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Structural analysis of polymers via solid-state dynamic nuclear polarization (DNP)-NMR

Polymer Journal volume 57, pages 25–32 (2025)Cite this article

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Abstract

Solid-state NMR is one of the most powerful analytical methods for the structural characterization and dynamics of polymers. Owing to its intrinsically low signal sensitivity, however, analysis of trace chemical species supported on polymers remains challenging. Solid-state NMR with dynamic nuclear polarization (DNP-NMR) has recently attracted attention as a highly sensitive NMR measurement method for analyzing polymers. We recently investigated DNP-NMR for insoluble polymers, particularly cross-linked polymers, engineering plastics, and polymer-supported catalysts, and achieved high NMR signal sensitivity at a routinely accessible level. In this focus review, we present case studies on DNP-NMR measurements for a wide range of polymers.

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References

  1. Kuptsov AH, Zhizhin GN. Handbook of fourier transform raman and infrared spectra of polymers, Elsevier, 1998.

  2. Wesdemiotis C, Williams‐Pavlantos KN, Keating AR, McGee AS, Bochenek C. Mass spectrometry of polymers: a tutorial review. Mass Spectrom Rev. 2023;43:427–76.

    Article  PubMed  Google Scholar 

  3. Chu B, Hsiao BS. Small-angle X-ray scattering of polymers. Chem Rev 2001;101:1727–62.

    Article  PubMed  CAS  Google Scholar 

  4. Wei Y, Hore MJA. Characterizing polymer structure with small-angle neutron scattering: a tutorial. J Appl Phys 2021;129:171101.

    Article  CAS  Google Scholar 

  5. Hatada K, Kitayama T, NMR spectroscopy of polymers, Springer, 2004.

  6. Hansen MR, Graf R, Spiess HW. Interplay of structure and dynamics in functional macromolecular and supramolecular systems as revealed by magnetic resonance spectroscopy. Chem Rev 2015;116:1272–308.

  7. Michaelis VK, Griffin RG, Corzilius B, Vega S, ed. Handbook of high-field dynamic nuclear polarization, John Wiley & Sons, 2020.

  8. Overhauser AW. Polarization of nuclei in metals. Phys Rev. 1953;92:411–5.

    Article  CAS  Google Scholar 

  9. Afeworki M, McKay RA, Schaefer J. Selective observation of the interface of heterogeneous polycarbonate/polystyrene blends by dynamic nuclear polarization carbon-13 NMR spectroscopy. Macromolecules. 1992;25:4084–91.

    Article  CAS  Google Scholar 

  10. Afeworki M, McKay RA, Schaefer J. Dynamic nuclear polarization enhanced nuclear magnetic resonance of polymer-blend interfaces. Mater Sci Eng: A. 1993;162:221–8.

    Article  Google Scholar 

  11. Becerra LR, Gerfen GJ, Temkin RJ, Singel DJ, Griffin RG. Dynamic nuclear-polarization with a cyclotron-resonance maser at 5-T. Phys Rev Lett. 1993;71:3561–4.

    Article  PubMed  CAS  Google Scholar 

  12. Horii F, Idehara T, Fujii Y, Ogawa I, Horii A, Entzminger G, et al. Development of DNP-enhanced high-resolution solid-state NMR system for the char- acterisation of the surface structure of polymer materials. J Infrared Millim Terahertz Waves. 2012;33:756–65.

    Article  CAS  Google Scholar 

  13. Hu KN, Yu HH, Swager TM, Griffin RG. Dynamic nuclear polarization with biradicals. J Am Chem Soc. 2004;126:10844–5.

    Article  PubMed  CAS  Google Scholar 

  14. Venkatesh A, Casano G, Wei R, Rao Y, Lingua H, Karoui H, et al. Rational design of dinitroxide polarizing agents for dynamic nuclear polarization to enhance overall NMR sensitivity. Angew Chem Int Ed 2024;63:e202317337.

    Article  CAS  Google Scholar 

  15. Venkatesh A, Casano G, Rao Y, De Biasi F, Perras FA, Kubicki DJ, et al. Deuterated TEKPol biradicals and the spin‐diffusion barrier in MAS DNP. Angew Chem Int Ed 2023;62:e202304844.

