title: Formation of Reactant Complex Structure for Initiation Reaction of Lactone Ring-Opening Polymerization by Cooperation of Multiple Cyclodextrin.
abstract: Ring-opening polymerization of lactones initiated by cyclodextrins has been reported as a promising polymer synthetic method. To investigate the unknown molecular level mechanism of the initiation reaction, we executed molecular dynamics simulations of model systems composed of single or multiple β-cyclodextrin (β-CD) molecules in δ-valerolactone (VL) solvent and explored the reactant complex structures satisfying three conditions (VL inclusion in the β-CD cavity, hydrogen bonding, and nucleophilic attack) at the same time. As a result, we confirmed the formation of the reactant complex structure. Comparison between the single and multiple β-CD models revealed that the formation is more frequent and the distance for the nucleophilic attack is shorter in the multiple model. Therefore, we anticipate that the reaction proceeds more efficiently by the cooperation of multiple β-CDs. This finding will contribute to understanding the reaction mechanism from the atomistic point of view.
authors.affiliation: Graduate School of Information Science, Nagoya University , Furo-cho, Chikusa-ku, Nagoya 464-8601, Japan.|Core Research for Evolutional Science and Technology, Japan Science and Technology Agency , Honmachi, Kawaguchi 332-0012, Japan.
authors.forename: Masayoshi
authors.initials: M
authors.lastname: Takayanagi
authors.affiliation: Graduate School of Information Science, Nagoya University , Furo-cho, Chikusa-ku, Nagoya 464-8601, Japan.
authors.forename: Shoko
authors.initials: S
authors.lastname: Ito
authors.affiliation: Graduate School of Information Science, Nagoya University , Furo-cho, Chikusa-ku, Nagoya 464-8601, Japan.
authors.forename: Kentaro
authors.initials: K
authors.lastname: Matsumoto
authors.affiliation: Graduate School of Information Science, Nagoya University , Furo-cho, Chikusa-ku, Nagoya 464-8601, Japan.|Core Research for Evolutional Science and Technology, Japan Science and Technology Agency , Honmachi, Kawaguchi 332-0012, Japan.|ESICB, Kyoto University , Kyodai Katsura, Nishikyo-ku, Kyoto 615-8520, Japan.
authors.forename: Masataka
authors.initials: M
authors.lastname: Nagaoka