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Stretching Elasticity and Flexibility of Single Polyformaldehyde Chain

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Abstract

In this work, the single-chain elasticity of polyformaldehyde (POM) is studied, for the first time, by employing atomic force microscopy (AFM)-based single molecule force spectroscopy (SMFS). We find that the single-chain elasticity of POM in a nonpolar organic solvent (nonane) can be described well by a theoretical model (QM-FRC model), when the rotating unit length is 0.144 nm (C-O bond length). After comparison, POM is more flexible than polystyrene (a typical polymer with C-C backbone) at the single-chain level, which is reasonable since the C-O bond has a lower rotation barrier than C-C bond. This result indicates that the flexibility of a polymer chain can be tuned by the C-O bond proportion in backbone, which casts new light on the rational design of new synthetic polymers in the future.

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References

  1. Mie, G.; Hengstenberg, J.; Staudinger, H.; Johner, H.; Signer, R. Der polymere Formaldehyd, ein Modell der Cellulose. Naturwissenschaften 1927, 15, 379–380.

    Article  CAS  Google Scholar 

  2. Mark, J. E. Physical properties of polymers handbook. Springer: New York, 2007.

    Book  Google Scholar 

  3. Hama, H.; Tashiro, K. Structural changes in non-isothermal crystallization process of melt-cooled polyoxymethylene[II] evolution of lamellar stacking structure derived from SAXS and WAXS data analysis. Polymer 2003, 44, 2159–2168.

    Article  CAS  Google Scholar 

  4. Bai, S.; Liu, J.; Wang, Q. Effect of PEO on nonisothermal crystallization of POM in POM/PEO blends. Polym. Mater. Sci. Eng. 2007, 23, 136–139.

    CAS  Google Scholar 

  5. Carazzolo, G. Structure of the normal crystal form of polyoxymethylene. J. Polym. Sci., Part A: Polym. Chem. 1963, 1, 1573–1583.

    Google Scholar 

  6. Komatsu, T.; Enoki, S.; Aoshima, A. The effects of pressure on drawing polyoxymethylene: 1. Processing. Polymer 1991, 32, 1983–1987.

    Article  CAS  Google Scholar 

  7. Brew, B.; Ward, I. M. Study of the production of ultra-high modulus polyoxymethylene by tensile drawing at high temperatures. Polymer 1978, 19, 1338–1344.

    Article  CAS  Google Scholar 

  8. Grassie, N.; Roche, R. S. Some solution properties of polyoxymethylenes. J. Polym. Sci., Part C: Polym. Symp. 1968, 16, 4207–4213.

    Article  Google Scholar 

  9. Stockmayer, W. H.; Chan, L. L. Solution properties of polyoxymethylene. J. Polym. Sci., Part A-2 1966, 4, 437–446.

    Article  CAS  Google Scholar 

  10. Dudina, L. A.; Zharova, T. È.; Karmilova, L. V.; Yenikolopyan, N. S. The effect of stabilizing additives in the degradation of polyformaldehyde. Polym. Sci. U.S.S.R. 1964, 6, 2137–2144.

    Article  Google Scholar 

  11. Janshoff, A.; Neitzert, M.; Oberdörfer, Y.; Fuchs, H. Force spectroscopy of molecular systems-single molecule spectroscopy of polymers and biomolecules. Angew. Chem. Int. Ed. 2000, 39, 3212–3237.

    Article  CAS  Google Scholar 

  12. Li, H.; Cao, Y. Protein mechanics: from single molecules to functional biomaterials. Acc. Chem. Res. 2010, 43, 1331–1341.

    Article  CAS  Google Scholar 

  13. Li, I. T. S.; Walker, G. C. Signature of Hydrophobic hydration in a single polymer. Proc. Natl. Acad. Sci. U. S. A. 2011, 108, 16527–16532.

    Article  CAS  Google Scholar 

  14. Liu, K.; Song, Y.; Feng, W.; Liu, N.; Zhang, W.; Zhang, X. Extracting a single polyethylene oxide chain from a single crystal by a combination of atomic force microscopy imaging and single-molecule force spectroscopy: toward the investigation of molecular interactions in their condensed states. J. Am. Chem. Soc. 2011, 133, 3226–3229.

