In Silico Design of DNP Polarizing Agents: Can Current Dinitroxides Be Improved?

Perras, Frédéric A.; Sadow, Aaron; Pruski, Marek

doi:10.1002/cphc.201700299

In Silico Design of DNP Polarizing Agents: Can Current Dinitroxides Be Improved?

Journal Article · Fri Jun 09 00:00:00 EDT 2017 · ChemPhysChem

DOI:https://doi.org/10.1002/cphc.201700299· OSTI ID:1371891

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Ames Lab., Ames, IA (United States)
Ames Lab., Ames, IA (United States); Iowa State Univ., Ames, IA (United States). Dept. of Chemistry

Numerical calculations of enhancement factors offered by dynamic nuclear polarization in solids under magic angle spinning (DNP-MAS) were performed to determine the optimal EPR parameters for a dinitroxide polarizing agent. We found that the DNP performance of a biradical is more tolerant to the relative orientation of the two nitroxide moieties than previously thought. In general, any condition in which the gyy tensor components of both radicals are perpendicular to one another is expected to have near-optimal DNP performance. These results highlight the important role of the exchange coupling, which can lessen the sensitivity of DNP performance to the inter-radical distance, but also lead to lower enhancements when the number of atoms in the linker becomes less than three. Finally, the calculations showed that the electron T1e value should be near 500μs to yield optimal performance. Importantly, the newest polarizing agents already feature all of the qualities of the optimal polarizing agent, leaving little room for further improvement. Further research into DNP polarizing agents should then target non-nitroxide radicals, as well as improvements in sample formulations to advance high-temperature DNP and limit quenching and reactivity.

View Accepted Manuscript (DOE)

Research Organization:: Ames Laboratory (AMES), Ames, IA (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)

Grant/Contract Number:: AC02-07CH11358

OSTI ID:: 1371891

Alternate ID(s):: OSTI ID: 1375526

Report Number(s):: IS-J--9360

Journal Information:: ChemPhysChem, Journal Name: ChemPhysChem Journal Issue: 16 Vol. 18; ISSN 1439-4235

Publisher:: ChemPubSoc EuropeCopyright Statement

Country of Publication:: United States

Language:: English

References (62)

