High-Field Solid-State NMR with Dynamic Nuclear Polarization

Living reference work entry


Microwave-induced dynamic nuclear polarization (DNP) can produce hyperpolarization of nuclear spins, leading to substantial signal enhancement in NMR. This chapter discusses the contemporary application of DNP for solid-state NMR spectroscopy at high magnetic fields. The main mechanisms and polarizing agents that enable this hyperpolarization are presented, along with more practical aspects such as the effect of decreasing sample temperature and analyzing the absolute sensitivity gain from these experiments. Examples of the exploitation of DNP for studies of biomolecules, biominerals, pharmaceuticals, self-assembled organic nanostructures, and mesoporous materials are given as is an outlook as to the future of this powerful technique.


Dynamic nuclear polarization Solid-state NMR Magnetic field Hyperpolarization Magic angle spinning Signal enhancement Polarizing agents Absolute sensitivity Microwave Biomolecules Materials 


  1. 1.
    Overhauser A. Polarization of nuclei in metals. Phys Rev. 1953;92:411–5.CrossRefGoogle Scholar
  2. 2.
    Carver TR, Slichter CP. Polarization of nuclear spins in metals. Phys Rev. 1953;92:212–3.CrossRefGoogle Scholar
  3. 3.
    Wind RA. Dynamic nuclear polarization and high-resolution NMR of solids. In: Harris RK, Wasylishen RL, editors. Encyclopedia of magnetic resonance. Chichester: Wiley; 2007. p. 1–10.Google Scholar
  4. 4.
    Hall DA, Maus DC, Gerfen GJ, Inati SJ, Becerra LR, Dahlquist FW, Griffin RG. Polarization-enhanced NMR spectroscopy of biomolecules in frozen solution. Science. 1997;276:930–2.CrossRefGoogle Scholar
  5. 5.
    Can TV, Ni QZ, Griffin RG. Mechanisms of dynamic nuclear polarization in insulating solids. J Magn Reson. 2015;253:23–35.CrossRefGoogle Scholar
  6. 6.
    Can TV, Caporini MA, Mentink-Vigier F, Corzilius B, Walish JJ, Rosay M, Maas WE, Baldus M, Vega S, Swager TM, Griffin RG. Overhauser effects in insulating solids. J Chem Phys. 2014;141:64202.CrossRefGoogle Scholar
  7. 7.
    Mentink-Vigier F, Akbey Ü, Hovav Y, Vega S, Oschkinat H, Feintuch A. Fast passage dynamic nuclear polarization on rotating solids. J Magn Reson. 2012;224:13–21.CrossRefGoogle Scholar
  8. 8.
    Thurber KR, Tycko R. Theory for cross effect dynamic nuclear polarization under magic-angle spinning in solid state nuclear magnetic resonance: the importance of level crossings. J Chem Phys. 2012;137:84508.CrossRefGoogle Scholar
  9. 9.
    Thurber KR, Tycko R. Perturbation of nuclear spin polarizations in solid state NMR of nitroxide-doped samples by magic-angle spinning without microwaves. J Chem Phys. 2014;140:184201.CrossRefGoogle Scholar
  10. 10.
    Mentink-Vigier F, Vega S, De Paëpe G. Large spin ensembles for MAS-DNP. Phys Chem Chem Phys. 2017;19:3506–22.Google Scholar
  11. 11.
    Mentink-Vigier F, Paul S, Lee D, Feintuch A, Hediger S, Vega S, De Paëpe G. Nuclear depolarization and absolute sensitivity in magic angle spinning cross effect dynamic nuclear polarization. Phys Chem Chem Phys. 2015;17:21824–36.CrossRefGoogle Scholar
  12. 12.
    Hu K-N, Yu H, Swager TM, Griffin RG. Dynamic nuclear polarization with biradicals. J Am Chem Soc. 2004;126:10844–5.CrossRefGoogle Scholar
