Morphology transition of polyion complex (PIC) micelles with carboxybetaine as a shell induced at different block ratios and their pH-responsivity

In this study, we investigated the morphology transition of polyion complex (PIC) micelles with the change in block ratio and pH-responsivity of PIC micelles or vesicles using entirely ionic diblock copolymers composed of carboxybetaine and ionic blocks. We used 2-((2-(methacryloylo-xy)ethyl)dimethy...

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Veröffentlicht in:Colloid and polymer science 2022-02, Vol.300 (2), p.125-138
Hauptverfasser: Kim, Dongwook, Honda, Hiro, Matsuoka, Hideki, Yusa, Shin-ichi, Saruwatari, Yoshiyuki
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container_start_page 125
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creator Kim, Dongwook
Honda, Hiro
Matsuoka, Hideki
Yusa, Shin-ichi
Saruwatari, Yoshiyuki
description In this study, we investigated the morphology transition of polyion complex (PIC) micelles with the change in block ratio and pH-responsivity of PIC micelles or vesicles using entirely ionic diblock copolymers composed of carboxybetaine and ionic blocks. We used 2-((2-(methacryloylo-xy)ethyl)dimethylammonio)acetate (PGLBT) as carboxybetaine, poly(sodium styrenesulfonate) (PSSNa) as the anionic polymer, and poly[3-(methacrylamido)propyltrimethylammonium chlorid-e] (PMAPTAC) as the cationic polymer. The effect of pH on the PGLBT homopolymer and the PGLBT-containing diblock copolymer was examined by DLS, ELS, and transmittance, and a rapid change of state was observed between pH 4 and 2. At this pH, the carboxyl group of PGLBT was protonated to form a hydrogen bond in the molecule. Furthermore, at a lower pH, diblock copolymer behaved like a cationic polymer. The formation behavior of PIC micelles at different block ratios in the diblock copolymers was investigated by DLS, SLS, TEM, and AFM. PIC vesicles formed when the block ratio of ionic blocks to the PGLBT block was equal or larger (the content of PGLBT was 52% or less). On the other hand, PIC micelles were formed when the block ratio of PGLBT to ionic blocks was larger (the content of PGLBT was 68% or more). The pH-responsivity of PIC micelles was different from that of PIC vesicles. The size of PIC vesicles decreased by lowering pH and increased when the below pH 3. The behavior was the same as the change of state of PGLBT homopolymer with the change in pH. However, the size of PIC micelles increased by lowering pH from pH 6 to 3 and decreased at pH below pH 3. The PGLBT, which became the shell, changed its state with the change in pH and affected the aggregation number of micelles. Graphical Abstract
doi_str_mv 10.1007/s00396-021-04921-7
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We used 2-((2-(methacryloylo-xy)ethyl)dimethylammonio)acetate (PGLBT) as carboxybetaine, poly(sodium styrenesulfonate) (PSSNa) as the anionic polymer, and poly[3-(methacrylamido)propyltrimethylammonium chlorid-e] (PMAPTAC) as the cationic polymer. The effect of pH on the PGLBT homopolymer and the PGLBT-containing diblock copolymer was examined by DLS, ELS, and transmittance, and a rapid change of state was observed between pH 4 and 2. At this pH, the carboxyl group of PGLBT was protonated to form a hydrogen bond in the molecule. Furthermore, at a lower pH, diblock copolymer behaved like a cationic polymer. The formation behavior of PIC micelles at different block ratios in the diblock copolymers was investigated by DLS, SLS, TEM, and AFM. PIC vesicles formed when the block ratio of ionic blocks to the PGLBT block was equal or larger (the content of PGLBT was 52% or less). On the other hand, PIC micelles were formed when the block ratio of PGLBT to ionic blocks was larger (the content of PGLBT was 68% or more). The pH-responsivity of PIC micelles was different from that of PIC vesicles. The size of PIC vesicles decreased by lowering pH and increased when the below pH 3. The behavior was the same as the change of state of PGLBT homopolymer with the change in pH. However, the size of PIC micelles increased by lowering pH from pH 6 to 3 and decreased at pH below pH 3. The PGLBT, which became the shell, changed its state with the change in pH and affected the aggregation number of micelles. 