Squaramide-directed Cooperative One-dimensional Assembly in Telechelic Polydimethylsiloxane for Hierarchical Network Formation

Yu-Hong Zhang; Jian-Fei Ma; Hao-Bo Wei; Jie Wang; Feng Wang

doi:10.1007/s10118-026-3700-z

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Squaramide-directed Cooperative One-dimensional Assembly in Telechelic Polydimethylsiloxane for Hierarchical Network Formation

RESEARCH ARTICLE | Updated：2026-07-06

- Squaramide-directed Cooperative One-dimensional Assembly in Telechelic Polydimethylsiloxane for Hierarchical Network Formation
- Squaramide-directed Cooperative One-dimensional Assembly in Telechelic Polydimethylsiloxane for Hierarchical Network Formation
- Chinese Journal of Polymer Science 2026年44卷页码：1-10
- Affiliations：
  
  a.Department of Polymer Science and Engineering, University of Science and Technology of China, Hefei 230026, China
  b.School of Chemistry and Pharmaceutical Engineering, Jilin University of Chemical Technology, Jilin 132022, China
- Author bio：
  
  drfwang@ustc.edu.cn
- Funds：
  
  This study was financially supported by the National Natural Science Foundation of China (Nos. 22371272 and 92356302) and the International Partnership Program of the Chinese Academy of Sciences (No. 123GJHZ2022064MI). We are grateful for the technical support provided by the High Performance Computing Center of the University of Science and Technology of China for the DFT and TD-DFT computations.;The authors declare no interest conflict.Electronic supplementary information (ESI) is available free of charge in the online version of this article at http://doi.org/10.1007/s10118-026-3700-z.The data supporting the findings of this study are available from the corresponding author upon reasonable request.
- DOI：10.1007/s10118-026-3700-z
  中图分类号：
- 收稿：2026-04-10，
  
  录用：2026-05-04，
  
  网络首发：2026-07-06，
  
  纸质出版：2026-06
- Accepted：
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Zhang, Y. H.; Ma, J. F.; Wei, H. B.; Wang, J.; Wang, F. Squaramide-directed cooperative one-dimensional assembly in telechelic polydimethylsiloxane for hierarchical network formation. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3700-z

Yu-Hong Zhang, Jian-Fei Ma, Hao-Bo Wei, et al. Squaramide-directed Cooperative One-dimensional Assembly in Telechelic Polydimethylsiloxane for Hierarchical Network Formation[J/OL]. Chinese Journal of Polymer Science, 2026, 441-10.
Zhang, Y. H.; Ma, J. F.; Wei, H. B.; Wang, J.; Wang, F. Squaramide-directed cooperative one-dimensional assembly in telechelic polydimethylsiloxane for hierarchical network formation. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3700-z DOI：

Yu-Hong Zhang, Jian-Fei Ma, Hao-Bo Wei, et al. Squaramide-directed Cooperative One-dimensional Assembly in Telechelic Polydimethylsiloxane for Hierarchical Network Formation[J/OL]. Chinese Journal of Polymer Science, 2026, 441-10. DOI： 10.1007/s10118-026-3700-z.

摘要

Abstract

Polymer crosslinked networks often face a fundamental trade-off between the mechanical robustness of covalent systems and the dynamic reversibility of supramolecular assemblies. Inspired by the hierarchical organization of biological extracellular matrix

where fibrous structures are reinforced by covalent crosslinking

we report a squaramide-directed cooperative assembly strategy that integrates one-dimensional (1D) supramolecular nanofiber formation with covalent macromolecular architecture to construct hierarchical polymer networks. Telechelic macromolecules were designed by tethering orthogonally arranged squaramide–amide hydrogen-bonding motifs to polydimethylsiloxane (PDMS) spacers. In the model system

these motifs undergo cooperative nucleation-elongation assembly into long-range nanofibers

while comparison with a urea analogue reveals enhanced intermolecular binding and assembly stability arising from the squaramide motif. Covalent integration of the assembling units transforms discrete nanofibers into microphase-separated networks with increased thermal stability and storage modulus. This work establishes a molecular design principle linking cooperative self-assembly with hierarchical polymer network formation and macroscopic mechanical performance.

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references

Chen, T.; Xu, J.; Wang, C.; Zhang, X.; Pei, X.; Wang, T.; Wang, Q. Shape-memory polyurethanes for polar wearables with ultrasensitive multi-monitoring. Nat. Commun. 2025 , 16 , 11329..

