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Giant Vesicles of Amphiphilic Diblock Copolymer with Branched Side Chains

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), 2021. 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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[3] Campbell, M., Naworal, J. (1969). Composition of the saturated and monounsaturated fatty acids of Mycobacterium phlei. Journal of Lipid Research, 10, 593-598.
[4] Clejan, S., Krulwich, T. A., Mondrus, K. R., Seto-Young, D. (1986). Membrane lipid composition of obligately and facultatively alkalophilic strains of Bacillus spp. Journal of Bacteriology, 168, 334-340.
[5] Kyte, J., Doolittle, R. F. (1982). A simple method for displaying the hydropathic character of a protein. Journal of Molecular Biology, 157, 105-132.
[6] Černoch, P., Jager, A., Černochová, Z., Sincari, V., Albuquerque, L. J. C., Konefal, R., Pavlova, E., Giacomelli, F. C., Jager, E. (2021). Engineering of pH-triggered nanoplatforms based on novel poly (2-methyl-2-oxazoline)-b-poly[2-(diisopropylamino)ethyl methacrylate] diblock copolymers with tunable morphologies for biomedical applications. Polymer Chemistry, 12, 2868-2880.
[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.
[11] Yoshida, E. (2018). Morphology transformation of giant vesicles by a polyelectrolyte for an artificial model of a membrane protein for endocytosis. Colloid and Surface Science, 3 (1), 6-11.
[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.
[13] Yoshida, E. (2014). Fission of giant vesicles accompanied by hydrophobic chain growth through polymerization-induced self-assembly. Colloid and Polymer Science, 292, 1463-1468.
[14] Yoshida, E. (2017). Fabrication of anastomosed tubular networks developed out of fenestrated sheets through thermo responsiveness of polymer giant vesicles. Chem Xpress, 10 (1), 118, 1-11.
[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.
[19] Miyazawa, T., Endo, T., Shiihashi, S., Ogawara, M. (1985). Selective oxidation of alcohols by oxoaminium salts (R2N:O+ X-). The Journal of Organic Chemistry, 50, 1332-1334.
[20] Yoshida, E. (2012). Effects of illuminance and heat rays on photo-controlled/living radical polymerization mediated by 4-methoxy-2,2,6,6-tetramethylpiperidine-1-oxyl. ISRN Polymer Science, 102186.
[21] Yoshida, E. (2010). Nitroxide-mediated photo-living radical polymerization of methyl methacrylate using (4-tert-butylphenyl)diphenylsulfonium triflate as a photo-acid generator. Colloid and Polymer Science, 288, 239-243.
[22] Yoshida, E. (2013). Nitroxide-mediated photo-controlled/living radical polymerization of methacrylic acid. Open Journal of Polymer Chemistry, 3, 16-22.
[23] Yoshida, E. (2014). Hydrophobic energy estimation for giant vesicle formation by amphiphilic poly(methacrylic acid)-block-poly(alkyl methacrylate-random-methacrylic acid) random block copolymers. Colloid and Polymer Science, 292, 2555-2561.
[24] Israelachvili, J. N. (2011). Intermolecular and Surface Forces, 3rd ed. Academic Press, Waltham.
Cite This Article
  • 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
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    JF  - Colloid and Surface Science
    JO  - Colloid and Surface Science
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    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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Author Information
  • Department of Applied Chemistry and Life Science, Toyohashi University of Technology, Toyohashi, Japan

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