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Precise placement of thioester bonds into sequence-controlled polymers containing ABAC-type units

Author

Listed:
  • Yanni Xia

    (Zhejiang University)

  • Tong Shao

    (Zhejiang University)

  • Yue Sun

    (Zhejiang University)

  • Jianuo Wang

    (Zhejiang University)

  • Chaoyuan Gu

    (Zhejiang University)

  • Chengjian Zhang

    (Zhejiang University)

  • Xinghong Zhang

    (Zhejiang University)

Abstract

The precise placement of thioester bonds into sequence-controlled polymers remains a grand challenge. Here, we demonstrate the versatile synthesis of sequence-controlled polymers from the step polymerization of cyclic thioanhydrides (A), diacrylates (B), and diols/diamines (C). In addition to easily accessible diverse monomers, the method is metal-free/catalyst-free, atom-economical, and wide in monomer scope, yielding 107 polymers with >90% yields and weight-average molecular weights of up to 175.4 kDa. The obtained polymers contain ABAC-type repeating units and precisely distributed in-chain thioester and ester (and amide) groups. The chemoselectivity of the polymerization is revealed by density functional theory calculations. The polymer library exhibits considerably tunable performance: glass-transition temperatures of −36–72 °C, melting temperatures of 43–133 °C, degradability, thermoplastics/elastomers, and thioester-based functions. This study furnishes a facile method to precisely incorporate thioester bonds into sequence-controlled polymers.

Suggested Citation

  • Yanni Xia & Tong Shao & Yue Sun & Jianuo Wang & Chaoyuan Gu & Chengjian Zhang & Xinghong Zhang, 2025. "Precise placement of thioester bonds into sequence-controlled polymers containing ABAC-type units," Nature Communications, Nature, vol. 16(1), pages 1-11, December.
    • Handle: RePEc:nat:natcom:v:16:y:2025:i:1:d:10.1038_s41467-025-57208-8
    DOI: 10.1038/s41467-025-57208-8
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    References listed on IDEAS

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    1. Moran Frenkel-Pinter & Marcos Bouza & Facundo M. Fernández & Luke J. Leman & Loren Dean Williams & Nicholas V. Hud & Aikomari Guzman-Martinez, 2022. "Thioesters provide a plausible prebiotic path to proto-peptides," Nature Communications, Nature, vol. 13(1), pages 1-8, December.
    2. Rihe Liu & Leslie E. Orgel, 1997. "Oxidative acylation using thioacids," Nature, Nature, vol. 389(6646), pages 52-54, September.
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