[Li, Y.; Sun, J. Reversibly cross-linked polymers: a new method for high-performance and sustainable polymer materials. Acc. Chem. Res. 2026 , 59 , 298−310..

Adane, A. M.; Park, S.Y. Photonic interpenetrating polymer network fibers comprising intertwined solid-state cholesteric liquid crystal and polyelectrolyte networks for sensor applications. ACS Appl. Mater. Interfaces 2024 , 16 , 16830−16843..

Zhang, Q.; Xu, Z. Y.; Liu, W. G. Hydrogen-bonding crosslinked supramolecular polymer materials: from design evolution of side-chain hydrogen-bonding to applications. Chinese J. Polym. Sci. 2024 , 42 , 1619−1641..

Ollier, R. C.; Webber, M. J. Mechanoresponsive hydrogels emerging from dynamic and non-covalent interactions. Adv. Mater. 2025 , 37 , 2507397..

Zhao, J.; Zhang, Z.; Wang, C.; Yan, X. Synergistic dual dynamic bonds in covalent adaptable networks. CCS Chem. 2024 , 6 , 41−56..

Gao, W.; Chen, Z.; Shao, M.; Huang, H.; Hong, J.; Zhang, Q.; Fang, Y.; Shi, W.; Dong, J.; Guo, Y.; Chen, J.; Liu, Y. Leveraging conformational locking to synthesize acylhydrazone-linked covalent organic frameworks with aggregation-induced-emission nodes. CCS Chem. 2026 , 8 , 989−1000..

Shi, C.Y.; Zhang, Q.; Wang, B.S.; He, D.D.; Tian, H.; Qu, D.H. Highly ordered supramolecular assembled networks tailored by bioinspired h-bonding confinement for recyclable ion-transport materials. CCS Chem. 2023 , 5 , 1422−1432..

Cao, Z.; Yang, Z.; Wang, W.; Li, P.; Sun, Y.; An, W.; Liu, G.; Zheng, X.; Niu, C.; Rao, S.; Zhang, W. Dynamic supramolecular network crosslinked by hydrogen bonds and pillar[5 ] arene-based host–guest interaction. Chin. Chemical Lett. 2026 , 37 , 112104..

Wang, Y.H.; Deng, J.X.; Zhao, J.; Ding, Y.; Yang, L.; Zhang, Z.M.; Yan, X.Z. Bolstering the mechanical robustness of supramolecular polymer network by mechanical bond. Chinese J. Polym. Sci. 2024 , 42 , 1536−1544..

Xue, Y.; Huang, Y.; Chen, S.; Ma, J.; Xiao, S.; Wang, F. Energy landscape modulation enables helicity overriding in supramolecular copolymers. Nat. Synth. 2026 , 5 , 84−94..

Zhang, Y.; Xue, Y.; Gao, L.; Liao, R.; Wang, F.; Wang, F. Merging non-covalent and covalent crosslinking: En route to single chain nanoparticles. Chin. Chem. Lett. 2024 , 35 , 109217..

Anton, C.; Lautenschläger, F.; Hawkins, R. J. Modeling cytoskeletal and cell dynamics. Curr. Opin. Cell Biol. 2025 , 97 , 102584..

Wang, S.; Zhang, L.; Wang, Z.; Song, Z.; Liu, H.; Tian, Z.; Xu, X. Humidity-adaptive, mechanically robust, and recyclable bioplastic films amplified by nanoconfined assembly. Aggregate 2024 , 5 , e643..

Zhou, X.; Li, Z. Advances and biomedical applications of polypeptide hydrogels derived from α-amino acid N-carboxyanhydride (NCA) polymerizations. Adv. Healthc. Mater. 2018 , 7 , 1800020..

ter Huurne, G. M.; Palmans, A. R.; Meijer, E. Supramolecular single-chain polymeric nanoparticles. CCS Chem. 2019 , 1 , 64−82..

Zhu, X.; Ma, J.; Zhang, D.; Fang, Z.; Zhang, J.; Wang, M.; Zhang, M.; Tang, B.-Z.; Li, Y. Mechanically active adhesive and NIR-II-activated zwitterionic hydrogel for infected maxillofacial wound repair and abscess elimination. Aggregate 2026 , 7 , e70309..

