Grant-in-Aid for Scientific Research (S)
|Allocation Type||Single-year Grants|
|Research Institution||Osaka University|
HARADA Akira Osaka University, Graduate School of Science, Professor, 大学院理学研究科, 教授 (80127282)
YAMAGUCHI Hiroyasu Osaka University, Graduate School of Science, Assistant Professor, 大学院理学研究科, 助手 (00314352)
TAKASHIMA Yoshinori Osaka University, Graduate School of Science, Assistant Professor, 大学院理学研究科, 助手 (40379277)
|Project Period (FY)
2002 – 2006
Completed(Fiscal Year 2006)
|Budget Amount *help
¥114,660,000 (Direct Cost : ¥88,200,000、Indirect Cost : ¥26,460,000)
Fiscal Year 2006 : ¥9,750,000 (Direct Cost : ¥7,500,000、Indirect Cost : ¥2,250,000)
Fiscal Year 2005 : ¥19,500,000 (Direct Cost : ¥15,000,000、Indirect Cost : ¥4,500,000)
Fiscal Year 2004 : ¥30,290,000 (Direct Cost : ¥23,300,000、Indirect Cost : ¥6,990,000)
Fiscal Year 2003 : ¥24,310,000 (Direct Cost : ¥18,700,000、Indirect Cost : ¥5,610,000)
Fiscal Year 2002 : ¥30,810,000 (Direct Cost : ¥23,700,000、Indirect Cost : ¥7,110,000)
|Keywords||Molecular Recognition / Inclusion / Supramolecular Polymer / Cyclodextrin / Rotaxane / Gel / Self-Assembly / Dynamics / 開環重合 / ポリエステル / シャペロン / 超分子化学 / 包接化合物 / らせん超分子 / ホストーゲスト化学 / ポリロタキサン / 超分子 / らせん / ポリロタキ / ホスト-ゲスト / ホスト分子 / ゲスト分子 / ラセン / チオフェン / ポリチオフェン / 導電性高分子 / 包接重合|
1.Construction of Supramolecular Polymers
When a guest part was covalently attached to cyclodextrin (CD), they formed supramolecular dimers, a cyclic daisy chain, supramolecular oligomers, and polymers. t-Boc-cinnamamide-α-CD was found to form chiral supramolecular polymers in aqueous solutions. Supramolecular polyrotaxane polymers and supramolecular α-, β-CD copolymers were obtained.
2.Dymanics of Supramolecular Polymers
We investigated a new one-pot method to prepare polyrotaxanes containing γ-CDs by the photocyclodimerization reactions of 9-anthryl groups at the ends of the polymer chain in the presence of γ-CDs.
We have constructed pseudo-rotaxanes of α-CD with axle molecules bearing pyridyl end caps via kinetic control of threading of α-CD onto axle molecules. A single substituted pyridyl group attached to the ends of the axle molecule regulated the rate for α-CD passing them. Two methyl substituents could govern the degree of complex formation of a-CD with guest molecules and resu
lted in the distinction of face direction of CD molecules entering the axle ends. α-CDs were arranged in one direction at two station units of the axle molecule.
Poly(ethylene glycol) (PEG)-substituted CDs with different chain lengths have been synthesized. PEG-substituted CDs formed self-threading complexes in aqueous solutions, and the conformational exchange dynamics between self-threading and dethreading could be regulated by its chain length.
3.Polymerization of lactones
CDs were found to initiate ring-opening polymerization of some cyclic esters selectively to give a polyester with a CD at the chain end.
4.Gel-to-Sol and Sol-to-Gel Transitions
Using molecular recognition of α-CD, we have successfully constructed a photoresponsive hydrogel system by combination of simple components, α-CD, dodecyl-modified poly(acrylic acid), and a photoresponsive competitive guest, 4,4'-azodibenzoic acid. Gel-to-sol and sol-to-gel transitions occurred repeatedly by repetitive irradiations of UV and visible light. Less