Giant Vesicles of Amphiphilic Diblock Copolymer with Branched Side Chains

Eri Yoshida

doi:doi:10.11648/j.css.20210601.11

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Giant Vesicles of Amphiphilic Diblock Copolymer with Branched Side Chains

Eri Yoshida

Published in Colloid and Surface Science (Volume 6, Issue 1)

Received: 12 September 2021 Accepted: 8 October 2021 Published: 15 October 2021

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Abstract

Biomolecules of lipids and proteins optimize the hydrophobicity to precisely form their three-dimensional structures. The branching of hydrocarbon chains is appropriate for fine-tuning the hydrophobicity of the molecules because it provides a slight reduction in hydrophobicity. This paper describes the morphological changes of vesicles formed by an amphiphilic diblock copolymer supporting branched side chains in the hydrophobic block to elucidate the steric effect of the side chains on the morphology. The vesicles consisting of poly(methacrylic acid)-block-poly(isopropyl methacrylate-random-methacrylic acid), PMAA-b-P(iPMA-r-MAA), were obtained by the polymerization-induced self-assembly using the photo-nitroxide mediated controlled/living radical polymerization (photo-NMP) in an aqueous methanol solution (methanol/water=3/1 v/v). PMAA-b-P(iPMA-r-MAA) with a very high ratio of the iPMA units produced spherical vesicles. As the iPMA ratio decreased, the vesicles shrank, expanded again, and changed into sheets. The chain length of the hydrophobic block also dominated the morphology. For the high iPMA ratio constant, the copolymers with a short block produced two domains of micron-sized spherical vesicles and unspecific nano-sized particles fused. An increase in the block length changed the nanoparticles into nanospheres, accompanied by an increase in the number of micron-sized spherical vesicles. By further extending the block length, most of the nanospheres grew into micron-sized spherical vesicles. On the other hand, for the low iPMA ratio constant, an increase in the length of the hydrophobic chain changed the unspecific nanoparticles sheets into aggregates with an inverted hexagonal phase reticularly perforated. The PMAA-b-P(n-propyl methacrylate-r-MAA) copolymer produced flexible sheets with a smooth surface without any pores, while PMAA-b-P(methyl methacrylate-r-MAA) provided rods of laminated sheets. It was found that the formation of the inverted hexagonal phase was due to the steric repulsion of the bulky isopropyl groups in the hydrophobic blocks. These findings indicate that the morphology of the vesicles is manipulated not only by the hydrophobicity of the copolymer, but also by the bulkiness of the branched side chain in the hydrophobic block.

Published in	Colloid and Surface Science (Volume 6, Issue 1)
DOI	10.11648/j.css.20210601.11
Page(s)	1-7
Creative Commons	This is an Open Access article, distributed under the terms of the Creative Commons Attribution 4.0 International License (http://creativecommons.org/licenses/by/4.0/), which permits unrestricted use, distribution and reproduction in any medium or format, provided the original work is properly cited.
Copyright	Copyright © The Author(s), 2024. Published by Science Publishing Group

Keywords

Giant Vesicles, Amphiphilic Diblock Copolymer, Morphology Changes, Branched Side Chains, Steric Repulsion, Inverted Hexagonal Phase

References

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[7]	Wei, P., Cornel, E. J., Du, J. (2021). Breaking the corona symmetry of vesicles. Macromolecules, 54, 7603-7611.
[8]	Yoshida, E. (2013). Giant vesicles prepared by nitroxide-mediated photo-controlled/living radical polymerization-induced self-assembly. Colloid and Polymer Science, 291, 2733-2739.
[9]	Yoshida, E. (2015). Fabrication of microvillus-like structure by photopolymerization-induced self-assembly of an amphiphilic random block copolymer. Colloid and Polymer Science, 293, 1841-1845.
[10]	Yoshida, E. (2019). Perforated giant vesicles composed of amphiphilic diblock copolymer: New artificial biomembrane model of nuclear envelope. Soft Matter, 15, 9849-9857.
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[12]	Yoshida, E. (2015). Morphological changes in polymer giant vesicles by intercalation of a segment copolymer as a sterol model in plasma membrane. Colloid and Polymer Science, 293, 1835-1840.
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[15]	Yoshida, E. (2015). PH response behavior of giant vesicles comprised of amphiphilic poly(methacrylic acid)-block-poly(methyl methacrylate-random-methacrylic acid). Colloid and Polymer Science, 293, 649-653.
[16]	Yoshida, E. (2015). Enhanced permeability of Rhodamine B into bilayers comprised of amphiphilic random block copolymers by incorporation of ionic segments in the hydrophobic chains. Colloid and Polymer Science, 293, 2437-2443.
[17]	Yoshida, E. (2014). Morphology control of giant vesicles by manipulating hydrophobic-hydrophilic balance of amphiphilic random block copolymers through polymerization-induced self-assembly. Colloid and Polymer Science, 292, 763-769.
[18]	Kobayashi, S., Uyama, H., Yamamoto, I., Matsumoto, Y. (1990). Preparation of monodispersed poly(methyl methacrylate) particle in the size of micron range. Polymer Journal, 22, 759-761.
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APA Style

