (2010). Chem. Eur. J. 16, 11797.

    Article  CAS  Google Scholar 

  22. O. A. Kholdeeva, G. M. Maksimov, R. I. Maksimovskaya, M. P. Vanina, T. A. Trubitsina, D. Y. Naumov, B. A. Kolesov, N. S. Antonova, J. J. Carbo, and J. M. Poblet (2006). Inorg. Chem. 45, 7224.

    Article  CAS  Google Scholar 

  23. M. Carraro, N. Nsouli, H. Oelrich, A. Sartorel, A. Soraru, S. S. Mal, G. Scorrano, L. Walder, U. Kortz, and M. Bonchio (2011). Chem. Eur. J. 17, 8371.

    Article  CAS  Google Scholar 

  24. S. S. Mal, N. H. Nsouli, M. Carraro, A. Sartorel, G. Scorrano, H. Oelrich, L. Walder, M. Bonchio, and U. Kortz (2010). Inorg. Chem. 49, 7.

    Article  CAS  Google Scholar 

  25. E. Derat, E. Lacote, B. Hasenknopf, S. Thorimbert, and M. Malacria (2008). J. Phys. Chem. A 112, 13002.

    Article  CAS  Google Scholar 

  26. A. Falber, B. P. Burton-Pye, I. Radivojevic, L. Todaro, R. Saleh, L. C. Francesconi, and C. M. Drain (2009) Eur. J. Inorg. Chem. 2459.

  27. K. F. Morris and C. S. Johnson (1992). J. Am. Chem. Soc. 114, 3139.

    Article  CAS  Google Scholar 

  28. C. S. Johnson (1999). Prog. Nucl. Magn. Reson. Spectrosc. 34, 203.

    Article  CAS  Google Scholar 

  29. Y. Cohen, L. Avram, and L. Frish (2005). Angewandte Chemie 44, 520.

    Article  CAS  Google Scholar 

  30. P. S. Denkova, L. Van Lokeren, and R. Willem (2009). J. Phys. Chem. B 113, 6703.

    Article  CAS  Google Scholar 

  31. S. Floquet, S. Brun, J.-F. Lemonnier, M. Henry, M.-A. Delsuc, Y. Prigent, E. Cadot, and F. Taulelle (2009). J. Am. Chem. Soc. 131, 17254.

    Article  CAS  Google Scholar 

  32. P. Yin, C. P. Pradeep, B. Zhang, F.-Y. Li, C. Lydon, M. H. Rosnes, D. Li, E. Bitterlich, L. Xu, L. Cronin, and T. Liu (2012). Chem. Eur. J. 18, 8157.

    Article  CAS  Google Scholar 

  33. M. F. Misdrahi, M. Wang, C. P. Pradeep, F.-Y. Li, C. Lydon, L. Xu, L. Cronin, and T. Liu (2011). Langmuir 27, 9193.

    Article  CAS  Google Scholar 

  34. L. Van Lokeren, E. Cartuyvels, G. Absillis, R. Willem, and T. N. Parac-Vogt (2008) Chem. Commun. 2774.

  35. A. P. Ginsberg (1990). Inorg. Synth. 27, 85.

    Article  Google Scholar 

  36. C. N. Kato, A. Shinohara, K. Hayashi, and K. Nomiya (2006). Inorg. Chem. 45, 8108.

    Article  CAS  Google Scholar 

  37. A. K. Covingto, M. Paabo, R. A. Robinson, and R. G. Bates (1968). Anal. Chem. 40, 700.

    Article  Google Scholar 

  38. O. Soderman and P. Stilbs (1994). Prog. Nucl. Magn. Reson. Spectrosc. 26, 445.

    Article  CAS  Google Scholar 

  39. C. Boglio, B. Hasenknopf, G. Lenoble, P. Remy, P. Gouzerh, S. Thorimbert, E. Lacote, M. Malacria, and R. Thouvenot (2008). Chem. Eur. J. 14, 1532.

    Article  CAS  Google Scholar 

  40. N. Dupre, P. Remy, K. Micoine, C. Boglio, S. Thorimbert, E. Lacote, B. Hasenknopf, and M. Malacria (2010). Chem. Eur. J. 16, 7256.

    Article  CAS  Google Scholar 

  41. Y. Saku, Y. Sakai, and K. Nomiya (2010). Inorg. Chim. Acta 363, 967.

    Article  CAS  Google Scholar 

Download references

Acknowledgments

K.S. thanks the FWO Flanders (Belgium) for the doctoral fellowship. G.A. acknowledges the FWO Flanders (Belgium) for the postdoctoral fellowship. T.N.P–V. thanks KU Leuven for the funding (OT/13/060) and P.S.S. acknowledges KU Leuven for a visiting Fellowship. (F+/12/019).

Author information

Authors and Affiliations

  1. Department of Chemistry, Molecular Design and Synthesis, Laboratory of Bioinorganic Chemistry, KU Leuven, Celestijnenlaan 200F, 3001, Louvain, Belgium

    Karen Stroobants, Gregory Absillis, Pavletta S. Shestakova & Tatjana N. Parac-Vogt

  2. NMR Laboratory, Institute of Organic Chemistry with Centre of Phytochemistry, Bulgarian Academy of Sciences, Acad. G. Bontchev Str., B1.9, 1113, Sofia, Bulgaria

    Pavletta S. Shestakova

  3. Department of Materials and Chemistry (MACH), Vrije Universiteit Brussel (VUB), Pleinlaan 2, 1050, Brussels, Belgium

    Rudolph Willem

Authors
  1. Karen Stroobants
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Gregory Absillis
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Pavletta S. Shestakova
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Rudolph Willem
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. Tatjana N. Parac-Vogt
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Tatjana N. Parac-Vogt.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Stroobants, K., Absillis, G., Shestakova, P.S. et al. Hydrolysis of Tetraglycine by a Zr(IV)-Substituted Wells–Dawson Polyoxotungstate Studied by Diffusion Ordered NMR Spectroscopy. J Clust Sci 25, 855–866 (2014). https://doi.org/10.1007/s10876-013-0664-2

Download citation

  • Received:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10876-013-0664-2

Keywords

Search

Navigation