Epoxy-terminated polydimethylsiloxanes (E-PDMSs) of different molecular weight Mn were proved to undergo inclusion complexation into the inner cavity of β-cyclodextrin (β-CD), resulting in polyrotaxanes (PRots). The dethreading of the macrocycle was prevented by blocking the siloxane chain with a bulky substituent derived from 4-aminophenyltriphenyl methane (APhTPhM). As revealed by thermogravimetric analysis, differential scanning calorimetry, scanning electron microscopy (SEM), wide-angle X-ray diffraction and statistical analysis of SEM images, the thermal properties and the morphology of polyrotoxanes are dependent upon Mn, β-CD/E-PDMS molar ratio and the presence of free β-CD in the complexes.
Schill, G. (1971). Catenanes, Rotaxanes, and Knots, Academic Press, New York & London .
2.
Bheda, C. and Engen, P.T. (1994). Rotaxanes, Catenanes, Polyrotaxanes, Polycatenanes and Related Materials, Progr . Polym. Sci.,19: 843-945.
3.
Huang, F. and Gibson, H.W. (2005). Polypseudorotaxanes and Polyrotaxanes, Progr . Polym. Sci., 30: 982-1010.
4.
Szejtli, J. (2004). Present, Past, and Future of Cyclodextrin Research, Pure . Appl. Chem., 76(10): 1825- 1832.
5.
Harada, A. and Kamachi, M. (1990). Complex Formation between Poly(ethylene glycol) and β-cyclodextrin , Macromolecules , 23: 2821-2823.
6.
Kamitori, S. , Matsuzaka, O. , Kondo, S. , Muraoka, S. , Okuyama, K. , Noguchi, K. , Okada, M. and Harada, A. (2000). A Novel Pseudo-Polyrotaxanes Structure Composed of Cyclodextrins and a Straight-Chain Polymer: Crystal Structures of Inclusion Complexes of β-Cyclodextrin with Poly(trimethylene oxide) and Poly(propylene glycol) , Macromolecules, 33: 1500-1502.
7.
Harada, A. , Li, J. and Kamachi, M. (1993). Complex Formation between Poly(methyl vinyl ether) and γ-Cyclodextrin , Chem. Lett. , 22(2): 237-240.
8.
Wenz, G. , Steinbrunn, M.B. and Landfester, K. (1997). Solid State Polycondensation within Cyclodextrin Channels Leading to Watersoluble Polyamide Rotaxanes , Tetrahedron , 53: 15575-15592.
9.
Kawaguchi, Y. , Nishiyama, T. , Okada, M. , Kamachi, M. and Harada, A. (2000). Complex Formation of Poly(ε-caprolactone) with Cyclodextrins , Macromolecules , 33: 4472-4477.
10.
Choi, H.S. , Ooya, T. , Lee, S.C. , Sasaki, S. , Kurisawa, M. , Uyama, H. and Yui, N. (2004). pH Dependence of Polypseudorotaxane Formation between Cationic Linear Polyethylenimine and Cyclodextrins , Macromolecules, 37(18): 6705-6710.
11.
Wenz, G. and Keller, B. (1992). Threading Cyclodextrin Rings on Polymer Chains, Angew . Chem. Int. Ed., 31: 197-199.
12.
Wenz, G. and Keller, B. (1993). Synthesis of Polyrotaxanes or How to Thread Many Cyclodextrin Rings on a Polymer Chain, Polym . Prepr., 34: 62-63.
13.
Herrmann, W. , Schneider, M. and Wenz, G. (1997). Photochemical Synthesis of Polyrotaxanes from Stilbene Polymers and Cyclodextrins, Angew . Chem. Int. Ed. , 36: 2511-2514.
14.
Harada, A. , Li, J. , Suzuki, S. and Kamachi, M. (1993). Complex Formation between Polyisobutylene and Cyclodextrins: Inversion of Chain-length Selectivity between β-cyclodextrin and γ-cyclodextrin , Macromolecules, 26: 5267-5268.
15.
Simionescu, C.I. , Grigoras, M. , Farcas, A. and Stoleru, A. (1998). Synthesis and characterization of poly(azomethine)s with rotaxane architecture, Macromol . Chem. Phys., 199: 1301-1306.
16.
Farcaş, A. and Grigoraş , M. (2003). Synthesis and Characterization of a Fully Aromatic Polyazomethine with Rotaxane Architecture, Polym . Int., 52: 1315-1320.
17.
Farcaş, A. and Grigoraş , M. (2001). Synthesis and Characterization of a Fully Aromatic Polyazomethine with Main Chain Rotaxane Architecture, High . Perform. Polym., 13: 201-210.
18.
Farcaş, A. , Grigoraş , M. and Simionescu, C.I. (2001). Poly(aromatic azomethines) Containing Non-covalently Bound Cyclodextrins in the Main-chains: Synthesis and Characterization , Rev. Roum. Chim., 46: 25-30.
19.
Panova, I.G. and Topchieva, I.N. (2001). Rotaxanes and Polyrotaxanes. Their Synthesis and the Supramolecular Devices based on Them, Russ . Chem. Rev., 70: 23-44.
20.
Takata, T. , Kihara, N. and Furusho, Y. (2004). Polyrotaxanes and Polycatenanes: Recent Advances in Syntheses and Applications of Polymers comprising of Interlocked Structures , Adv. Polym. Sci., 171: 1-75.
21.
