Skip to main content
SpringerLink
Log in

Vibrational dynamics and hydrogen bond properties of β-CD nanosponges: an FTIR-ATR, Raman and solid-state NMR spectroscopic study

  • Original Article
  • Published:
Journal of Inclusion Phenomena and Macrocyclic Chemistry Aims and scope Submit manuscript

Abstract

Cyclodextrin nanosponges (CDNS) are cross-linked polymers with remarkable inclusion/release properties. CDNS show swelling capability and a hydrophilicity/hydrophobicity balance that can be dramatically modified by the type and quantity of cross-linking agents. Here, we focus our attention on samples of β-cyclodextrin nanosponges (β-CDNS) obtained by reacting β-cyclodextrin (β-CD) with the cross-linking agent carbonyldiimidazole at different β-CD:cross-linking agent molar ratio. The vibrational properties of CDNS thus synthesized have been investigated by Fourier transform infrared spectroscopy in attenuated total reflectance geometry and Raman spectroscopy in the dry state at room temperature. The quantitative analysis of the O–H stretching region (3,000–3,800 cm−1) allowed us to obtain structural information on the role played by primary and secondary OH groups in the hydrogen bond network of the polymer. Also, the contribution of interstitial and intracavity crystallization water molecules is reported. Solid-state NMR spectroscopy is used to study the molecular mobility of the polymer by measuring the 1H spin–lattice relaxation time in the rotating frame (T1ρ). The T1ρ values obtained for the polymer β-CDNS are compared with free β-CD. The observed relaxation parameters point out that the ester formation occurs mainly at the primary OH groups of CDs, also supporting the interpretation of vibrational spectra.

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

Similar content being viewed by others

References

  1. Bender, M.L., Komiyama, M.: Cyclodextrin chemistry. Springer, New York (1978)

    Book  Google Scholar 

  2. Trotta, F., Tumiatti, W.: Patent WO 03/085002 (2003)

  3. Li, D., Ma, M.: New organic nanoporous polymers and their inclusion complexes. Chem. Mater. 11, 872–874 (1999)

    Article  Google Scholar 

  4. Trotta, F., Tumiatti, W., Cavalli, R., Zerbinati, O., Roggero, C. M., Vallero, R.: Ultrasound-assisted synthesis of cyclodextrin-based nanosponges. Patent number WO 06/002814 (2006)

  5. Cavalli, R., Trotta, F., Tumiatti, W.: Cyclodextrin-based nanosponges for drug delivery. J. Incl. Phenom. Macrocycl. Chem. 56, 209–213 (2006)

    Article  CAS  Google Scholar 

  6. Trotta, F., Cavalli, R.: Characterization and applications of new hyper-cross-linked cyclodextrins. Compos. Interface 16, 39–48 (2009)

    Article  CAS  Google Scholar 

  7. Mele, A., Castiglione, F., Malpezzi, L., Ganazzoli, F., Raffaini, G., Trotta, F., Rossi, B., Fontana, A., Giunchi, G.: HR MAS NMR, powder XRD and Raman spectroscopy study of inclusion phenomena in βCD nanosponges. J. Incl. Phenom. Macrocycl. Chem. 69, 403–409 (2011)

    Article  CAS  Google Scholar 

  8. Arkas, M., Allabashi, R., Tsiourvas, D., Mattausch, E.-M., Perfler, R.: Organic/inorganic hybrid filters based on dendritic and cyclodextrin ‘‘nanosponges’’ for the removal of organic pollutants from water. Environ. Sci. Technol. 40, 2771–2777 (2006)

    Article  CAS  Google Scholar 

  9. Mhlanga, S.D., Mamba, B.B., Krause, R.W., Malefetse, T.J.: Removal of organic contaminants from water using nanosponge cyclodextrin polyurethanes. J. Chem. Technol. Biotechnol. 82, 382–388 (2007)

    Article  CAS  Google Scholar 

  10. Mamba, B.B., Krause, R.W., Malefetse, T.J., Nxumalo, E.N.: Monofunctionalized cyclodextrin polymers for the removal of organic pollutants fromwater. Environ. Chem. Lett. 5, 79–84 (2007)

    Article  CAS  Google Scholar 

  11. Mamba, B.B., Krause, R.W., Malefetse, T.J., Gericke, G., Sithole, S.P.: Cyclodextrin nanosponges in the removal of organic matter to produce water for power generation. Water SA 34, 657–660 (2008)

    CAS  Google Scholar 

  12. Swaminathan, S., Vavia, P.R., Trotta, F., Torne, S.: Formulation of beta-cyclodextrin based nanosponges of itraconazole. J. Incl. Phenom. Macrocycl. Chem. 57, 89–94 (2007)

    Article  CAS  Google Scholar 

  13. Vyas, A., Shailendra, S., Swarnlata, S.: Cyclodextrin based novel drug delivery systems. J. Incl. Phenom. Macrocycl. Chem. 62, 23–42 (2008)

    Article  CAS  Google Scholar 

  14. Ansari, K.A., Vavia, P.R., Trotta, F., Cavalli, R.: Cyclodextrin-based nanosponges for delivery of resveratrol: in vitro characterisation, stability, cytotoxicity and permeation study. AAPS Pharm. Sci. Tech. 12, 279–286 (2011)

    Article  CAS  Google Scholar 

  15. Pines, A., Gibby, M., Waugh, J.S.: Proton-enhanced NMR in dilute spins in solids. J. Chem. Phys. 59, 569–573 (1973)

    Article  CAS  Google Scholar 

  16. Mehring, M.: High-Resolution NMR Spectroscopy in Solids. Springer, New York (1983)

    Book  Google Scholar 

  17. Stejskal, E.O., Memory, J.D.: High-Resolution NMR in the Solid State. Fundamental of CP/MAS. Oxford University Press, Oxford (1994)