Dynamic Nuclear Polarization with a Rigid Biradical Matsuki, Yoh; Maly, Thorsten; Ouari, Olivier Angewandte Chemie, Vol. 121, Issue 27 https://doi.org/10.1002/ange.200805940	journal	June 2009
Highly Efficient, Water-Soluble Polarizing Agents for Dynamic Nuclear Polarization at High Frequency Sauvée, Claire; Rosay, Melanie; Casano, Gilles Angewandte Chemie, Vol. 125, Issue 41 https://doi.org/10.1002/ange.201304657	journal	August 2013
Efficient Dynamic Nuclear Polarization at 800 MHz/527 GHz with Trityl-Nitroxide Biradicals Mathies, Guinevere; Caporini, Marc A.; Michaelis, Vladimir K. Angewandte Chemie, Vol. 127, Issue 40 https://doi.org/10.1002/ange.201504292	journal	September 2015
Dynamic Nuclear Polarization with a Rigid Biradical Matsuki, Yoh; Maly, Thorsten; Ouari, Olivier Angewandte Chemie International Edition, Vol. 48, Issue 27 https://doi.org/10.1002/anie.200805940	journal	June 2009
Highly Efficient, Water-Soluble Polarizing Agents for Dynamic Nuclear Polarization at High Frequency Sauvée, Claire; Rosay, Melanie; Casano, Gilles Angewandte Chemie International Edition, Vol. 52, Issue 41 https://doi.org/10.1002/anie.201304657	journal	August 2013
Efficient Dynamic Nuclear Polarization at 800 MHz/527 GHz with Trityl-Nitroxide Biradicals Mathies, Guinevere; Caporini, Marc A.; Michaelis, Vladimir K. Angewandte Chemie International Edition, Vol. 54, Issue 40 https://doi.org/10.1002/anie.201504292	journal	August 2015
Tailoring of Polarizing Agents in the bTurea Series for Cross-Effect Dynamic Nuclear Polarization in Aqueous Media Sauvée, Claire; Casano, Gilles; Abel, Sébastien Chemistry - A European Journal, Vol. 22, Issue 16 https://doi.org/10.1002/chem.201504693	journal	March 2016
On Mechanisms of Dynamic Nuclear Polarization in Solids Thurber, Kent R.; Tycko, Robert Israel Journal of Chemistry, Vol. 54, Issue 1-2 https://doi.org/10.1002/ijch.201300116	journal	January 2014
Regularities of the spin exchange coupling through a bridge in nitroxide biradicals Kokorin, A. I. Applied Magnetic Resonance, Vol. 26, Issue 1-2 https://doi.org/10.1007/BF03166576	journal	March 2004
High-Field Dynamic Nuclear Polarization for Solid and Solution Biological NMR Barnes, A. B.; De Paëpe, G.; van der Wel, P. C. A. Applied Magnetic Resonance, Vol. 34, Issue 3-4 https://doi.org/10.1007/s00723-008-0129-1	journal	August 2008
Dinitroxides for Solid State Dynamic Nuclear Polarization Ysacco, Cédric; Karoui, Hakim; Casano, Gilles Applied Magnetic Resonance, Vol. 43, Issue 1-2 https://doi.org/10.1007/s00723-012-0356-3	journal	May 2012
MO theoretical studies of magnetic interactions in clusters of nitronyl nitroxide and related species Yamaguchi, K.; Okumura, M.; Maki, J. Chemical Physics Letters, Vol. 190, Issue 3-4 https://doi.org/10.1016/0009-2614(92)85351-A	journal	March 1992
A high-resolution NMR probe in which the coil and preamplifier are cooled with liquid helium Styles, P.; Soffe, N. F.; Scott, C. A. Journal of Magnetic Resonance (1969), Vol. 60, Issue 3 https://doi.org/10.1016/0022-2364(84)90050-7	journal	December 1984
Fast passage dynamic nuclear polarization on rotating solids Mentink-Vigier, Frederic; Akbey, Ümit; Hovav, Yonatan Journal of Magnetic Resonance, Vol. 224 https://doi.org/10.1016/j.jmr.2012.08.013	journal	November 2012
Theoretical aspects of Magic Angle Spinning - Dynamic Nuclear Polarization Mentink-Vigier, Frederic; Akbey, Ümit; Oschkinat, Hartmut Journal of Magnetic Resonance, Vol. 258 https://doi.org/10.1016/j.jmr.2015.07.001	journal	September 2015
Magnetic resonance imaging of DNP enhancements in a rotor spinning at the magic angle Perras, Frédéric A.; Kobayashi, Takeshi; Pruski, Marek Journal of Magnetic Resonance, Vol. 264 https://doi.org/10.1016/j.jmr.2016.01.004	journal	March 2016
Structural biology applications of solid state MAS DNP NMR Akbey, Ümit; Oschkinat, Hartmut Journal of Magnetic Resonance, Vol. 269 https://doi.org/10.1016/j.jmr.2016.04.003	journal	August 2016
Polarizing agents and mechanisms for high-field dynamic nuclear polarization of frozen dielectric solids Hu, Kan-Nian Solid State Nuclear Magnetic Resonance, Vol. 40, Issue 2 https://doi.org/10.1016/j.ssnmr.2011.08.001	journal	September 2011
Dynamic Nuclear Polarization Solid-State NMR in Heterogeneous Catalysis Research Kobayashi, Takeshi; Perras, Frédéric A.; Slowing, Igor I. ACS Catalysis, Vol. 5, Issue 12 https://doi.org/10.1021/acscatal.5b02039	journal	October 2015
Dynamic Nuclear Polarization Surface Enhanced NMR Spectroscopy Rossini, Aaron J.; Zagdoun, Alexandre; Lelli, Moreno Accounts of Chemical Research, Vol. 46, Issue 9 https://doi.org/10.1021/ar300322x	journal	March 2013
