Trefoil polymers from a knotted synthon
13 affiliations
- 1School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, People's Republic of China
- 2State Key Laboratory of Radio Frequency Heterogeneous Integration, College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen, Guangdong, People's Republic of China
- 3State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai, People's Republic of China
- 4Department of Chemistry, Fudan University, Shanghai, People's Republic of China
- 5Department of Macromolecular Sciences, State Key Laboratory of Molecular Engineering of Polymers, Fudan University, Shanghai, People's Republic of China
- 6Instrumental Analytical Center of Shanghai Jiao Tong University, Shanghai, People's Republic of China
- 7Department of Physics, City University of Hong Kong, Kowloon, Hong Kong, People's Republic of China. [email protected]
- 8State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, University of Chinese Academy of Sciences, Chinese Academy of Sciences, Shanghai, People's Republic of China. [email protected]
- 9State Key Laboratory of Radio Frequency Heterogeneous Integration, College of Chemistry and Environmental Engineering, Shenzhen University, Shenzhen, Guangdong, People's Republic of China. [email protected]
- 10Department of Chemistry, University of Manchester, Manchester, UK. [email protected]
- 11School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, People's Republic of China. [email protected]
- 12Department of Chemistry, Fudan University, Shanghai, People's Republic of China. [email protected]
- 13School of Chemistry and Molecular Engineering, East China Normal University, Shanghai, People's Republic of China. [email protected]
Abstract
Precise control over the presence and position of knots in polymers remains a long-standing synthetic challenge, with theory indicating broad implications for properties and function. Here we report on a topological synthon approach-extension and macrocyclization of an overhand knot-that enables the high yielding synthesis of closed-loop trefoiled polymers with narrow polydispersity and tunable topological parameters. From the same set of building blocks we prepared linear, cyclic and trefoiled topoisomers of matched chemical composition, allowing topology-property relationships to be examined directly. Low-temperature ultrahigh-vacuum scanning tunnelling microscopy resolved three conformers of trefoiled polystyrene, with high-, medium- and low-symmetry forms whose populations depend on chain length, local flexibility and solvation. Coarse‑grained Langevin dynamics reproduce these distributions and indicate that bending energy and conformational entropy govern conformer stability. Metal binding localizes the knotted region, reminiscent of protein/DNA knot translocation. The synthon also affords trefoiled poly(ethylene glycol) and trefoiled polystyrene-poly(ethylene glycol) diblock copolymers, demonstrating the generality of the approach across polymer backbones.
Related
- Investigating Topological Parameters in Polymers: Precision Synthesis of Trefoil Polymers from a Knotted Synthon.
- A protein–foldamer supramolecular synthon for self-assembled hybrid architectures
- Chemoselective Generation of the 1,3-Benzdiyne Synthon.
- Near-Complete Synthon Library via Retrosynthetic Analysis for Automated Organic Synthesis
- Ligand-directed symmetry reduction and stereoselective assembly of C₃-symmetric topologically chiral trefoil knots.
BibTeX
@article{du2026trefoil,
title = {{Trefoil polymers from a knotted synthon}},
author = {Chenchen Du and Zhi Chen and Changqing Xu and Zhanhu Sun and Zhi-Hui Zhang and X K Liu and Binhua Chen and Chenxin Zhang and Zhikai Li and Yin Rao and Deao Xu and Ningjin Zhang and Qiaowei Li and Heng Wang and Hai Qian and Liang Dai and Xiaopeng Li and David A. Leigh and Liang Zhang},
journal = {Nature Chemistry},
year = {2026},
month = jun,
doi = {10.1038/s41557-026-02197-4},
url = {https://doi.org/10.1038/s41557-026-02197-4},
note = {CC BY},
}
RIS
TY - JOUR
TI - Trefoil polymers from a knotted synthon
AU - Chenchen Du
AU - Zhi Chen
AU - Changqing Xu
AU - Zhanhu Sun
AU - Zhi-Hui Zhang
AU - X K Liu
AU - Binhua Chen
AU - Chenxin Zhang
AU - Zhikai Li
AU - Yin Rao
AU - Deao Xu
AU - Ningjin Zhang
AU - Qiaowei Li
AU - Heng Wang
AU - Hai Qian
AU - Liang Dai
AU - Xiaopeng Li
AU - David A. Leigh
AU - Liang Zhang
PY - 2026
DA - 2026/06/29
JO - Nature Chemistry
DO - 10.1038/s41557-026-02197-4
UR - https://doi.org/10.1038/s41557-026-02197-4
AB - Precise control over the presence and position of knots in polymers remains a long-standing synthetic challenge, with theory indicating broad implications for properties and function. Here we report on a topological synthon approach-extension and macrocyclization of an overhand knot-that enables the high yielding synthesis of closed-loop trefoiled polymers with narrow polydispersity and tunable topological parameters. From the same set of building blocks we prepared linear, cyclic and trefoiled topoisomers of matched chemical composition, allowing topology-property relationships to be examined directly. Low-temperature ultrahigh-vacuum scanning tunnelling microscopy resolved three conformers of trefoiled polystyrene, with high-, medium- and low-symmetry forms whose populations depend on chain length, local flexibility and solvation. Coarse‑grained Langevin dynamics reproduce these distributions and indicate that bending energy and conformational entropy govern conformer stability. Metal binding localizes the knotted region, reminiscent of protein/DNA knot translocation. The synthon also affords trefoiled poly(ethylene glycol) and trefoiled polystyrene-poly(ethylene glycol) diblock copolymers, demonstrating the generality of the approach across polymer backbones.
SN - 1755-4330
SN - 1755-4349
ER -