    Google Scholar 

  18. Maréchal, Y.: Observing the water molecule in macromolecules and aqueous media using infrared spectrometry. J. Mol. Struct. 648, 27–47 (2003)

    Article  Google Scholar 

  19. Bennett, A.E., Rienstra, C.M., Auger, M., Lakshmi, K.V., Griffin, R.G.: Heteronuclear decoupling in rotating solids. J. Chem. Phys. 103, 6951–6958 (1995)

    Article  CAS  Google Scholar 

  20. Crupi, V., Longo, F., Majolino, D., Venuti, V.: Vibrational properties of water molecules adsorbed in different zeolitic frameworks. J. Phys. Condens. Matter 18, 3563–3580 (2006)

    Article  CAS  Google Scholar 

  21. Crupi, V., Longo, F., Majolino, D., Venuti, V.: T dependence of vibrational dynamics of water in ion-exchanged zeolites A: a detailed Fourier transform infrared attenuated total reflection study. J. Chem. Phys. 123, 154702 (2005)

    Article  Google Scholar 

  22. Mallamace, F., Broccio, M., Corsaro, C., Faraone, A., Majolino, D., Venuti, V., Liu, L., Mou, C.Y., Chen, S.H.: Evidence of the existence of the low-density liquid phase in supercooled, confined water. Proc. Natl. Acad. Sci. USA 104, 424–428 (2007)

    Article  CAS  Google Scholar 

  23. Crupi, V., Ficarra, R., Guardo, M., Majolino, D., Stancanelli, R., Venuti, V.: UV–vis and FTIR–ATR spectroscopic techniques to study the inclusion complexes of genistein with β-cyclodextrins. J. Pharm. Biomed. Anal. 44, 110–117 (2007)

    Article  CAS  Google Scholar 

  24. Gavira, J.M., Hernanz, A., Bratu, I.: Dehydration of β-cyclodextrin: an IR ν(OH) band profile analysis. Vib. Spectrosc. 32, 137–146 (2003)

    Article  CAS  Google Scholar 

  25. Bratu, I., Veiga, F., Fernandes, C., Hernanz, A., Gavira, J.M.: Infrared spectroscopic study of triacetyl-β-cyclodextrin and its inclusion complex with nicapiridine. Spectroscopy 18, 459–467 (2004)

    Article  CAS  Google Scholar 

  26. Stancanelli, R., Ficarra, R., Cannavà, C., Guardo, M., Calabrò, M.L., Ficarra, P., Ottanà, R., Maccari, R., Crupi, V., Majolino, D., Venuti, V.: UV–vis and FTIR-ATR characterization of 9-fluorenon-2-carboxyester/(2-hydroxypropyl)-β-cyclodextrin inclusion complex. J. Pharm. Biomed. Anal. 47, 704–709 (2008)

    Article  CAS  Google Scholar 

  27. Cannavà, C., Crupi, V., Ficarra, P., Guardo, M., Majolino, D., Stancanelli, R., Venuti, V.: Physicochemical characterization of coumestrol/β-cyclodextrins inclusion complexes by UV–vis and FTIR-ATR spectroscopies. Vib. Spectrosc. 48, 172–178 (2008)

    Article  Google Scholar 

  28. Crini, G., Cosentino, C., Bertini, S., Naggi, A., Torri, G., Vecchi, C., Janus, L., Morcellet, M.: Solid state NMR spectroscopy study of molecular motion in cyclomaltoheptanose (β-cyclodextrin) crosslinked with epichlorohydrin. Carbohydr. Res. 308, 37–45 (1998)

    Article  CAS  Google Scholar 

  29. Kolodziejski, W., Klinowski, J.: Kinetics of cross-polarization in solid-state NMR: a guide for chemists. Chem. Rev. 102, 613–628 (2002)

    Article  CAS  Google Scholar 

Download references

Author information

Authors and Affiliations

  1. Dipartimento di Chimica, Materiali e Ing. Chimica “G. Natta”, Politecnico di Milano, via Mancinelli 7, 20131, Milano, Italy

    F. Castiglione & A. Mele

  2. Dipartimento di Fisica, Università di Messina, and CNISM, UdR Messina, Viale Ferdinando Stagno D’Alcontres 31, 98166, Messina, Italy

    V. Crupi, D. Majolino & V. Venuti

  3. CNR-Istituto di Chimica del Riconoscimento Molecolare, Milano, Italy

    A. Mele

  4. CNR-Istituto di Chimica del Riconoscimento Molecolare, Sez. Quil., 20131, Milano, Italy

    W. Panzeri

  5. Dipartimento di Fisica, Università di Trento, via Sommarive 14, 38123, Povo, Trento, Italy

    B. Rossi

  6. Dipartimento di Chimica IFM, Università di Torino, via Pietro Giuria, 10125, Torino, Italy

    F. Trotta

Authors
  1. F. Castiglione
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. V. Crupi
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. D. Majolino
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. A. Mele
    View author publications

    You can also search for this author in PubMed Google Scholar

  5. W. Panzeri
    View author publications

    You can also search for this author in PubMed Google Scholar

  6. B. Rossi
    View author publications

    You can also search for this author in PubMed Google Scholar

  7. F. Trotta
    View author publications

    You can also search for this author in PubMed Google Scholar

  8. V. Venuti
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to B. Rossi.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Castiglione, F., Crupi, V., Majolino, D. et al. Vibrational dynamics and hydrogen bond properties of β-CD nanosponges: an FTIR-ATR, Raman and solid-state NMR spectroscopic study. J Incl Phenom Macrocycl Chem 75, 247–254 (2013). https://doi.org/10.1007/s10847-012-0106-z

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s10847-012-0106-z

Keywords

Search

Navigation