Electron spin resonance studies of anisotropic rotational reorientation and slow tumbling in liquid and frozen media. III. Perdeuterated 2,2,6,6-tetramethyl-4-piperidone N-oxide and an analysis of fluctuating torques Hwang, James S.; Mason, Ronald P.; Hwang, Lian Pin The Journal of Physical Chemistry, Vol. 79, Issue 5 https://doi.org/10.1021/j100572a017	journal	February 1975
Spin exchange in nitroxyl biradicals Metzner, E. Kurt; Libertini, Louis J.; Calvin, M. Journal of the American Chemical Society, Vol. 96, Issue 20 https://doi.org/10.1021/ja00827a045	journal	January 1974
Dynamic Nuclear Polarization with Biradicals Hu, Kan-Nian; Yu, Hsiao-hua; Swager, Timothy M. Journal of the American Chemical Society, Vol. 126, Issue 35 https://doi.org/10.1021/ja039749a	journal	September 2004
TOTAPOL: A Biradical Polarizing Agent for Dynamic Nuclear Polarization Experiments in Aqueous Media Song, Changsik; Hu, Kan-Nian; Joo, Chan-Gyu Journal of the American Chemical Society, Vol. 128, Issue 35 https://doi.org/10.1021/ja061284b	journal	September 2006
Dynamic Nuclear Polarization of Amyloidogenic Peptide Nanocrystals: GNNQQNY, a Core Segment of the Yeast Prion Protein Sup35p van der Wel, Patrick C. A.; Hu, Kan-Nian; Lewandowski, Józef Journal of the American Chemical Society, Vol. 128, Issue 33 https://doi.org/10.1021/ja0626685	journal	August 2006
Surface Enhanced NMR Spectroscopy by Dynamic Nuclear Polarization Lesage, Anne; Lelli, Moreno; Gajan, David Journal of the American Chemical Society, Vol. 132, Issue 44 https://doi.org/10.1021/ja104771z	journal	November 2010
High-Field Dynamic Nuclear Polarization with High-Spin Transition Metal Ions Corzilius, Björn; Smith, Albert A.; Barnes, Alexander B. Journal of the American Chemical Society, Vol. 133, Issue 15 https://doi.org/10.1021/ja1109002	journal	April 2011
A Slowly Relaxing Rigid Biradical for Efficient Dynamic Nuclear Polarization Surface-Enhanced NMR Spectroscopy: Expeditious Characterization of Functional Group Manipulation in Hybrid Materials Zagdoun, Alexandre; Casano, Gilles; Ouari, Olivier Journal of the American Chemical Society, Vol. 134, Issue 4 https://doi.org/10.1021/ja210177v	journal	January 2012
Dynamic Nuclear Polarization with a Water-Soluble Rigid Biradical Kiesewetter, Matthew K.; Corzilius, Björn; Smith, Albert A. Journal of the American Chemical Society, Vol. 134, Issue 10 https://doi.org/10.1021/ja212054e	journal	February 2012
Dynamic Nuclear Polarization NMR Spectroscopy of Microcrystalline Solids Rossini, Aaron J.; Zagdoun, Alexandre; Hegner, Franziska Journal of the American Chemical Society, Vol. 134, Issue 40 https://doi.org/10.1021/ja308135r	journal	September 2012
Large Molecular Weight Nitroxide Biradicals Providing Efficient Dynamic Nuclear Polarization at Temperatures up to 200 K Zagdoun, Alexandre; Casano, Gilles; Ouari, Olivier Journal of the American Chemical Society, Vol. 135, Issue 34 https://doi.org/10.1021/ja405813t	journal	August 2013
Dynamic Nuclear Polarization NMR Enables the Analysis of Sn-Beta Zeolite Prepared with Natural Abundance ¹¹⁹ Sn Precursors Gunther, William R.; Michaelis, Vladimir K.; Caporini, Marc A. Journal of the American Chemical Society, Vol. 136, Issue 17 https://doi.org/10.1021/ja502113d	journal	April 2014
Dynamic Nuclear Polarization of ¹ H, ¹³ C, and ⁵⁹ Co in a Tris(ethylenediamine)cobalt(III) Crystalline Lattice Doped with Cr(III) Corzilius, Björn; Michaelis, Vladimir K.; Penzel, Susanne A. Journal of the American Chemical Society, Vol. 136, Issue 33 https://doi.org/10.1021/ja5044374	journal	August 2014
Amplifying Dynamic Nuclear Polarization of Frozen Solutions by Incorporating Dielectric Particles Kubicki, Dominik J.; Rossini, Aaron J.; Purea, Armin Journal of the American Chemical Society, Vol. 136, Issue 44 https://doi.org/10.1021/ja5088453	journal	October 2014
Influences of Dilute Organic Adsorbates on the Hydration of Low-Surface-Area Silicates Sangodkar, Rahul P.; Smith, Benjamin J.; Gajan, David Journal of the American Chemical Society, Vol. 137, Issue 25 https://doi.org/10.1021/jacs.5b00622	journal	June 2015
Brute-Force Hyperpolarization for NMR and MRI Hirsch, Matthew L.; Kalechofsky, Neal; Belzer, Avrum Journal of the American Chemical Society, Vol. 137, Issue 26 https://doi.org/10.1021/jacs.5b01252	journal	June 2015
Rigid Orthogonal Bis-TEMPO Biradicals with Improved Solubility for Dynamic Nuclear Polarization Dane, Eric L.; Corzilius, Björn; Rizzato, Egon The Journal of Organic Chemistry, Vol. 77, Issue 4 https://doi.org/10.1021/jo202349j	journal	February 2012
