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.
Similar content being viewed by others
References
Bender, M.L., Komiyama, M.: Cyclodextrin chemistry. Springer, New York (1978)
Trotta, F., Tumiatti, W.: Patent WO 03/085002 (2003)
Li, D., Ma, M.: New organic nanoporous polymers and their inclusion complexes. Chem. Mater. 11, 872–874 (1999)
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)
Cavalli, R., Trotta, F., Tumiatti, W.: Cyclodextrin-based nanosponges for drug delivery. J. Incl. Phenom. Macrocycl. Chem. 56, 209–213 (2006)
Trotta, F., Cavalli, R.: Characterization and applications of new hyper-cross-linked cyclodextrins. Compos. Interface 16, 39–48 (2009)
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)
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)
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)
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)
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)
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)
Vyas, A., Shailendra, S., Swarnlata, S.: Cyclodextrin based novel drug delivery systems. J. Incl. Phenom. Macrocycl. Chem. 62, 23–42 (2008)
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)
Pines, A., Gibby, M., Waugh, J.S.: Proton-enhanced NMR in dilute spins in solids. J. Chem. Phys. 59, 569–573 (1973)
Mehring, M.: High-Resolution NMR Spectroscopy in Solids. Springer, New York (1983)
Stejskal, E.O., Memory, J.D.: High-Resolution NMR in the Solid State. Fundamental of CP/MAS. Oxford University Press, Oxford (1994)
Maréchal, Y.: Observing the water molecule in macromolecules and aqueous media using infrared spectrometry. J. Mol. Struct. 648, 27–47 (2003)
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)
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)
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)
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)
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)
Gavira, J.M., Hernanz, A., Bratu, I.: Dehydration of β-cyclodextrin: an IR ν(OH) band profile analysis. Vib. Spectrosc. 32, 137–146 (2003)
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)
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)
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)
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)
Kolodziejski, W., Klinowski, J.: Kinetics of cross-polarization in solid-state NMR: a guide for chemists. Chem. Rev. 102, 613–628 (2002)
Author information
Authors and Affiliations
Corresponding author
Rights 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
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10847-012-0106-z