    Article  Google Scholar 

  16. Kobayashi T, Perras FA, Slowing II, Sadow AD, Pruski M. Dynamic nuclear polarization solid-state NMR in heterogeneous catalysis research. ACS Catal. 2015;5:7055–62.

    Article  CAS  Google Scholar 

  17. Mollica G, Ziarelli F, Thureau P, Viel S. Structural investigations of polymer materials by dynamic nuclear polarisation solid-state NMR. In NMR methods for characterization of synthetic and natural polymers 2019; 533-54.

  18. Tanaka S. Ann Rep. NMR Spectrosc. 2022;105:1.

    Article  CAS  Google Scholar 

  19. Le D, Casano G, Phan TNT, Ziarelli F, Ouari O, Aussenac F, et al. Optimizing sample preparation methods for dynamic nuclear polarization solid-state NMR of synthetic polymers. Macromolecules. 2014;47:3909–16.

    Article  CAS  Google Scholar 

  20. Tanaka S, Liao W-C, Ogawa A, Sato K, Copéret C. DNP NMR spectroscopy of cross-linked organic polymers: rational guidelines towards optimal sample preparation. Phys Chem Chem Phys 2020;22:3184–90.

    Article  PubMed  CAS  Google Scholar 

  21. Naudin C, Bonhomme F, Bruneel JL, Ducasse L, Grondin J, Lassegues JC, et al. Rotational isomerism of the tetraethylammonium cation in solution and in the solid state. J Raman Spectrosc. 2000;31:979–85.

  22. Takekiyo T, Yoshimura Y. Drastic change in the conformational equilibria of tetraethylammonium bromide in the glassy aqueous solution. Chem Phys Lett. 2006;420:8–11.

  23. Melton GH, Peters EN, Arisman RK, in Applied Plastics Engineering Handbook, 2011, 7-21.

  24. Oyama HT, Matsushita M, Furuta M. High performance reactive blends composed of poly(p-phenylene sulfide) and ethylene copolymers. Polym J. 2011;43:991–9.

    Article  CAS  Google Scholar 

  25. Nara S, Oyama HT. Effects of partial miscibility on the structure and properties of novel high performance blends composed of poly(p-phenylene sulfide) and poly(phenylsulfone). Polym J. 2014;46:568–75.

    Article  CAS  Google Scholar 

  26. Tanaka S, Takada S, Suzuki T, Nakajima Y, Sato K. End-Groups of Poly(p-phenylene sulfide) Characterized by DNP NMR Spectroscopy. Macromolecules 2022;55:2806–12.

  27. Hodge P. Organic synthesis using polymer-supported reagents, catalysts and scavengers in simple laboratory flow systems. Curr Opin Chem Biol. 2003;7:362–73.

    Article  PubMed  CAS  Google Scholar 

  28. Tanaka S, Nakashima T, Maeda T, Ratanasak M, Hasegawa J, Kon Y, et al. Quaternary alkyl ammonium salt-catalyzed transformation of glycidol to glycidyl esters by transesterifcation of methyl esters. ACS Catal. 2018;8:1097–103.

    Article  CAS  Google Scholar 

  29. Tanaka S, Nakajima Y, Ogawa A, Kuragano T, Kon Y, Tamura M, et al. DNP NMR spectroscopy enabled direct characterization of polystyrene-supported catalyst species for synthesis of glycidyl esters by transesterification. Chem Sci. 2022;13:4490–7.

    Article  PubMed  PubMed Central  CAS  Google Scholar 

  30. Sawahara K, Tanaka S, Kodaira T, Kanega R, Kwanam H. Iridium catalyst immobilized on crosslinked polyethyleneimine for continuous hydrogen production using formic acid. ChemSusChem. 2024;17:åe2023012.

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  1. Interdisciplinary Research Center for Catalytic Chemistry, National Institute of Advanced Industrial Science and Technology (AIST), 1-1-1 Higashi, Tsukuba, Ibaraki, 305-8565, Japan

    Shinji Tanaka

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  1. Shinji Tanaka
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Correspondence to Shinji Tanaka.

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Tanaka, S. Structural analysis of polymers via solid-state dynamic nuclear polarization (DNP)-NMR. Polym J 57, 25–32 (2025). https://doi.org/10.1038/s41428-024-00965-y

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