Bouchemal, Kawthar
Couvreur, Patrick
[UCL]
Daoud-Mahammed, Samia
Poupaert, Jacques
[UCL]
Gref, Ruxandra
In this study, the entrapment of benzophenone (BZ) into supramolecular nanoassemblies prepared by mixing two water-soluble associative polymers (i.e. polymerized beta-CD (p beta-CD) and dextran grafted with lauryl-side chains (MD)) has been investigated by using isothermal titration microcalorimetry (ITC) and molecular modeling. ITC experiments have been performed at various temperatures (4 degrees C (277 K), 25 degrees C (298 K), and 37 degrees C (310 K)) to evaluate the interaction of BZ with p beta-CD in comparison with beta-CD. The inclusion complexation for both beta-CD/BZ and p beta-CD/BZ interactions was entropy-driven (vertical bar Delta H vertical barvertical bar T Delta S vertical bar) when the temperature of the experiment was low (4 degrees C) and enthalpy-driven (vertical bar Delta H vertical bar>vertical bar T Delta S vertical bar) with minor entropic contribution when the temperature was increased (25 and 37 degrees C). Using all the thermodynamic data obtained for beta-CD/BZ and beta b-CD/BZ interactions when the temperature of the experiment was varied, the Delta H = f (T Delta S) plot was perfectly linear, which reflected an enthalpy-entropy compensation process. Finally, the combination of ITC data with molecular modeling provided consistent information in regard to the location of MD side chains and BZ inside the cyclodextrin cavity, as well as concerning the stability of the nanoassemblies loaded with BZ.
- Daoud-Mahammed S, Couvreur P, Bouchemal K, Chéron M, Lebas G, Amiel C, et al. Cyclodextrin and polysaccharide-based nanogels: entrapment of two hydrophobic molecules, benzophenone and tamoxifen. Biomacromolecules. 2009;10:547–54.
- Duchêne D, Wouessidjewe D, Ponchel G. Cyclodextrins and carrier systems. J Control Release. 1999;62:263–8.
- Segura-Sanchez F, Bouchemal K, Lebas G, Vauthier C, Santos-Magalhaes NS, Ponchel G. Elucidation of the complexation mechanism between (+)-usnic acid and cyclodextrins studied by isothermal titration calorimetry and phase-solubility diagram experiments. J Mol Recognit. 2009;22:232–41.
- Gref R, Amiel C, Molinard K, Daoud-Mahammed S, Sébille B, Gillet B, et al. New self-assembled nanogels based on host–guest interactions: characterization and drug loading. J Control Release. 2006;111:316–24.
- Othman M, Bouchemal K, Couvreur P, Gref R. Microcalorimetric investigation on the formation of supramolecular nanoassemblies of associative polymers loaded with gadolinium chelate derivatives. Int J Pharm. 2009;379:218–25.
- Higuchi T, Connors KA. Phase-solubility techniques. In: Reilley CN, editor. Advances in analytical chemistry and instrumentation, vol. 4. New York: Interscience; 1965. p. 117–212.
- Bouchemal K, Couenne F, Briançon S, Fessi H, Tayakout M. Stability studies on colloidal suspensions of polyurethane nanocapsules. J Nanosci Nanotechnol. 2006;6:3187–92.
- Bouchemal K. New challenges for pharmaceutical formulations and drug delivery system characterisation using isothermal titration calorimetry. Drug Discov Today. 2008;13:960–72.
- Renard E, Deratani A, Volet G, Sebille B. Characterization of water soluble high molecular weight β-cyclodextrin-epichlorhydrin polymers. Eur Polym J. 1997;33:49–57.
- Arranz F, Sanchez-Chaves M. 13C nuclear magnetic resonance spectral study on the distribution of substituents in relation to the preparation method of partially acetylated dextrans. Polymer. 1988;29:507–12.
