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Prismatic Block Copolymer Hexosomes
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    Prismatic Block Copolymer Hexosomes
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    • André H. Gröschel*
      André H. Gröschel
      Institute for Physical Chemistry and Center for Soft Nanoscience (SoN), University of Münster, Corrensstraße 28-30, 48149 Münster, Germany
      Polymer Materials for Energy Storage (PES), Bavarian Centre for Battery Technology (BayBatt) and Bavarian Polymer Institute (BPI), University of Bayreuth, Universitätsstr. 30, 95448 Bayreuth, Germany
      *Email for A.H.G.: [email protected]
    • Tina Gröschel
      Tina Gröschel
      Evonik Industries AG, High-Performance Polymers, Paul-Baumann-Straße 1, 45772 Marl, Germany
    • Suna Azhdari
      Suna Azhdari
      Institute for Physical Chemistry and Center for Soft Nanoscience (SoN), University of Münster, Corrensstraße 28-30, 48149 Münster, Germany
      More by Suna Azhdari
    • Marcel Schumacher
      Marcel Schumacher
      Institute for Physical Chemistry and Center for Soft Nanoscience (SoN), University of Münster, Corrensstraße 28-30, 48149 Münster, Germany
    • Hui Chen
      Hui Chen
      Institute for Physical Chemistry and Center for Soft Nanoscience (SoN), University of Münster, Corrensstraße 28-30, 48149 Münster, Germany
      More by Hui Chen
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    ACS Nano

    Cite this: ACS Nano 2023, 17, 16, 16069–16079
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acsnano.3c04827
    Published August 11, 2023
    Copyright © 2023 The Authors. Published by American Chemical Society

    Abstract

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    Cubosomes and hexosomes are recent solution morphologies with an ordered porous structure and are observed for lipids and amphiphilic block copolymers (BCPs) with high hydrophobic fractions. Whereas lipid hexosomes typically exhibit a prismatic shape, BCP hexosomes have so far only been observed as closed microspheres where inner channels are not connected to the surrounding medium. Here, we describe the formation of flat, prismatic BCP hexosomes with pronounced faceting and a highly ordered lattice of hexagonally packed channels. We assemble polystyrene-block-poly(4-vinylpyridine) (PS-b-P4VP or SV) into the hexosome framework using polystyrene-block-poly(4-vinylpyridine)-block-poly(tert-butyl methacrylate) (PS-b-P4VP-b-PT or SVT) as a macromolecular surfactant in low-χ solvents. During solvent exchange, SV-rich domains form through liquid–liquid phase separation, followed by solidification and confined assembly within these domains. Since the final solvent (acetone) has a very low χ parameter toward PS and P4VP (equaling low interfacial tension), solidification of the hexosome occurs under confinement conditions that we term “supersoft”. The low interfacial tension allows the stabilization of the hexagonal-prismatic shape, which originates from the hexagonal lattice of channels. Increasing the interfacial tension with polar cosolvents at some point dominates the particle shape, resulting in deformation of prismatic BCP hexosomes into spinning-top structures. The use of low-χ solvents for confined assembly of BCPs may allow the formation of unusual particle shapes simply by tuning the polymer–solvent interaction.

    Copyright © 2023 The Authors. Published by American Chemical Society

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    Supporting Information

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    The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acsnano.3c04827.

    • Supporting TEM and cryo-TEM images, grayscale analyses of channel diameter, electron tomography, SEM of SVT micelles, SEM images of micrometer-sized BCP hexosomes, loading and redispersion of SiO2-loaded BCP hexosomes, and spinning-top structures (PDF)

    • Cryo-TEM tilt series of a BCP hexosome (AVI)

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    Cited By

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    This article is cited by 5 publications.

    1. Hairui Huang, Hanyu Wu, Yizhou Zhang, Xunda Feng. Polyhedral Polymeric Microparticles with Interwoven 1 nm Gyroid Pores for Precise Adsorption and Nanoconfined Degradation. ACS Nano 2025, 19 (9) , 8926-8938. https://doi.org/10.1021/acsnano.4c16888
    2. Min Ren, Mengmeng Zhang, Zaiyan Hou, Xinghao Yan, Lianbin Zhang, Jiangping Xu, Jintao Zhu. Bicontinuous Block Copolymer Microparticles through Hydrogen-Bonding-Mediated Dual Phase Separation between Polymer Segments and Fluorinated Additives. ACS Nano 2025, 19 (1) , 1159-1166. https://doi.org/10.1021/acsnano.4c13152
    3. Hui Chen, Marcel Schumacher, Alessandro Ianiro, Tim Julian Stank, Nicole Janoszka, Chen Chen, Suna Azhdari, Thomas Hellweg, André H. Gröschel. Photocleavable Polymer Cubosomes: Synthesis, Self-Assembly, and Photorelease. Journal of the American Chemical Society 2024, 146 (21) , 14776-14784. https://doi.org/10.1021/jacs.4c02651
    4. Marcel Schumacher, Nadine Tänzer, Marius G. Braun, Manuel Trömer, Giada Quintieri, Mahima Goel, Markus Heidelmann, André H. Gröschel. Poly(4‐Vinylpyridine)‐Based Cubosomes: Synthesis, Assembly, and Loading Capabilities. Small Science 2024, 4 (12) https://doi.org/10.1002/smsc.202400274
    5. Hyunkyu Oh, Young Jun Lee, Eun Ji Kim, Jinseok Park, Hee-Eun Kim, Hyunsoo Lee, Hyunjoo Lee, Bumjoon J. Kim. Impact of channel nanostructures of porous carbon particles on their catalytic performance. Nanoscale 2024, 16 (2) , 879-886. https://doi.org/10.1039/D3NR05384A

    ACS Nano

    Cite this: ACS Nano 2023, 17, 16, 16069–16079
    Click to copy citationCitation copied!
    https://doi.org/10.1021/acsnano.3c04827
    Published August 11, 2023
    Copyright © 2023 The Authors. Published by American Chemical Society

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