Eri Yoshida. (2021). Giant Vesicles of Amphiphilic Diblock Copolymer with Branched Side Chains. Colloid and Surface Science, 6(1), 1-7. https://doi.org/10.11648/j.css.20210601.11

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Eri Yoshida. Giant Vesicles of Amphiphilic Diblock Copolymer with Branched Side Chains. Colloid Surf. Sci. 2021, 6(1), 1-7. doi: 10.11648/j.css.20210601.11

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AMA Style

Eri Yoshida. Giant Vesicles of Amphiphilic Diblock Copolymer with Branched Side Chains. Colloid Surf Sci. 2021;6(1):1-7. doi: 10.11648/j.css.20210601.11

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@article{10.11648/j.css.20210601.11,
  author = {Eri Yoshida},
  title = {Giant Vesicles of Amphiphilic Diblock Copolymer with Branched Side Chains},
  journal = {Colloid and Surface Science},
  volume = {6},
  number = {1},
  pages = {1-7},
  doi = {10.11648/j.css.20210601.11},
  url = {https://doi.org/10.11648/j.css.20210601.11},
  eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.css.20210601.11},
  abstract = {Biomolecules of lipids and proteins optimize the hydrophobicity to precisely form their three-dimensional structures. The branching of hydrocarbon chains is appropriate for fine-tuning the hydrophobicity of the molecules because it provides a slight reduction in hydrophobicity. This paper describes the morphological changes of vesicles formed by an amphiphilic diblock copolymer supporting branched side chains in the hydrophobic block to elucidate the steric effect of the side chains on the morphology. The vesicles consisting of poly(methacrylic acid)-block-poly(isopropyl methacrylate-random-methacrylic acid), PMAA-b-P(iPMA-r-MAA), were obtained by the polymerization-induced self-assembly using the photo-nitroxide mediated controlled/living radical polymerization (photo-NMP) in an aqueous methanol solution (methanol/water=3/1 v/v). PMAA-b-P(iPMA-r-MAA) with a very high ratio of the iPMA units produced spherical vesicles. As the iPMA ratio decreased, the vesicles shrank, expanded again, and changed into sheets. The chain length of the hydrophobic block also dominated the morphology. For the high iPMA ratio constant, the copolymers with a short block produced two domains of micron-sized spherical vesicles and unspecific nano-sized particles fused. An increase in the block length changed the nanoparticles into nanospheres, accompanied by an increase in the number of micron-sized spherical vesicles. By further extending the block length, most of the nanospheres grew into micron-sized spherical vesicles. On the other hand, for the low iPMA ratio constant, an increase in the length of the hydrophobic chain changed the unspecific nanoparticles sheets into aggregates with an inverted hexagonal phase reticularly perforated. The PMAA-b-P(n-propyl methacrylate-r-MAA) copolymer produced flexible sheets with a smooth surface without any pores, while PMAA-b-P(methyl methacrylate-r-MAA) provided rods of laminated sheets. It was found that the formation of the inverted hexagonal phase was due to the steric repulsion of the bulky isopropyl groups in the hydrophobic blocks. These findings indicate that the morphology of the vesicles is manipulated not only by the hydrophobicity of the copolymer, but also by the bulkiness of the branched side chain in the hydrophobic block.},
 year = {2021}
}