    Article  CAS  Google Scholar 

  15. Lv, S.; Dudek, D. M.; Cao, Y.; Balamurali, M. M.; Gosline, J.; Li, H. Designed biomaterials to mimic the mechanical properties of muscles. Nature 2010, 465, 69–73.

    Article  CAS  Google Scholar 

  16. Tian, F.; Li, G.; Zheng, B.; Liu, Y.; Shi, S.; Deng, Y.; Zheng, P. Verification of sortase for protein conjugation by single-molecule force spectroscopy and molecular dynamics simulations. Chem. Commun. 2020, 56, 3943–3946.

    Article  CAS  Google Scholar 

  17. Wu, J.; Li, P.; Dong, C.; Jiang, H.; Bin, X.; Gao, X.; Qin, M.; Wang, W.; Bin, C.; Cao, Y. Rationally designed synthetic protein hydrogels with predictable mechanical properties. Nat. Commun. 2018, 9, 620.

    Article  Google Scholar 

  18. Yang, P.; Song, Y.; Feng, W.; Zhang, W. Unfolding of a single polymer chain from the single crystal by air-phase single-molecule force spectroscopy: toward better force precision and more accurate description of molecular behaviors. Macromolecules 2018, 51, 7052–7060.

    Article  CAS  Google Scholar 

  19. Zhao, P.; Xu, C.; Sun, C.; Xia, J.; Sun, L.; Li, J.; Xu, H. Exploring the difference of bonding strength between silver (I) and chalcogenides in block copolymer systems. Polym. Chem. 2020, 11, 7087–7093.

    Article  CAS  Google Scholar 

  20. Cheng, B.; Cui, S. The important roles of water in protein folding: an approach by single molecule force spectroscopy. Chinese J. Polym. Sci. 2018, 36, 379–384.

    Article  CAS  Google Scholar 

  21. Fu, L.; Wang, H.; Li, H. Harvesting mechanical work from folding-based protein engines: from single-molecule mechanochemical cycles to macroscopic devices. CCS Chem. 2019, 1, 138–147.

    Article  CAS  Google Scholar 

  22. Xing, H.; Li, Z.; Wang, W.; Liu, P.; Liu, J.; Song, Y.; Wu, Z. L.; Zhang, W.; Huang, F. Mechanochemistry of an interlocked poly[2]catenane: from single molecule to bulk gel. CCS Chem. 2020, 2, 513–523.

    Article  CAS  Google Scholar 

  23. Xia, J.; Li, H.; Xu, H. Measuring the strength of S/Se based dynamic covalent bonds. Acta Polymerica Sinica (in Chinese) 2020, 51, 205–213.

    CAS  Google Scholar 

  24. Xiang, W.; Li, Z.; Xu, C. Q.; Li, J.; Zhang, W.; Xu, H. Quantifying the bonding strength of gold-chalcogen bonds in block copolymer systems. Chem. — Asian J. 2019, 14, 1481–1486.

    Article  CAS  Google Scholar 

  25. Cai, W.; Xu, D.; Qian, L.; Wei, J.; Xiao, C.; Qian, L.; Lu, Z.; Cui, S. Force-induced transition of π-π stacking in a single polystyrene chain. J. Am. Chem. Soc. 2019, 141, 9500–9503.

    Article  CAS  Google Scholar 

  26. Zhang, F.; Gong, Z.; Cai, W.; Qian, H.; Lu, Z.; Cui, S. Single-chain mechanics of cis-1,4-polyisoprene and polysulfide. Polymer 2022, 240, 124473.

  27. Cao, M.; Liu, X.; Cui, S. Single-molecule mechanics of polyacrylamide under different liquid environments. Chem. J. Chinese Univ. 2021, 42, 2982–2988.

    Google Scholar 

  28. Oesterhelt, F.; Rief, M.; Gaub, H. E. Single molecule force spectroscopy by AFM indicates helical structure of poly(ethyleneglycol) in water. New J. Phys. 1999, 1, 6.1–6.11.

