Abstract
The structural dynamics of biopolymers, such as proteins and DNA, feature the unique combination of simultaneous conformational adaptivity and configurational reversibility. However, it remains challenging to design a synthetic system featuring dynamic covalent bonds with secondary structural folding and full recycling capabilities. Here we present a synthetic covalent polymer, constructed from biologically relevant units (amino acids and disulfides), that can reversibly adapt between disordered and helical conformations and can recycle itself to the original small molecules. This dual dynamic feature arises from the subtle synergy of noncovalent bonds (H bonds) and dynamic covalent bonds within a coupled chemical equilibrium, of which thermodynamics is found to follow a nonlinear van’t Hoff equation with nonzero heat capacity change. The covalent polymers show conformational dynamics between structured helices and disordered coils and the ability to convert back to the original monomers. This system demonstrates how dual dynamic function can control helical and recyclable polymer formation.
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Acknowledgements
This work was supported by the National Natural Science Foundation of China (grant nos. 22588101, 22025503, 22220102004 and 22475070), Shanghai Municipal Science and Technology Major Project (grant no. 2018SHZDZX03), the Fundamental Research Funds for the Central Universities, the Program of Introducing Talents of Discipline to Universities (grant no. B16017), Science and Technology Commission of Shanghai Municipality (grant no. 24DX1400200) and the Starry Night Science Fund of Zhejiang University Shanghai Institute for Advanced Study (grant no. SN-ZJU-SIAS-006). B.L.F. acknowledges the financial support from the European Research Council (advanced grant no. 694345 to B.L.F.) and the Dutch Ministry of Education, Culture and Science (Gravitation program no. 024.001.035). Q.Z. acknowledges the funding from the European Union’s Horizon 2020 research and innovation programme under the Marie Skłodowska-Curie actions grant (no. 101025041). V.P.N. acknowledges funding from UEFISCDI (grant no. PN-III-P4-ID-PCE-2020-2783-P, contract no. PCE 2/2022). We thank Y. Ke and the staff members of the Small Angle Neutron Scattering (https://cstr.cn/31113.02.CSNS.SANS) at the China Spallation Neutron Source (https://cstr.cn/31113.02.CSNS) for providing technical support and assistance in data collection and analysis. We thank N. Li and the staff members of BL19U2 beamline (https://cstr.cn/31129.02.NFPS.BL19U2) at the National Facility for Protein Science in Shanghai (https://cstr.cn/31129.02.NFPS), for providing technical support and assistance in data collection and analysis. We thank B. Sun, Y. Qiu, J. Wang and Y. Wang for their assistance on dynamic and static light scattering experiments. We thank J. Fan, Y. Shan, C. Shi, B. Wang, Y. Feng, J. Baas, C. Ye, A. J. J. Woortman, K. Loos, W. Roos, M. C. A. Stuart, Z. Zheng, J. Aizenberg and R. J. M. Nolte for their assistance with experiments or discussions of this research. This manuscript is dedicated in memory of Roeland J. M. Nolte (1944−2024).
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Q.Z., D.-H.Q. and B.L.F. conceived the project. D.-H.Q. and B.L.F. supervised the research. Q.Z. carried out the synthesis, characterizations and data acquisition. Q.Z., V.P.N. and W.J.B. performed vibrational circular dichroism experiments and related simulations. V.P.N. carried out DFT calculations. Q.Z., B.L.F., D.-H.Q., V.P.N., W.J.B. and H.T. analysed the data and prepared the manuscript.
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Materials and methods, Supplementary Figs. 1–44 and references.
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DFT-optimized conformers of monomers and polymers.
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Zhang, Q., Nicu, V.P., Buma, W.J. et al. Dual dynamic helical poly(disulfide)s with conformational adaptivity and configurational recyclability. Nat. Chem. 17, 1462–1468 (2025). https://doi.org/10.1038/s41557-025-01947-0
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DOI: https://doi.org/10.1038/s41557-025-01947-0