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TY - JOUR
T1 - Giant Vesicles of Amphiphilic Diblock Copolymer with Branched Side Chains
AU - Eri Yoshida
Y1 - 2021/10/15
PY - 2021
N1 - https://doi.org/10.11648/j.css.20210601.11
DO - 10.11648/j.css.20210601.11
T2 - Colloid and Surface Science
JF - Colloid and Surface Science
JO - Colloid and Surface Science
SP - 1
EP - 7
PB - Science Publishing Group
SN - 2578-9236
UR - https://doi.org/10.11648/j.css.20210601.11
AB - Biomolecules of lipids and proteins optimize the hydrophobicity to precisely form their three-dimensional structures. The branching of hydrocarbon chains is appropriate for fine-tuning the hydrophobicity of the molecules because it provides a slight reduction in hydrophobicity. This paper describes the morphological changes of vesicles formed by an amphiphilic diblock copolymer supporting branched side chains in the hydrophobic block to elucidate the steric effect of the side chains on the morphology. The vesicles consisting of poly(methacrylic acid)-block-poly(isopropyl methacrylate-random-methacrylic acid), PMAA-b-P(iPMA-r-MAA), were obtained by the polymerization-induced self-assembly using the photo-nitroxide mediated controlled/living radical polymerization (photo-NMP) in an aqueous methanol solution (methanol/water=3/1 v/v). PMAA-b-P(iPMA-r-MAA) with a very high ratio of the iPMA units produced spherical vesicles. As the iPMA ratio decreased, the vesicles shrank, expanded again, and changed into sheets. The chain length of the hydrophobic block also dominated the morphology. For the high iPMA ratio constant, the copolymers with a short block produced two domains of micron-sized spherical vesicles and unspecific nano-sized particles fused. An increase in the block length changed the nanoparticles into nanospheres, accompanied by an increase in the number of micron-sized spherical vesicles. By further extending the block length, most of the nanospheres grew into micron-sized spherical vesicles. On the other hand, for the low iPMA ratio constant, an increase in the length of the hydrophobic chain changed the unspecific nanoparticles sheets into aggregates with an inverted hexagonal phase reticularly perforated. The PMAA-b-P(n-propyl methacrylate-r-MAA) copolymer produced flexible sheets with a smooth surface without any pores, while PMAA-b-P(methyl methacrylate-r-MAA) provided rods of laminated sheets. It was found that the formation of the inverted hexagonal phase was due to the steric repulsion of the bulky isopropyl groups in the hydrophobic blocks. These findings indicate that the morphology of the vesicles is manipulated not only by the hydrophobicity of the copolymer, but also by the bulkiness of the branched side chain in the hydrophobic block.
VL - 6
IS - 1
ER -

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Eri Yoshida

Department of Applied Chemistry and Life Science, Toyohashi University of Technology, Toyohashi, Japan

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Eri Yoshida. (2021). Giant Vesicles of Amphiphilic Diblock Copolymer with Branched Side Chains. Colloid and Surface Science, 6(1), 1-7. https://doi.org/10.11648/j.css.20210601.11

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ACS Style

Eri Yoshida. Giant Vesicles of Amphiphilic Diblock Copolymer with Branched Side Chains. Colloid Surf. Sci. 2021, 6(1), 1-7. doi: 10.11648/j.css.20210601.11

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AMA Style

Eri Yoshida. Giant Vesicles of Amphiphilic Diblock Copolymer with Branched Side Chains. Colloid Surf Sci. 2021;6(1):1-7. doi: 10.11648/j.css.20210601.11

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@article{10.11648/j.css.20210601.11,
  author = {Eri Yoshida},
  title = {Giant Vesicles of Amphiphilic Diblock Copolymer with Branched Side Chains},
  journal = {Colloid and Surface Science},
  volume = {6},
  number = {1},
  pages = {1-7},
  doi = {10.11648/j.css.20210601.11},
  url = {https://doi.org/10.11648/j.css.20210601.11},
  eprint = {https://article.sciencepublishinggroup.com/pdf/10.11648.j.css.20210601.11},
  abstract = {Biomolecules of lipids and proteins optimize the hydrophobicity to precisely form their three-dimensional structures. The branching of hydrocarbon chains is appropriate for fine-tuning the hydrophobicity of the molecules because it provides a slight reduction in hydrophobicity. This paper describes the morphological changes of vesicles formed by an amphiphilic diblock copolymer supporting branched side chains in the hydrophobic block to elucidate the steric effect of the side chains on the morphology. The vesicles consisting of poly(methacrylic acid)-block-poly(isopropyl methacrylate-random-methacrylic acid), PMAA-b-P(iPMA-r-MAA), were obtained by the polymerization-induced self-assembly using the photo-nitroxide mediated controlled/living radical polymerization (photo-NMP) in an aqueous methanol solution (methanol/water=3/1 v/v). PMAA-b-P(iPMA-r-MAA) with a very high ratio of the iPMA units produced spherical vesicles. As the iPMA ratio decreased, the vesicles shrank, expanded again, and changed into sheets. The chain length of the hydrophobic block also dominated the morphology. For the high iPMA ratio constant, the copolymers with a short block produced two domains of micron-sized spherical vesicles and unspecific nano-sized particles fused. An increase in the block length changed the nanoparticles into nanospheres, accompanied by an increase in the number of micron-sized spherical vesicles. By further extending the block length, most of the nanospheres grew into micron-sized spherical vesicles. On the other hand, for the low iPMA ratio constant, an increase in the length of the hydrophobic chain changed the unspecific nanoparticles sheets into aggregates with an inverted hexagonal phase reticularly perforated. The PMAA-b-P(n-propyl methacrylate-r-MAA) copolymer produced flexible sheets with a smooth surface without any pores, while PMAA-b-P(methyl methacrylate-r-MAA) provided rods of laminated sheets. It was found that the formation of the inverted hexagonal phase was due to the steric repulsion of the bulky isopropyl groups in the hydrophobic blocks. These findings indicate that the morphology of the vesicles is manipulated not only by the hydrophobicity of the copolymer, but also by the bulkiness of the branched side chain in the hydrophobic block.},
 year = {2021}
}

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