    Article  Google Scholar 

  29. Zhang, W.; Zhang, X. Single molecule mechanochemistry of macromolecules. Prog. Polym. Sci. 2003, 28, 1271–1295.

    Article  CAS  Google Scholar 

  30. Bao, Y.; Luo, Z.; Cui, S. Environment-dependent single-chain mechanics of synthetic polymers and biomacromolecules by atomic force microscopy-based single-molecule force spectroscopy and the implications on advanced polymer materials. Chem. Soc. Rev. 2020, 49, 2799–2827.

    Article  CAS  Google Scholar 

  31. Li, I. T. S.; Walker, G. C. Interfacial free energy governs single polystyrene chain collapse in water and aqueous solutions. J. Am. Chem. Soc. 2010, 132, 6530–6540.

    Article  CAS  Google Scholar 

  32. Qian, L.; Cai, W.; Xu, D.; Bao, Y.; Lu, Z.; Cui, S. Single-molecule studies reveal that water is a special solvent for amylose and natural cellulose. Macromolecules 2019, 52, 5006–5013.

    Article  CAS  Google Scholar 

  33. Luo, Z.; Zhang, A.; Chen, Y.; Shen, Z.; Cui, S. How big is big enough? Effect of length and shape of side chains on the single-chain enthalpic elasticity of a macromolecule Macromolecules 2016, 49, 3559–3565.

    Article  CAS  Google Scholar 

  34. Hugel, T.; Rief, M.; Seitz, M.; Gaub, H. E.; Netz, R. R. Highly stretched single polymers: atomic-force-microscope experiments versus ab-initio theory. Phys. Rev. Lett. 2005, 94, 48301–48304.

    Article  Google Scholar 

  35. Cui, S.; Yu, Y.; Lin, Z. Modeling single chain elasticity of single-stranded DNA: a comparison of three models. Polymer 2009, 50, 930–935.

    Article  CAS  Google Scholar 

  36. Wang, K.; Pang, X.; Cui, S. Inherent stretching elasticity of a single polymer chain with a carbon-carbon backbone. Langmuir 2013, 29, 4315–4319.

    Article  CAS  Google Scholar 

  37. Tadokoro, H.; Chatani, Y.; Yoshihara, T.; Tahara, S.; Murahashi, S. Structural studies on polyethers, [-CH2)m-O-]n. II. Molecular structure of polyethylene oxide. Macromol. Chem. Phys. 1964, 73, 109–127.

    Article  CAS  Google Scholar 

  38. Price, C. C. Polyethers. American Chemical Society: Washington, 1975; Vol. 1.

    Book  Google Scholar 

  39. Xu, J.; Cao, N.; Xiao, Y.; Luo, Z.; Bao, Y.; Cui, S. Revealing the relationship between the biocompatibility and the bound water of poly(ethylene glycol) by single-molecule force spectroscopy. Acta Polymerica Sinica (in Chinese) 2020, 51, 754–761.

    CAS  Google Scholar 

  40. Liu, C.; Cui, S.; Wang, Z.; Zhang, X. Single chain mechanical property of poly(N-vinyl-2-pyrrolidone) and interaction with small molecules. J. Phys. Chem. B 2005, 109, 14807–14812.

    Article  CAS  Google Scholar 

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Acknowledgments

This work was financially supported by the National Natural Science Foundation of China (No. 21774102).

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Authors and Affiliations

  1. Key Laboratory of Advanced Technologies of Materials (Ministry of Education), Southwest Jiaotong University, Chengdu, 610031, China

    Jin-Xia Yang & Shu-Xun Cui

  2. State Key Laboratory of Supramolecular Structure and Materials, Institute of Theoretical Chemistry, Jilin University, Changchun, 130023, China

    Hu-Jun Qian & Zhong-Yuan Lu

  3. School of Life Science and Engineering, Southwest Jiaotong University, Chengdu, 610031, China

    Zheng Gong & Shu-Xun Cui

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  1. Jin-Xia Yang
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  2. Hu-Jun Qian
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  3. Zheng Gong
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  5. Shu-Xun Cui
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Correspondence to Shu-Xun Cui.

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Yang, JX., Qian, HJ., Gong, Z. et al. Stretching Elasticity and Flexibility of Single Polyformaldehyde Chain. Chin J Polym Sci 40, 333–337 (2022). https://doi.org/10.1007/s10118-022-2679-3

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  • DOI: https://doi.org/10.1007/s10118-022-2679-3

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