Nepolgodiev, S.A. and Stoddart, J.F. (1998). Cyclodextrin-Based Catenanes and Rotaxanes , Chem. Rev., 98: 1959-1976.
22.
Gibson, H.W. (1996). Rotaxanes. In: Semlyen, J.A. (ed.) Ring Molecules, Wiley and Sons, New York, 191-262.
23.
Mahan, E. and Gibson, H.W. (2000). In: Semlyen, J.A. (ed.) Cyclic Polymers, 2nd edn, Kluwer Publishers, Dordrecht, 415-560.
24.
Gong, C. and Gibson, H.W. (1999). Polyrotaxanes: syntheses and properties, In: Sauvage, J.P. and Dietrich-Buchecker, C.O. (eds) Molecular Catenanes, Rotaxanes and Knots, Wiley-VCH, Weinheim, 277- 321.
Gibson, H.W. and Liu, S. (1996). Polyrotaxanes: past, present and future, Macromol . Symp., 102: 55-61.
27.
Farcas, A. , Marangoci, N. , Fifere, A. , Pinteala, M. , Harabagiu, V. and Simionescu, B.C. (2006). In: Dragan, S.E. (ed.) New Trends in Nonionic (co)polymers and Hybrids, NoveScience Publishers., Inc., New York, 53-77.
28.
Harada, A. , Li, J. and Kamachi, M. (1993). Synthesis of a Tubular Polymer from Threaded Cyclodextrins , Nature, (London)1364: 516-518.
29.
Ikeda. T. , Ooya, T. and Yui, N. (2000). Supramolecular network formation through inclusion complexation of an α-cyclodextrin-based molecular tube, Macromol . Rapid. Commun., 21: 1257-1262.
30.
Ikeda, T. , Lee, W.K. , Ooya, T. and Yui, N. (2003). Thermodynamic Analysis of Inclusion Complexation between α-Cyclodextrin-Based Molecular Tube and Poly(ethylene oxide)-block-poly(tetrahydrofuran)-block-poly(ethylene oxide) Triblock Copolymer , J. Phys. Chem., 107: 14-19.
31.
Balzani, V. , Gumez-Lipez, M. and Stoddart, J.F. (1998). Molecular Machines, Acc . Chem. Res., 31: 405-411.
32.
Lee, J-Y. and Park, S-M. (1998). Electrochemistry of Guest Molecules in Thiolated Cyclodextrin Self-Assembled Monolayers: an Implication for Size-Selective Sensors , J. Phys. Chem. B, 102: 9940-9945.
33.
Balzani, V. , Credi, A. , Raymo, F.M. and Stoddart, J.F. (2000). Artificial Molecular Machines, Angew . Chem. Int., 39: 3348-3391.
34.
Ooya, T. , Fujita, H. and Yui, N. (1999). Temperature-Dependent Localization of Cyclodextrins Threaded onto a Poly(ethylene glycol)-Poly(propylene glycol) Triblock-copolimer in a Polyrotaxane, Polym . Prepr., 40: 480-481.
35.
Han, B.H. and Antonietti, M. (2002). Cyclodextrin-Based Pseudopolyrotaxanes as Templates for the Generation of Porous Silica, Mater . Chem. Mater., 14: 3477-3488.
36.
Ooga, T. , Eguchi, M. , Ozaki, A. and Yui, N. (2002). Carboxyethyl Ester-polyrotaxanes as a New Calcium Binding and Mechanism of Trypsin Inhibition , Int. J. Pharm. , 242: 47-52.
37.
Okumura, H. , Okada, M. , Kawaguchi, Y. and Harada, A. (2000). Complex Formation between Poly(dimethylsiloxane) and Cyclodextrins: New Pseudo-Polyrotaxanes containing Inorganic Polymers , Macromolecules, 33: 4297-4298.
38.
Okumura, H. , Okada, M. , Kawaguchi, Y. and Harada, A. (2002). Complex Formation between Poly(dimethylsilane) and Cyclodextrins, Macromol . Rap. Commun., 23: 781-785.
39.
Witten, B. and Reid, E.E. (1963). Organic Synthesis, John Wiley and Sons , New-York & London, vol. 4, pp. 47-63.
40.
Pinteala, M. , Harabagiu, V. , Holerca, M.N. , Negulescu, I.I. and Simionescu , B.C. (1995). Functional Siloxanes 4. An Approach to Multifunctional Cyclic Carbosiloxanes , J. Macromol. Sci. Macromol. Reports, A32: 671-677.
41.
Manca, M.L. , Zaru, M. , Ennas, G. , Valenti, D. , Sinico, C. , Loy, G. and Fadda, A.M. (2005). Lipid Synthesis Inhibitors: Effect on Epidermal Lipid Conformational Changes and Percutaneous Permeation of Levodopa AAPS , Pharm. Sci. Tech., 6(3): article 58.
42.
Mukne, A.P. and Nagarsenker , (2004). Triamterene-β-cyclodextrin Systems: Preparation, Characterization and in vivo Evaluation AAPS , Pharm. Sci.Tech. , 5(1): article 19.
43.
Kilian, H.G. , Metzler, R. and Zink, B. (1997). Aggregate Model of Liquids , Chem. Phys., 107: 8697-8704.
44.
Kilian, H.G. , Bronnikov, S. and Sukhanova, T. (2003). Transformations of the Micro-Domain Structure of Polyimide Films during Thermally Induced Chemical Conversion: Characterization via Thermodynamics of Irreversible Processes , J. Phys. Chem. B., 107: 13575-13582.
