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Colloidal inverse bicontinuous cubic membranes of block copolymers with tunable surface functional groups

Nature Chemistry volume 6, pages 534–541 (2014)Cite this article

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Abstract

Analogous to the complex membranes found in cellular organelles, such as the endoplasmic reticulum, the inverse cubic mesophases of lipids and their colloidal forms (cubosomes) possess internal networks of water channels arranged in crystalline order, which provide a unique nanospace for membrane-protein crystallization and guest encapsulation. Polymeric analogues of cubosomes formed by the direct self-assembly of block copolymers in solution could provide new polymeric mesoporous materials with a three-dimensionally organized internal maze of large water channels. Here we report the self-assembly of amphiphilic dendritic–linear block copolymers into polymer cubosomes in aqueous solution. The presence of precisely defined bulky dendritic blocks drives the block copolymers to form spontaneously highly curved bilayers in aqueous solution. This results in the formation of colloidal inverse bicontinuous cubic mesophases. The internal networks of water channels provide a high surface area with tunable surface functional groups that can serve as anchoring points for large guests such as proteins and enzymes.

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Figure 1: Chemical structures and schematic diagrams of dendritic–linear block copolymers and their self-assembly.
Figure 2: Representative SEM and TEM images of the polymer cubosomes.
Figure 3: Structural analysis of the polymer cubosomes.
Figure 4: Polymer cubosomes of 3223.
Figure 5: Surface-functionalized polymer cubosomes.
Figure 6: Surface-functionalized polymer cubosomes.

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Acknowledgements

This research was supported by the National Research Foundation (NRF) of Korea (NRF-2013R1A1A013075) and Ulsan National Institute of Science and Technology (2012 Future Challenge Research Fund, 1.130014). C.P. acknowledges the NRF for a research fellowship (2013R1A1A2063049): S.H.J. and S.K. thank NRF for financial support (2013R1A1A2012960, ARC 2010-0028684). K.T.K also thanks KUCC for financial support (2V03280). We thank the Unist Central Research Facilities and the Unist-Olympus Biomed Imaging Center for microscopy facilities. We thank J. Y. Cheon and Y. J. Kang for the help with adsorption experiments and protein labelling. We also thank M. G. Jeong for the graphical illustrations.

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Authors and Affiliations

  1. Department of Chemistry, Ulsan National Institute of Science and Technology, 50 UNIST Road, Ulsan, 689-798, Korea

    Yunju La, Chiyoung Park, Sang Hoon Joo & Kyoung Taek Kim

  2. School of Nano-Bioscience and Chemical Engineering, Ulsan National Institute of Science and Technology, 50 UNIST Road, Ulsan, 689-798, Korea

    Sang Hoon Joo, Sebyung Kang & Kyoung Taek Kim

  3. Pohang Accelerator Laboratory, POSTECH, Pohang, 790-784, Korea

    Tae Joo Shin

  4. KIST–UNIST–Ulsan Center for Convergence Materials, Ulsan, 689-798, Korea

    Kyoung Taek Kim

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  1. Yunju La
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Contributions

K.T.K. conceived and designed the experiments. Y.L. carried out most of the experiments, C.P. performed the experiments on surface functionalization and T.J.S. conducted SAXS experiments. S.H. Joo and S.K. carried out porosimetry and protein labelling. All the authors contributed to the analysis and interpretation of the data. K.T.K. wrote the manuscript. All the authors commented on the manuscript.

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Correspondence to Kyoung Taek Kim.

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La, Y., Park, C., Shin, T. et al. Colloidal inverse bicontinuous cubic membranes of block copolymers with tunable surface functional groups. Nature Chem 6, 534–541 (2014). https://doi.org/10.1038/nchem.1946

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