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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Main Authors: Tomohisa Watanabe, Yubo Wang, Tomoko Ono, Satoru Chimura, Takuya Isono, Kenji Tajima, Toshifumi Satoh, Shin-ichiro Sato, Daichi Ida, Takuya Yamamoto
Format: Article
Language:English
Published: MDPI AG 2022-04-01
Series:Polymers
Subjects:
Online Access:https://www.mdpi.com/2073-4360/14/9/1823
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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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