Polypseudorotaxanes based on biodegradable poly(L-lactic acid)/poly(ethylene glycol) multiblock copolymers

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Hak Soo Choi1, Tooru Ooya1, Shintaro Sasaki1, Nobuhiko Yui1, Yuichi Ohya2, Takao Nakai2, and Tatsuro Ouchi2. (1) School of Materials Science, JAIST, 1-1 Asahidai, Tatsunokuchi, Ishikawa, 923-1292, Japan, (2) Department of Applied Chemistry, Faculty of Engineering, Kansai University, 3-3-35 Yamate-cho, Suita, Osaka, 564-8680, Japan
A variation of A-B-A-type triblock copolymers consisting of poly(L-lactide) (PLLA) and poly(ethylene glycol) (PEG) was synthesized and examined for complexation with α-cyclodextrins (α-CDs). Although the PLLA block has bulky methyl groups as side chains, stable polypseudorotaxanes of PLLA-PEG-PLLA triblock copolymers as well as PLLA were obtained and confirmed by 1H NMR, solid-state 13C CP/MAS NMR, FT-IR, and X-ray spectroscopies. From the results, it was hypothesized that the guest molecules threaded into the hydrophobic CD cavities, and they form stable pseudorotaxanes in both PEG and PLLA blocks. The α-CDs slide over the flanking bulky PLLA blocks to form an inclusion complex with PEG block; in addition, they form very stick pseudorotaxanes with the end-blocks of PLLA parts. The copolymers confined to the CD channels lost their original crystalline properties but formed a channel-type hydrophobic crystalline structure with CDs due to long chain nature of the copolymers. Such a polymeric inclusion complex can have an important role for constructing supramolecular architectures such as polyrotaxanes and molecular tubes for the use of the bioactive agent delivery system.