  13. 13.
    Sauvée C, Casano G, Abel S, Rockenbauer A, Akhmetzyanov D, Karoui H, Siri D, Aussenac F, Maas W, Weber RT, Prisner T, Rosay M, Tordo P, Ouari O. Tailoring of polarizing agents in the bTurea series for cross-effect dynamic nuclear polarization in aqueous media. Chem A Eur J. 2016;22:5598–606.CrossRefGoogle Scholar
  14. 14.
    Vitzthum V, Borcard F, Jannin S, Morin M, Mieville P, Caporini MA, Sienkiewicz A, Gerber-Lemaire S, Bodenhausen G. Fractional spin-labeling of polymers for enhancing NMR sensitivity by solvent-free dynamic nuclear polarization. Chemphyschem. 2011;12:2929–32.CrossRefGoogle Scholar
  15. 15.
    Fernández-de-Alba C, Takahashi H, Richard A, Chenavier Y, Dubois L, Maurel V, Lee D, Hediger S, De Paëpe G. Matrix-free DNP-enhanced NMR spectroscopy of liposomes using a lipid-anchored biradical. Chem A Eur J. 2015;21:4512–7.CrossRefGoogle Scholar
  16. 16.
    Maly T, Cui D, Griffin RG, Miller A-F. 1H dynamic nuclear polarization based on an endogenous radical. J Phys Chem B. 2012;116:7055–65.CrossRefGoogle Scholar
  17. 17.
    Riikonen J, Rigolet S, Marichal C, Aussenac F, Lalevée J, Morlet-Savary F, Fioux P, Dietlin C, Bonne M, Lebeau B, Lehto V-P. Endogenous stable radicals for characterization of thermally carbonized porous silicon by solid-state dynamic nuclear polarization 13C NMR. J Phys Chem C. 2015;119:19272–8.CrossRefGoogle Scholar
  18. 18.
    Armstrong BD, Edwards DT, Wylde RJ, Walker SA, Han S. A 200 GHz dynamic nuclear polarization spectrometer. Phys Chem Chem Phys. 2010;12:5920–6.CrossRefGoogle Scholar
  19. 19.
    Salnikov ES, Aisenbrey C, Aussenac F, Ouari O, Sarrouj H, Reiter C, Tordo P, Engelke F, Bechinger B. Membrane topologies of the PGLa antimicrobial peptide and a transmembrane anchor sequence by Dynamic Nuclear Polarization/solid-state NMR spectroscopy. Sci Rep. 2016;6:20895.CrossRefGoogle Scholar
  20. 20.
    Hirsh DA, Rossini AJ, Emsley L, Schurko RW. 35 Cl dynamic nuclear polarization solid-state NMR of active pharmaceutical ingredients. Phys Chem Chem Phys. 2016;18:25893–904.CrossRefGoogle Scholar
  21. 21.
    Kobayashi T, Perras FA, Goh TW, Metz TL, Huang W, Pruski M. DNP-enhanced ultrawideline solid-state NMR spectroscopy: studies of platinum in metal–organic frameworks. J Phys Chem Lett. 2016;7:2322–7.CrossRefGoogle Scholar
  22. 22.
    Lee D, Bouleau E, Saint-Bonnet P, Hediger S, De Paëpe G. Ultra-low temperature MAS-DNP. J Magn Reson. 2016;264:116–24.CrossRefGoogle Scholar
  23. 23.
    Sauvée C, Rosay M, Casano G, Aussenac F, Weber RT, Ouari O, Tordo P. Highly efficient, water-soluble polarizing agents for dynamic nuclear polarization at high frequency. Angew Chem Int Ed. 2013;52:10858–61.CrossRefGoogle Scholar
  24. 24.
    Bouleau E, Saint-Bonnet P, Mentink-Vigier F, Takahashi H, Jacquot J-F, Bardet M, Aussenac F, Purea A, Engelke F, Hediger S, Lee D, De Paëpe G. Pushing NMR sensitivity limits using dynamic nuclear polarization with closed-loop cryogenic helium sample spinning. Chem Sci. 2015;6:6806–12.CrossRefGoogle Scholar
  25. 25.
    Takahashi H, Lee D, Dubois L, Bardet M, Hediger S, De Paëpe G. Rapid natural-abundance 2D 13C-13C correlation spectroscopy using dynamic nuclear polarization enhanced solid-state NMR and matrix-free sample preparation. Angew Chem Int Ed Engl. 2012;51:11766–9.CrossRefGoogle Scholar
