Topology and Sequence-Dependent Micellization and Phase Separation of Pluronic L35, L64, 10R5, and 17R4: Effects of Cyclization and the Chain Ends
The topology effects of cyclization on thermal phase transition behaviors were investigated for a series of amphiphilic Pluronic copolymers of both hydrophilic–hydrophobic–hydrophilic and hydrophobic–hydrophilic–hydrophobic block sequences. The dye solubilization measurements revealed the lowered cr...
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2022-04-01
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author | Tomohisa Watanabe Yubo Wang Tomoko Ono Satoru Chimura Takuya Isono Kenji Tajima Toshifumi Satoh Shin-ichiro Sato Daichi Ida Takuya Yamamoto |
author_facet | Tomohisa Watanabe Yubo Wang Tomoko Ono Satoru Chimura Takuya Isono Kenji Tajima Toshifumi Satoh Shin-ichiro Sato Daichi Ida Takuya Yamamoto |
author_sort | Tomohisa Watanabe |
collection | DOAJ |
description | The topology effects of cyclization on thermal phase transition behaviors were investigated for a series of amphiphilic Pluronic copolymers of both hydrophilic–hydrophobic–hydrophilic and hydrophobic–hydrophilic–hydrophobic block sequences. The dye solubilization measurements revealed the lowered critical micelle temperatures (<i>T</i><sub>CMT</sub>) along with the decreased micellization enthalpy (Δ<i>H</i><sub>mic</sub>) and entropy (Δ<i>S</i><sub>mic</sub>) for the cyclized species. Furthermore, the transmittance and dynamic light scattering (DLS) measurements indicated a block sequence-dependent effect on the clouding phenomena, where a profound decrease in cloud point (<i>T</i><sub>c</sub>) was only found for the copolymers with a hydrophilic–hydrophobic–hydrophilic block sequence. Thus, the effect of cyclization on these critical temperatures was manifested differently depending on its block sequence. Finally, a comparison of the linear hydroxy-terminated, methoxy-terminated, and cyclized species indicated the effect of cyclization to be unique from a simple elimination of the terminal hydrophilic moieties. |
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spelling | doaj.art-5dd8a86b309c4396aba981c4ff812ea92023-11-23T09:06:48ZengMDPI AGPolymers2073-43602022-04-01149182310.3390/polym14091823Topology and Sequence-Dependent Micellization and Phase Separation of Pluronic L35, L64, 10R5, and 17R4: Effects of Cyclization and the Chain EndsTomohisa Watanabe0Yubo Wang1Tomoko Ono2Satoru Chimura3Takuya Isono4Kenji Tajima5Toshifumi Satoh6Shin-ichiro Sato7Daichi Ida8Takuya Yamamoto9Graduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo 060-8628, Hokkaido, JapanGraduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo 060-8628, Hokkaido, JapanDivision of Applied Chemistry, Faculty of Engineering, Hokkaido University, Sapporo 060-8628, Hokkaido, JapanGraduate School of Chemical Sciences and Engineering, Hokkaido University, Sapporo 060-8628, Hokkaido, JapanDivision of Applied Chemistry, Faculty of Engineering, Hokkaido University, Sapporo 060-8628, Hokkaido, JapanDivision of Applied Chemistry, Faculty of Engineering, Hokkaido University, Sapporo 060-8628, Hokkaido, JapanDivision of Applied Chemistry, Faculty of Engineering, Hokkaido University, Sapporo 060-8628, Hokkaido, JapanDivision of Applied Chemistry, Faculty of Engineering, Hokkaido University, Sapporo 060-8628, Hokkaido, JapanDepartment of Polymer Chemistry, Graduate School of Engineering, Kyoto University, Katsura 615-8510, Kyoto, JapanDivision of Applied Chemistry, Faculty of Engineering, Hokkaido University, Sapporo 060-8628, Hokkaido, JapanThe topology effects of cyclization on thermal phase transition behaviors were investigated for a series of amphiphilic Pluronic copolymers of both hydrophilic–hydrophobic–hydrophilic and hydrophobic–hydrophilic–hydrophobic block sequences. The dye solubilization measurements revealed the lowered critical micelle temperatures (<i>T</i><sub>CMT</sub>) along with the decreased micellization enthalpy (Δ<i>H</i><sub>mic</sub>) and entropy (Δ<i>S</i><sub>mic</sub>) for the cyclized species. Furthermore, the transmittance and dynamic light scattering (DLS) measurements indicated a block sequence-dependent effect on the clouding phenomena, where a profound decrease in cloud point (<i>T</i><sub>c</sub>) was only found for the copolymers with a hydrophilic–hydrophobic–hydrophilic block sequence. Thus, the effect of cyclization on these critical temperatures was manifested differently depending on its block sequence. Finally, a comparison of the linear hydroxy-terminated, methoxy-terminated, and cyclized species indicated the effect of cyclization to be unique from a simple elimination of the terminal hydrophilic moieties.https://www.mdpi.com/2073-4360/14/9/1823cyclic polymerblock copolymerPluronicmicellizationcloud pointphase transition |
spellingShingle | Tomohisa Watanabe Yubo Wang Tomoko Ono Satoru Chimura Takuya Isono Kenji Tajima Toshifumi Satoh Shin-ichiro Sato Daichi Ida Takuya Yamamoto Topology and Sequence-Dependent Micellization and Phase Separation of Pluronic L35, L64, 10R5, and 17R4: Effects of Cyclization and the Chain Ends Polymers cyclic polymer block copolymer Pluronic micellization cloud point phase transition |
title | Topology and Sequence-Dependent Micellization and Phase Separation of Pluronic L35, L64, 10R5, and 17R4: Effects of Cyclization and the Chain Ends |
title_full | Topology and Sequence-Dependent Micellization and Phase Separation of Pluronic L35, L64, 10R5, and 17R4: Effects of Cyclization and the Chain Ends |
title_fullStr | Topology and Sequence-Dependent Micellization and Phase Separation of Pluronic L35, L64, 10R5, and 17R4: Effects of Cyclization and the Chain Ends |
title_full_unstemmed | Topology and Sequence-Dependent Micellization and Phase Separation of Pluronic L35, L64, 10R5, and 17R4: Effects of Cyclization and the Chain Ends |
title_short | Topology and Sequence-Dependent Micellization and Phase Separation of Pluronic L35, L64, 10R5, and 17R4: Effects of Cyclization and the Chain Ends |
title_sort | topology and sequence dependent micellization and phase separation of pluronic l35 l64 10r5 and 17r4 effects of cyclization and the chain ends |
topic | cyclic polymer block copolymer Pluronic micellization cloud point phase transition |
url | https://www.mdpi.com/2073-4360/14/9/1823 |
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