Precise placement of thioester bonds into sequence-controlled polymers containing ABAC-type units
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...
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| Format: | Article |
| Language: | English |
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Nature Portfolio
2025-02-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-57208-8 |
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| author | Yanni Xia Tong Shao Yue Sun Jianuo Wang Chaoyuan Gu Chengjian Zhang Xinghong Zhang |
| author_facet | Yanni Xia Tong Shao Yue Sun Jianuo Wang Chaoyuan Gu Chengjian Zhang Xinghong Zhang |
| author_sort | Yanni Xia |
| collection | DOAJ |
| description | 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. |
| format | Article |
| id | doaj-art-cb1aff3a91284f7c9fd4b33ba89b5e9e |
| institution | OA Journals |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-02-01 |
| publisher | Nature Portfolio |
| record_format | Article |
| series | Nature Communications |
| spelling | doaj-art-cb1aff3a91284f7c9fd4b33ba89b5e9e2025-08-20T02:16:49ZengNature PortfolioNature Communications2041-17232025-02-0116111110.1038/s41467-025-57208-8Precise placement of thioester bonds into sequence-controlled polymers containing ABAC-type unitsYanni Xia0Tong Shao1Yue Sun2Jianuo Wang3Chaoyuan Gu4Chengjian Zhang5Xinghong Zhang6State Key Laboratory of Biobased Transportation Fuel Technology, International Research Center for X Polymers, Department of Polymer Science and Engineering, Zhejiang UniversityState Key Laboratory of Biobased Transportation Fuel Technology, International Research Center for X Polymers, Department of Polymer Science and Engineering, Zhejiang UniversityState Key Laboratory of Biobased Transportation Fuel Technology, International Research Center for X Polymers, Department of Polymer Science and Engineering, Zhejiang UniversityState Key Laboratory of Biobased Transportation Fuel Technology, International Research Center for X Polymers, Department of Polymer Science and Engineering, Zhejiang UniversityState Key Laboratory of Biobased Transportation Fuel Technology, International Research Center for X Polymers, Department of Polymer Science and Engineering, Zhejiang UniversityState Key Laboratory of Biobased Transportation Fuel Technology, International Research Center for X Polymers, Department of Polymer Science and Engineering, Zhejiang UniversityState Key Laboratory of Biobased Transportation Fuel Technology, International Research Center for X Polymers, Department of Polymer Science and Engineering, Zhejiang UniversityAbstract 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.https://doi.org/10.1038/s41467-025-57208-8 |
| spellingShingle | Yanni Xia Tong Shao Yue Sun Jianuo Wang Chaoyuan Gu Chengjian Zhang Xinghong Zhang Precise placement of thioester bonds into sequence-controlled polymers containing ABAC-type units Nature Communications |
| title | Precise placement of thioester bonds into sequence-controlled polymers containing ABAC-type units |
| title_full | Precise placement of thioester bonds into sequence-controlled polymers containing ABAC-type units |
| title_fullStr | Precise placement of thioester bonds into sequence-controlled polymers containing ABAC-type units |
| title_full_unstemmed | Precise placement of thioester bonds into sequence-controlled polymers containing ABAC-type units |
| title_short | Precise placement of thioester bonds into sequence-controlled polymers containing ABAC-type units |
| title_sort | precise placement of thioester bonds into sequence controlled polymers containing abac type units |
| url | https://doi.org/10.1038/s41467-025-57208-8 |
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