  26. 26.
    Lee D, Hediger S, De Paëpe G. Is solid-state NMR enhanced by dynamic nuclear polarization? Solid State Nucl Magn Reson. 2015;66–67:6–20.CrossRefGoogle Scholar
  27. 27.
    Su Y, Andreas L, Griffin RG. Magic angle spinning NMR of proteins: high-frequency dynamic nuclear polarization and 1 H detection. Annu Rev Biochem. 2015;84:465–97.CrossRefGoogle Scholar
  28. 28.
    Frederick KK, Michaelis VK, Corzilius B, Ong T-C, Jacavone AC, Griffin RG, Lindquist S. Sensitivity-enhanced NMR reveals alterations in protein structure by cellular milieus. Cell. 2015;163:620–8.CrossRefGoogle Scholar
  29. 29.
    Mathies G, Caporini MA, Michaelis VK, Liu Y, Hu K-N, Mance D, Zweier JL, Rosay M, Baldus M, Griffin RG. Efficient dynamic nuclear polarization at 800 MHz/527 GHz with trityl-nitroxide biradicals. Angew Chem Int Ed. 2015;54:11770–4.CrossRefGoogle Scholar
  30. 30.
    Koers EJ, van der Cruijsen EAW, Rosay M, Weingarth M, Prokofyev A, Sauvée C, Ouari O, van der Zwan J, Pongs O, Tordo P, Maas WE, Baldus M. NMR-based structural biology enhanced by dynamic nuclear polarization at high magnetic field. J Biomol NMR. 2014;60:157–68.CrossRefGoogle Scholar
  31. 31.
    Kaplan M, Cukkemane A, van Zundert GCP, Narasimhan S, Daniëls M, Mance D, Waksman G, Bonvin AMJJ, Fronzes R, Folkers GE, Baldus M. Probing a cell-embedded megadalton protein complex by DNP-supported solid-state NMR. Nat Methods. 2015;12:649–52.CrossRefGoogle Scholar
  32. 32.
    Liao SY, Lee M, Wang T, Sergeyev IV, Hong M. Efficient DNP NMR of membrane proteins: sample preparation protocols, sensitivity, and radical location. J Biomol NMR. 2016;64:223–37.CrossRefGoogle Scholar
  33. 33.
    Maciejko J, Mehler M, Kaur J, Lieblein T, Morgner N, Ouari O, Tordo P, Becker-Baldus J, Glaubitz C. Visualizing specific cross-protomer interactions in the homo-oligomeric membrane protein proteorhodopsin by dynamic-nuclear-polarization-enhanced solid-state NMR. J Am Chem Soc. 2015;137:9032–43.CrossRefGoogle Scholar
  34. 34.
    Akbey Ü, Franks WT, Linden AH, Lange S, Griffin RG, van Rossum B-J, Oschkinat H. Dynamic nuclear polarization of deuterated proteins. Angew Chem Int Ed Engl. 2010;49:7803–6.CrossRefGoogle Scholar
  35. 35.
    Jakdetchai O, Denysenkov V, Becker-Baldus J, Dutagaci B, Prisner TF, Glaubitz C. Dynamic nuclear polarization-enhanced NMR on aligned lipid bilayers at ambient temperature. J Am Chem Soc. 2014;136:15533–6.CrossRefGoogle Scholar
  36. 36.
    Lee D, Leroy C, Crevant C, Bonhomme-Coury L, Babonneau F, Laurencin D, Bonhomme C, De Paëpe G. Interfacial Ca2+ environments in nanocrystalline apatites revealed by dynamic nuclear polarization enhanced 43Ca NMR spectroscopy. Nat Commun. 2017;8:14104.Google Scholar
  37. 37.
    Rossini AJ, Zagdoun A, Lelli M, Lesage A, Copéret C, Emsley L. Dynamic nuclear polarization surface enhanced NMR spectroscopy. Acc Chem Res. 2013;46:1942–51.CrossRefGoogle Scholar
  38. 38.
    Rossini AJ, Zagdoun A, Lelli M, Canivet J, Aguado S, Ouari O, Tordo P, Rosay M, Maas WE, Copéret C, Farrusseng D, Emsley L, Lesage A. Dynamic nuclear polarization enhanced solid-state NMR spectroscopy of functionalized metal-organic frameworks. Angew Chem Int Ed. 2012;51:123–7.CrossRefGoogle Scholar
