[en] The associative behavior of monodisperse diblock copolymers consisting of a hydrophilic poly(ethylene oxide) block and a hydrophobic poly(epsilon-caprolactone) or poly(gamma-methyl-epsilon-caprolactone) block has been studied in aqueous solution. Copolymers have been directly dissolved in water. The solution properties have been studied by surface tension, in relation to mesoscopic analyses by NMR (self-diffusion coefficients), transmission electron microscopy, and small-angle neutron and X-ray scattering. The experimental results suggest that micellization occurs at low concentration (approximately 0.002 wt %) and results in a mixture of unimers and spherical micelles that exchange slowly. The radius of the micelles has been measured (ca. 11 nm), and the micellar substructure has been extracted from the fitting of the SANS data with two analytical models. The core radius and the aggregation number change with the hydrophobic block length according to scaling laws as reported in the scientific literature. The poly(ethylene oxide) blocks are in a moderately extended conformation in the corona, which corresponds to about 25% of the completely extended chain. No significant modification is observed when poly(gamma-methyl-epsilon-caprolactone) replaces poly(epsilon-caprolactone) in the diblocks.
Research center :
Center for Education and Research on Macromolecules (CERM)
Disciplines :
Materials science & engineering Chemistry
Author, co-author :
Vangeyte, Pattrick; Université de Liège - ULiège > Department of Chemistry > Center for Education and Research on Macromolecules (CERM)
Leyh, Bernard ; Université de Liège - ULiège > Department of Chemistry > Laboratoire de Dynamique Moléculaire
Heinrich, M.; Institut für Festkörperforschung, Forschungszentrum Jülich, Germany
Grandjean, Jean ; Université de Liège - ULiège > Department of Chemistry > Chimie organique et spectroscopie multinucléaire (COSM)
Bourgaux, C.; University of Paris-Sud, Orsay, France > Laboratoire pour l‘Utilisation du Rayonnement Electromagnétique
Jérôme, Robert ; Université de Liège - ULiège > Centre d'études et de rech. sur les macromolécules (CERM)
Language :
English
Title :
Self-assembly of poly(ethylene oxide)-b-poly(epsilon-caprolactone) copolymers in aqueous solution
Publication date :
28 September 2004
Journal title :
Langmuir
ISSN :
0743-7463
eISSN :
1520-5827
Publisher :
Amer Chemical Soc, Washington, United States - Washington
FRIA - Fonds pour la Formation à la Recherche dans l'Industrie et dans l'Agriculture [BE] BELSPO - SPP Politique scientifique - Service Public Fédéral de Programmation Politique scientifique F.R.S.-FNRS - Fonds de la Recherche Scientifique [BE] the European Community-Access to Research Infrastructures action of the ImprovingHumanPotential program (HPRI)
Lin, Y.; Alexandridis, P. J. Phys. Chem. B 2002, 106, 12124.
Kositza, M. J.; Bohne, C.; Alexandridis, P.; Hatton, T. A.; Holzwarth, J. F. Macromolecules 1999, 32, 5539.
Goldmints, I.; Yu, G.; Booth, C.; Smith, K.A.; Hatton, T. A. Langmuir 1999, 25, 1651.
Kelarakis, A.; Havredaki, V.; Yu, G. E.; Derici, L.; Booth, C. Macromolecules 1998, 31, 944.
Chu, B. Langmuir 1995, 11, 414.
Almgren, M.; Brown, W.; Hvidt, S. Colloid Polym. Sci. 1995, 273, 2.
Xu, R.; Winnik, M. A.; Riess, G.; Chu, B.; Croueher, M. D. Macromolecules 1992, 25, 644.
Yu, G.; Yang, Z.; Ameri, M.; Attwood, D.; Collett, J. H.; Price, C.; Booth, C. J. Phys. Chem. B 1997, 101, 4394.
Chlebicki, J. J. Colloid Interface Sci. 1998, 206, 77.
Derici, L.; Ledger, S.; Mai, S.; Booth, C.; Hamley, I. W.; Pedersen, J. S. Phys. Chem. Chem. Phys. 1999, 1, 2773.