- Amiel C, Moine L, Sandier A, Brown W, David C, Hauss F, et al. Macromolecular assemblies generated by inclusion complexes between amphiphatic polymers and β-cyclodextrin polymers in aqueous media. In: McCormick CL, editor. Stimuli-responsive water soluble and amphiphilic polymers, vol. 780. Washington, DC: American Chemical Society; 2001. p. 58–81.
- Rekharsky MV, Inoue Y. Complexation and chiral recognition thermodynamics of 6-amino-6-deoxy-β-cyclodextrin with anionic, cationic, and neutral chiral guests: counterbalance between van der Waals and coulombic interactions. J Am Chem Soc. 2002;124:813–26.
- Wiggins PM. Hydrophobic hydration, hydrophobic forces and protein folding. Physica A. 1997;238:113–28.
- Rekharsky MV, Inoue Y. Chiral recognition thermodynamics of β-cyclodextrin: the thermodynamic origin of enantioselectivity and the enthalpy–entropy compensation effect. J Am Chem Soc. 2000;122:4418–35.
- Rekharsky MV, Inoue Y. 1:1 and 1:2 complexation thermodynamics of γ-cyclodextrin with N-carbobenzyloxy aromatic amino acids and ω-phenylalkanoic acids. J Am Chem Soc. 2000;122:10949–55.
- Illapakurthy AC, Wyandt CM, Stodghill SP. Isothermal titration calorimetry method for determination of cyclodextrin complexation thermodynamics between artemisinin and naproxen under varying environmental conditions. Eur J Pharm Biopharm. 2005;59:325–32.
- Inoue Y, Hakushi T, Liu Y, Tong L, Shen B, Jin D. Thermodynamics of molecular recognition by cyclodextrins. 1. Calorimetric titration of inclusion complexation of naphthalenesulfonates with α-, β-, and γ-cyclodextrins: enthalpy–entropy compensation. J Am Chem Soc. 1993;115:475–81.
- Cooper A. Thermodynamic analysis of biomolecular interactions. Curr Opin Chem Biol. 1999;3:557–63.
- Cooper A, Johnson CM, Lakey JH, Nöllmann M. Heat does not come in different colours: entropy–enthalpy compensation, free energy windows, quantum confinement, pressure perturbation calorimetry, solvation and the multiple causes of heat capacity effects in biomolecular interactions. Biophys Chem. 2001;93:215–30.
- Lopez MM, Makhatadze GI. Solvent isotope effect on thermodynamics of hydration. Biophys Chem. 1998;74:117–25.
- Dam TK, Oscarson S, Brewer CF. Thermodynamics of binding of the core trimannoside of asparagine-linked carbohydrates and deoxy analogs to Dioclea grandiflora Lectin. J Biol Chem. 1998;273:32812–7.
- Ross PD, Rekharsky MV. Thermodynamics of hydrogen bond and hydrophobic interactions in cyclodextrin complexes. Biophys J. 1996;71:2144–54.
- Crini G, Cosentino V, Bertini S, Naggi A, Torri G, Vecchi C, et al. Solid state NMR spectroscopy study of molecular motion in cyclomaltoheptaose (β-cyclodextrin) crosslinked with epichlorohydrin. Carbohydr Res. 1998;308:37–45.
- Wintgens V, Daoud-Mahammed S, Gref R, Bouteiller L, Amiel C. Aqueous polysaccharide associations mediated by β-cyclodextrin polymers. Biomacromolecules. 2008;9:1434–42.
Bibliographic reference |
Bouchemal, Kawthar ; Couvreur, Patrick ; Daoud-Mahammed, Samia ; Poupaert, Jacques ; Gref, Ruxandra. A comprehensive study on the inclusion mechanism of benzophenone into supramolecular nanoassemblies prepared using two water-soluble associative polymers. In: Journal of Thermal Analysis and Calorimetry : an international forum for thermal studies, Vol. 98, no. 1, p. 57-64 (2009) |
Permanent URL |
http://hdl.handle.net/2078.1/35199 |