  39. 39.
    Blanc F, Sperrin L, Jefferson DA, Pawsey S, Rosay M, Grey CP. Dynamic nuclear polarization enhanced natural abundance 17O spectroscopy. J Am Chem Soc. 2013;135:2975–8.CrossRefGoogle Scholar
  40. 40.
    Rossini AJ, Schlagnitweit J, Lesage A, Emsley L. High-resolution NMR of hydrogen in organic solids by DNP enhanced natural abundance deuterium spectroscopy. J Magn Reson. 2015;259:192–8.CrossRefGoogle Scholar
  41. 41.
    Rossini AJ, Widdifield CM, Zagdoun A, Lelli M, Schwarzwälder M, Coperet C, Lesage A, Emsley L. DNP enhanced NMR spectroscopy for pharmaceutical formulations. J Am Chem Soc. 2014;136:2324–34.CrossRefGoogle Scholar
  42. 42.
    Märker K, Pingret M, Mouesca J-M, Gasparutto D, Hediger S, De Paëpe G. A new tool for NMR crystallography: complete 13C/15N assignment of organic molecules at natural isotopic abundance using DNP-enhanced solid-state NMR. J Am Chem Soc. 2015;137:13796–9.CrossRefGoogle Scholar
  43. 43.
    Lee D, Monin G, Duong NT, Zamanillo Lopez I, Bardet M, Mareau V, Gonon L, De Paëpe G. Untangling the condensation network of organosiloxanes on nanoparticles using 2D 29 Si- 29 Si solid-state NMR enhanced by dynamic nuclear polarization. J Am Chem Soc. 2014;136:13781–8.CrossRefGoogle Scholar
  44. 44.
    Perras FA, Chaudhary U, Slowing II, Pruski M. Probing surface hydrogen bonding and dynamics by natural abundance, multidimensional, 17O DNP-NMR spectroscopy. J Phys Chem C. 2016;120:11535–44.CrossRefGoogle Scholar
  45. 45.
    Lafon O, Rosay M, Aussenac F, Lu X, Trébosc J, Cristini O, Kinowski C, Touati N, Vezin H, Amoureux J-P. Beyond the silica surface by direct silicon-29 dynamic nuclear polarization. Angew Chem Int Ed. 2011;50:8367–70.CrossRefGoogle Scholar
  46. 46.
    Lee D, Duong NT, Lafon O, De Paëpe G. Primostrato solid-state NMR enhanced by dynamic nuclear polarization: penta-coordinated Al are only located at the surface of hydrated γ-alumina. J Phys Chem C. 2014;118:25065–76.CrossRefGoogle Scholar
  47. 47.
    Vitzthum V, Miéville P, Carnevale D, Caporini M a, Gajan D, Copéret C, Lelli M, Zagdoun A, Rossini AJ, Lesage A, Emsley L, Bodenhausen G. Dynamic nuclear polarization of quadrupolar nuclei using cross polarization from protons: surface-enhanced aluminium-27 NMR. Chem Commun (Camb). 2012;48:1988–90.CrossRefGoogle Scholar
  48. 48.
    Lee D, Takahashi H, Thankamony ASL, Dacquin J-P, Bardet M, Lafon O, Paëpe GD. Enhanced solid-state NMR correlation spectroscopy of quadrupolar nuclei using dynamic nuclear polarization. J Am Chem Soc. 2012;134:18491–4.CrossRefGoogle Scholar
  49. 49.
    Rossini AJ, Emsley L, O’Dell LA. Dynamic nuclear polarisation enhanced (14)N overtone MAS NMR spectroscopy. Phys Chem Chem Phys. 2014;16:12890–9.CrossRefGoogle Scholar
  50. 50.
    Chaudhari SR, Berruyer P, Gajan D, Reiter C, Engelke F, Silverio DL, Copéret C, Lelli M, Lesage A, Emsley L. Dynamic nuclear polarization at 40 kHz magic angle spinning. Phys Chem Chem Phys. 2016;18:10616–22.CrossRefGoogle Scholar

Authors and Affiliations

  1. 1.INACUniversity of Grenoble AlpesGrenobleFrance
  2. 2.INACCEAGrenobleFrance
  3. 3.INACCNRSGrenobleFrance

Personalised recommendations