Abstract
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.
Similar content being viewed by others
References
Overhauser A. Polarization of nuclei in metals. Phys Rev. 1953;92:411–5.
Carver TR, Slichter CP. Polarization of nuclear spins in metals. Phys Rev. 1953;92:212–3.
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.
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.
Can TV, Ni QZ, Griffin RG. Mechanisms of dynamic nuclear polarization in insulating solids. J Magn Reson. 2015;253:23–35.
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.
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.
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.
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.
Mentink-Vigier F, Vega S, De Paëpe G. Large spin ensembles for MAS-DNP. Phys Chem Chem Phys. 2017;19:3506–22.
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.
Hu K-N, Yu H, Swager TM, Griffin RG. Dynamic nuclear polarization with biradicals. J Am Chem Soc. 2004;126:10844–5.
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.
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.
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.
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.
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.
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.
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.
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.
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.
Lee D, Bouleau E, Saint-Bonnet P, Hediger S, De Paëpe G. Ultra-low temperature MAS-DNP. J Magn Reson. 2016;264:116–24.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
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.
Author information
Authors and Affiliations
Corresponding author
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 2017 Springer International Publishing AG
About this entry
Cite this entry
Lee, D., Hediger, S., Paëpe, G.D. (2017). High-Field Solid-State NMR with Dynamic Nuclear Polarization. In: Webb, G. (eds) Modern Magnetic Resonance. Springer, Cham. https://doi.org/10.1007/978-3-319-28275-6_73-1
Download citation
DOI: https://doi.org/10.1007/978-3-319-28275-6_73-1
Received:
Accepted:
Published:
Publisher Name: Springer, Cham
Print ISBN: 978-3-319-28275-6
Online ISBN: 978-3-319-28275-6
eBook Packages: Springer Reference Chemistry and Mat. ScienceReference Module Physical and Materials ScienceReference Module Chemistry, Materials and Physics