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Honda, Hiro ; Matsuoka, Hideki ; Yusa, Shin-ichi ; Saruwatari, Yoshiyuki</author></sort><facets><frbrtype>5</frbrtype><frbrgroupid>cdi_FETCH-LOGICAL-c319t-eb5416fa74412cef141c411e88896780a955dc15682a9f80d35c4dcfe53200d83</frbrgroupid><rsrctype>articles</rsrctype><prefilter>articles</prefilter><language>eng</language><creationdate>2022</creationdate><topic>Block copolymers</topic><topic>Carboxyl group</topic><topic>Cationic polymerization</topic><topic>Characterization and Evaluation of Materials</topic><topic>Chemical bonds</topic><topic>Chemistry</topic><topic>Chemistry and Materials Science</topic><topic>Complex Fluids and Microfluidics</topic><topic>Food Science</topic><topic>Hydrogen bonds</topic><topic>Micelles</topic><topic>Morphology</topic><topic>Nanotechnology and Microengineering</topic><topic>Original Contribution</topic><topic>Physical Chemistry</topic><topic>Polymer Sciences</topic><topic>Polymers</topic><topic>Soft and Granular Matter</topic><topic>Vesicles</topic><toplevel>peer_reviewed</toplevel><toplevel>online_resources</toplevel><creatorcontrib>Kim, Dongwook</creatorcontrib><creatorcontrib>Honda, Hiro</creatorcontrib><creatorcontrib>Matsuoka, Hideki</creatorcontrib><creatorcontrib>Yusa, Shin-ichi</creatorcontrib><creatorcontrib>Saruwatari, Yoshiyuki</creatorcontrib><collection>CrossRef</collection><collection>Engineered Materials Abstracts</collection><collection>Technology Research Database</collection><collection>ProQuest SciTech Collection</collection><collection>ProQuest Technology Collection</collection><collection>Materials Science &amp; 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We used 2-((2-(methacryloylo-xy)ethyl)dimethylammonio)acetate (PGLBT) as carboxybetaine, poly(sodium styrenesulfonate) (PSSNa) as the anionic polymer, and poly[3-(methacrylamido)propyltrimethylammonium chlorid-e] (PMAPTAC) as the cationic polymer. The effect of pH on the PGLBT homopolymer and the PGLBT-containing diblock copolymer was examined by DLS, ELS, and transmittance, and a rapid change of state was observed between pH 4 and 2. At this pH, the carboxyl group of PGLBT was protonated to form a hydrogen bond in the molecule. Furthermore, at a lower pH, diblock copolymer behaved like a cationic polymer. The formation behavior of PIC micelles at different block ratios in the diblock copolymers was investigated by DLS, SLS, TEM, and AFM. PIC vesicles formed when the block ratio of ionic blocks to the PGLBT block was equal or larger (the content of PGLBT was 52% or less). On the other hand, PIC micelles were formed when the block ratio of PGLBT to ionic blocks was larger (the content of PGLBT was 68% or more). The pH-responsivity of PIC micelles was different from that of PIC vesicles. The size of PIC vesicles decreased by lowering pH and increased when the below pH 3. The behavior was the same as the change of state of PGLBT homopolymer with the change in pH. However, the size of PIC micelles increased by lowering pH from pH 6 to 3 and decreased at pH below pH 3. The PGLBT, which became the shell, changed its state with the change in pH and affected the aggregation number of micelles. Graphical Abstract</abstract><cop>Berlin/Heidelberg</cop><pub>Springer Berlin Heidelberg</pub><doi>10.1007/s00396-021-04921-7</doi><tpages>14</tpages></addata></record>
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subjects Block copolymers
Carboxyl group
Cationic polymerization
Characterization and Evaluation of Materials
Chemical bonds
Chemistry
Chemistry and Materials Science
Complex Fluids and Microfluidics
Food Science
Hydrogen bonds
Micelles
Morphology
Nanotechnology and Microengineering
Original Contribution
Physical Chemistry
Polymer Sciences
Polymers
Soft and Granular Matter
Vesicles
title Morphology transition of polyion complex (PIC) micelles with carboxybetaine as a shell induced at different block ratios and their pH-responsivity
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