Zhang, L.; Zhou, X.; Xiong, X.; Cui, J. Polymer fibers based on dynamic covalent chemistry. Chinese J. Polym. Sci. 2025 , 43 , 245−260..

Goor, O. J.; Hendrikse, S. I.; Dankers, P. Y.; Meijer, E. From supramolecular polymers to multi-component biomaterials. Chem. Soc. Rev. 2017 , 46 , 6621−6637..

Li, Z.; Lin, Z. Recent advances in polysaccharide-based hydrogels for synthesis and applications. Aggregate 2021 , 2 , e21..

Storm, C.; Pastore, J. J.; MacKintosh, F. C.; Lubensky, T. C.; Janmey, P. A. Nonlinear elasticity in biological gels. Nature 2005 , 435 , 191−194..

[Hafeez, S.; Decarli, M. C.; Aldana, A.; Ebrahimi, M.; Ruiter, F. A. A.; Duimel, H.; van Blitterswijk, C.; Pitet, L. M.; Moroni, L.; Baker, M. B. In situ covalent reinforcement of a benzene-1, 3, 5-tricarboxamide supramolecular polymer enables biomimetic, tough, and fibrous hydrogels and bioinks. Adv. Mater. Deerfield Beach Fla 2023 , 35 , e2301242..

Sathyan, A.; Deng, L.; Loman, T.; Palmans, A. R. Bioorthogonal catalysis in complex media: consequences of using polymeric scaffold materials on catalyst stability and activity. Catal. Today 2023 , 418 , 114116..

Liu, X.; Sun, J. Polymeric materials reinforced by noncovalent aggregates of polymer chains. Aggregate 2021 , 2 , e109..

Lu, F.; Chen, Y.; Fu, B.; Chen, S.; Wang, L. Multistimuli responsive supramolecular polymer networks via host-guest complexation of pillararene-containing polymers and sulfonium salts. Chin. Chemical Lett 2022 , 33 , 5111−5115..

Dai, W. T.; Xie, Z. H.; Ke, Y. B.; You, Y.; Rong, M. Z.; Zhang, M. Q. Topological confinement in reversibly interlocked polymer networks. Chinese J. Polym. Sci. 2024 , 42 , 133−140..

Jin, B.; Li, Q.; Hu, L.; Liu, Q.; Chen, Y.; Luo, Y.; Chi, S.; Li, X. In situ nucleation-growth strategy for controllable heterogeneous supramolecular polymerization of liquid crystalline block copolymers and their hierarchical assembly. Angew. Chim. 2023 , 135 , e202219067..

Ma, J.; Jiang, S.; Tan, X.; Tian, Y.; Dong, S.; Wang, F. Tough supramolecular glasses enabled by frustrated non-covalent complexation. Angew. Chim. 2025 , 137 , e202519907..

Duong, T. K. N.; Truong, T. T.; Phan, T. N. L.; Nguyen, T. X.; Doan, V. H. M.; Vo, T. T.; Choi, J.; Pal, U.; Dhar, P.; Lee, B.; Oh, J.; Mondal, S. Hydrogel-based smart materials for wound healing and sensing. Aggregate 2025 , 6 , e70047..

Li, Z.; Zhu, Y. L.; Niu, W.; Yang, X.; Jiang, Z.; Lu, Z. Y.; Liu, X.; Sun, J. Healable and recyclable elastomers with record-high mechanical robustness, unprecedented crack tolerance, and superhigh elastic restorability. Adv. Mater. 2021 , 33 , 210 1498..

Guang, L. Y.; Zhou, Z. F.; Zhang, Y. F.; Gao, L.W.; Wang, F.; Liao, R. Cooperative supramolecular polymerization of propeller-shaped triphenylamine cyanostilbenes for explosive detection. Chinese J. Polym. Sci. 2023 , 41 , 585−592..

Xiao, T.; Zhou, L.; Sun, X.Q.; Huang, F.; Lin, C.; Wang, L. Supramolecular polymers fabricated by orthogonal self-assembly based on multiple hydrogen bonding and macrocyclic host–guest interactions. Chin. Chem. Lett. 2020 , 31 , 1−9..

Zhao, Y.K.; Gao, Z.Z.; Wang, H.; Zhang, D.W.; Li, Z.T. Self-assembly of supramolecular polymers in water from tetracationic and tetraanionic monomers in water through cooperative electrostatic attraction and aromatic stacking. Chin. Chemical Lett. 2019 , 30 , 127−130..