Soni, S. S.; Sastry, N. V.; Patra, A. K.; Joshi, J. V.; Goyal, P. S. J. Phys. Chem. B 2002, 106, 13069.
Won, Y.; Davis, H. T.; Bates, P. S.; Agamalian, M.; Wignall, G. D. J. Phys. Chem. B. 2000, 104, 7134.
Alexandridis, P. Curr. Opin. Colloid Interface Sci. 1996, 1, 490.
Luo, L.; Tam, J.; Maysinger, D.; Eisenberg, A. Bioconjugate Chem. 2002, 13, 1259.
Soo, P. L.; Luo, L.; Maysinger, D.; Eisenberg, A. Langmuir 2002, 18, 9996 (and references therein).
Yu, Y.; Eisenberg, A. J. Am. Chem. Soc. 1997, 119, 8383.
Zhang, L.; Eisenberg, A. Sciences 1995, 268, 1728.
Kataoka, K.; Harada, A.; Nagasaki, Y. Adv. Drug Delivery Rev. 2001, 41, 113.
De Jaeghere, F.; Allémann, E.; Feijen, J.; Kissel, T.; Doelker, E.; Gurny, R. J. Drug Targeting 2000, 8, 143.
Gohy, J. F.; Creutz, S.; Garcia, M.; Mahltig, B.; Stamm, M.; Jérôme, R. Macromolecules 2000, 33, 6378.
Zhao, Y.; Liang, H.; Wang, S.; Wu, C. J. Phys. Chem. B 2001, 105, 848.
Kim, S. Y.; Lee, Y. M. Biomaterials 2001, 22, 1697.
Martini, L.; Attwood, D.; Collett, J. H.; Nicholas, C. V.; Tanodekaew, S.; Deng, N.; Heatley, F.; Booth, C. J. Chem. Soc., Faraday Trans. 1994, 90, 1961.
Vangeyte, P.; Gautier, S.; Jérôme, R. Colloids Surf., A 2004, 242 203
Trollsas, M.; Kelly, M. A.; Claesson, H.; Siemens, R.; Hedrick, J. L. Macromolecules 1999, 32, 4917.
Vion, J. M. Ph.D. Thesis, University of Liège, Liège, Belgium, 1986.
Vangeyte, P.; Jérôme, R. J. Polym. Sci., Part A: Polym. Chem. 2004, 42, 1132.
Rosen, M. J., Ed. Surfactants and Interfacial Phenomena; Wiley: New York, 1989.
Gibbs, S. J.; Johnson, C. S. J. Magn. Reson. 1991, 93, 395.
Wu, D.; Chen, A.; Johnson, C. S. J: Magn. Reson. 1995, 115, 260.
Abrahmsen-Alami, A.; Persson, K.; Stilbs, P.; Alami, E. J. Phys. Chem. 1996, 100, 4598.
Herden, H.; Karger, J.; Pfeifer, H.; Kube, C.; Schollner, J. J. Colloid Interface Sci. 1992, 152, 281.
Pedersen, J. S.; Svaneborg, C. Curr. Opin. Colloid Interface Sci. 2002, 7, 158.
Castelletto, V.; Hamley, I. W. Curr. Opin. Colloid Interface Sci. 2002, 7, 167.
Yang, L.; Alexandridis, P.; Steyler, D. C.; Kositza, M. J.; Holzwarth, J. F. Langmuir 2000, 16, 8555.
Fati, D. Master thesis, University of Liège, Liège, Belgium, 1999.
Pedersen, J. S.; Gerstenberg, M. C. Macromolecules 1996, 29, 1363.
Pedersen, J. S. Adv. Colloid Interface Sci. 1997, 70, 171.
Leyh, B. To be submitted.
Waseda, Y. The Structure of Liquid Transition Metals and their Alloys. In Liquid Metals; Evans, R., Greenwood, D. A., Eds.; Institute of Physics: Bristol, U.K., 1976; Vol. 30, pp 230-240.
Bogdanov, B.; Vidts, A.; Van Den Bulcke, A.; Verbeek, R.; Schacht, E. Polymer 1998, 39, 1631.
