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Synthesis and self-assembly in bulk of star-shaped block copolymers based on helical polypeptides

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Abstract

A series of star-shaped copolymers containing poly (styrene) (PS) and poly(γ-benzyl-l-glutamate) (PBLG) were synthesized by click reaction from alkyne- and azide-functionalized homopolymers. The α-azide PS star-shaped homopolymer was synthesized by copper-mediated atom transfer radical polymerization from a bromine-containing star-shaped initiator, and α-alkyne PBLG homopolymers were synthesized by ring-opening polymerization of γ-benzyl-l-glutamate N-carboxyanhydride with an amino-containing α-alkyne initiator. The molecular structures of the homopolymers and star-shaped block copolymers were confirmed by 1H nuclear magnetic resonance spectroscopy, Fourier transform infrared spectroscopy (FTIR), and gel permeation chromatography analysis. The self-assembling behavior of the star-shaped block copolymers in bulk was investigated using wide-angle X-ray diffraction, and small-angle X-ray scattering. For star-shaped block copolymer at lower f PS of ~0.27, PBLG segment was assigned to a hexagonally packed-cylinder structure (Φ H) based on the rod-like α-helix conformation as shown in FTIR spectra. By increasing f PS to ~0.42, a proposed microphase-separated double-hexagonal morphology was observed, in which PBLG rods formed the core of the columns by interdigitated packing in Φ H phase with PS domain as the matrix in a larger hexagonal columnar structure. The proposed structure was based on calculation from the simulated molecular length of each block of the copolymer and experimental analyses.

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Acknowledgments

This research was supported by the research project of Sichuan Education Office (10ZC091, 14ZB0406) and Natural Science Foundation of the Chengdu Medical College (CYZ11-010).

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Authors and Affiliations

  1. School of Biomedical Sciences, Chengdu Medical College, 601 Tianhui Road, Chengdu, Sichuan, 610083, China

    Juan Lin

  2. College of Chemical and Environment Protection, Southwest University for Nationalities, First Ring Road, 4th Section No.16, Chengdu, Sichuan, 610041, China

    Qing-Han Zhou, Li-Dong Li & Zhi-Nian Li

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  1. Juan Lin
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Correspondence to Qing-Han Zhou.

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Lin, J., Zhou, QH., Li, LD. et al. Synthesis and self-assembly in bulk of star-shaped block copolymers based on helical polypeptides. Colloid Polym Sci 292, 3177–3185 (2014). https://doi.org/10.1007/s00396-014-3345-2

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  • DOI: https://doi.org/10.1007/s00396-014-3345-2

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