Hafeez, S.; Aldana, A. A.; Duimel, H.; Ruiter, F. A.; Decarli, M. C.; Lapointe, V.; van Blitterswijk, C.; Moroni, L.; Baker, M. B. Molecular tuning of a benzene-1,3,5-tricarboxamide supramolecular fibrous hydrogel enables control over viscoelasticity and creates tunable ECM-mimetic hydrogels and bioinks. Adv. Mater. 2023 , 35 , 2207053..

Li, Y.; Wang, Y.; Wang, S.; Ye, Z.; Bian, C.; Xing, X.; Hong, T.; Jing, X. Highly tunable and robust dynamic polymer networks via conjugated–hindered urea bonds. Macromolecules 2022 , 55 , 9091−9102..

Deng, Y.; Zhang, Q.; Qu, D.H. Emerging hydrogen-bond design for high-performance dynamic polymeric materials. ACS Mater. Lett. 2023 , 5 , 480−490..

Wei, P.; Yan, X.; Huang, F. Supramolecular polymers constructed by orthogonal self-assembly based on host–guest and metal–ligand interactions. Chem. Soc. Rev. 2015 , 44 , 815−832..

Wu, J.; Cai, L. H.; Weitz, D. A. Tough self-healing elastomers by molecular enforced integration of covalent and reversible networks. Adv. Mater. 2017 , 29 , 1702616..

Xue, Y.; Jiang, S.; Zhong, H.; Chen, Z.; Wang, F. Photo-induced polymer cyclization via supramolecular confinement of cyanostilbenes. Angew. Chim. Int. Ed. 2022 , 61 , e202110766..

[Lv, T.; Wu, S.; Jin, Y.; Ma, J.; Jiang, S.; Xue, Y.; Wang, F. Enhancing the circularly polarized luminescence of self-assembled cyanostilbenes through extended π-conjugation. Chin. J. Chem. 2024 , 42 , 135−141..

Nishikawa, J.; Imase, T.; Koike, M.; Fukuda, K.; Tokita, M.; Watanabe, J.; Kawauchi, S. Internal rotations of aromatic polyamides: a density functional theory study. J. Mol. Struct. 2005 , 741 , 221−228..

Saez Talens, V.; Englebienne, P.; Trinh, T. T.; Noteborn, W. E.; Voets, I. K.; Kieltyka, R. E. Aromatic gain ina supramolecular polymer. Angew. Chim. Int. Ed. 2015 , 54 , 10502−10506..

Bujosa, S.; Rubert, L.; Rotger, C.; Soberats, B. Modulating self-assembly and polymorph transitions in bisdendronized squaramides. Commun. Chem. 2024 , 7 , 296..

Chen, J.; Yu, N.; Zhang, H.; Wei, Y.; He, Y.; Sha, Y.; Li, G.; Zhang, M.; Luo, Y.; Luo, Z. Strong and colorless transparent polyurethanes enabled by squaramide units: from flexibility to stiffness. ACS Appl. Polym. Mater. 2025 , 7 , 8300−8310..

Konar, D.; Stewart, K. A.; Moerschel, J.; Rynk, J. F.; Sumerlin, B. S. Polysquaramides. ACS Macro Lett. 2024 , 13 , 972−978..

Cao, H.; Li, B.; Jiang, X.; Zhu, X.; Kong, X. Z. Fluorescent linear polyurea based on toluene diisocyanate: Easy preparation, broad emission and potential applications. ACS Appl. Polym. Mater. 2020 , 399 , 125867..

Bujosa, S.; Castellanos, E.; Frontera, A.; Rotger, C.; Costa, A.; Soberats, B. Self-assembly of amphiphilic aryl-squaramides in water driven by dipolar π–π interactions. Org. Biomol. Chem. 2020 , 18 , 888−894..

Storer, R. I.; Aciro, C.; Jones, L. H. Squaramides: physical properties, synthesis and applications. Chem. Soc. Rev. 2011 , 40 , 2330−2346..

Tian, J.; Zhou, Z.; Miao, X.; Wang, S.; Ming, Y.; Nie,Y.; Ma, Y.; Li, Z. Supertough, resilient, and healable thermoplastic poly (urethane urea) elastomers by dense packing of hydrogen-bonding arrays. Adv. Funct. Mater. 2026 , 36 , e04882..

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