Mesoporous Silica Nanoparticles Loaded with Surfactant: Low Temperature Magic Angle Spinning ¹³ C and ²⁹ Si NMR Enhanced by Dynamic Nuclear Polarization Lafon, Olivier; Thankamony, Aany S. Lilly; Kobayashi, Takeshi The Journal of Physical Chemistry C, Vol. 117, Issue 3 https://doi.org/10.1021/jp310109s	journal	January 2013
Identifying low-coverage surface species on supported noble metal nanoparticle catalysts by DNP-NMR Johnson, Robert L.; Perras, Frédéric A.; Kobayashi, Takeshi Chemical Communications, Vol. 52, Issue 9 https://doi.org/10.1039/C5CC06788J	journal	January 2016
Nuclear depolarization and absolute sensitivity in magic-angle spinning cross effect dynamic nuclear polarization Mentink-Vigier, Frédéric; Paul, Subhradip; Lee, Daniel Physical Chemistry Chemical Physics, Vol. 17, Issue 34 https://doi.org/10.1039/C5CP03457D	journal	January 2015
Effects of biradical deuteration on the performance of DNP: towards better performing polarizing agents Perras, Frédéric A.; Reinig, Regina R.; Slowing, Igor I. Physical Chemistry Chemical Physics, Vol. 18, Issue 1 https://doi.org/10.1039/C5CP06505D	journal	January 2016
Rational design of dinitroxide biradicals for efficient cross-effect dynamic nuclear polarization Kubicki, Dominik J.; Casano, Gilles; Schwarzwälder, Martin Chemical Science, Vol. 7, Issue 1 https://doi.org/10.1039/C5SC02921J	journal	January 2016
bcTol: a highly water-soluble biradical for efficient dynamic nuclear polarization of biomolecules Jagtap, Anil P.; Geiger, Michel-Andreas; Stöppler, Daniel Chemical Communications, Vol. 52, Issue 43 https://doi.org/10.1039/C6CC01813K	journal	January 2016
Theory of solid effect and cross effect dynamic nuclear polarization with half-integer high-spin metal polarizing agents in rotating solids Corzilius, Björn Physical Chemistry Chemical Physics, Vol. 18, Issue 39 https://doi.org/10.1039/C6CP04621E	journal	January 2016
A tailored multi-frequency EPR approach to accurately determine the magnetic resonance parameters of dynamic nuclear polarization agents: application to AMUPol Gast, P.; Mance, D.; Zurlo, E. Physical Chemistry Chemical Physics, Vol. 19, Issue 5 https://doi.org/10.1039/C6CP05864G	journal	January 2017
Fast and accurate MAS–DNP simulations of large spin ensembles Mentink-Vigier, Frédéric; Vega, Shimon; De Paëpe, Gaël Physical Chemistry Chemical Physics, Vol. 19, Issue 5 https://doi.org/10.1039/C6CP07881H	journal	January 2017
Reactive surface organometallic complexes observed using dynamic nuclear polarization surface enhanced NMR spectroscopy Pump, Eva; Viger-Gravel, Jasmine; Abou-Hamad, Edy Chemical Science, Vol. 8, Issue 1 https://doi.org/10.1039/C6SC02379G	journal	January 2017
Dendritic polarizing agents for DNP SENS Liao, Wei-Chih; Ong, Ta-Chung; Gajan, David Chemical Science, Vol. 8, Issue 1 https://doi.org/10.1039/C6SC03139K	journal	January 2017
Solid-state dynamic nuclear polarization at 263 GHz: spectrometer design and experimental results Rosay, Melanie; Tometich, Leo; Pawsey, Shane Physical Chemistry Chemical Physics, Vol. 12, Issue 22 https://doi.org/10.1039/c003685b	journal	January 2010
Mechanism of dynamic nuclear polarization in high magnetic fields Farrar, C. T.; Hall, D. A.; Gerfen, G. J. The Journal of Chemical Physics, Vol. 114, Issue 11 https://doi.org/10.1063/1.1346640	journal	March 2001
Nuclear Magnetic Resonance Powder Patterns of the Second‐Order Nuclear Quadrupole Interaction in Solids with Asymmetric Field Gradient Narita, Koziro; Umeda, Jun‐ichi; Kusumoto, Hazime The Journal of Chemical Physics, Vol. 44, Issue 7 https://doi.org/10.1063/1.1727118	journal	April 1966
High-frequency dynamic nuclear polarization using mixtures of TEMPO and trityl radicals Hu, Kan-Nian; Bajaj, Vikram S.; Rosay, Melanie The Journal of Chemical Physics, Vol. 126, Issue 4 https://doi.org/10.1063/1.2429658	journal	January 2007
High-frequency dynamic nuclear polarization using biradicals: A multifrequency EPR lineshape analysis Hu, Kan-Nian; Song, Changsik; Yu, Hsiao-hua The Journal of Chemical Physics, Vol. 128, Issue 5 https://doi.org/10.1063/1.2816783	journal	February 2008
Dynamic nuclear polarization at high magnetic fields Maly, Thorsten; Debelouchina, Galia T.; Bajaj, Vikram S. The Journal of Chemical Physics, Vol. 128, Issue 5 https://doi.org/10.1063/1.2833582	journal	February 2008
Theory for cross effect dynamic nuclear polarization under magic-angle spinning in solid state nuclear magnetic resonance: The importance of level crossings Thurber, Kent R.; Tycko, Robert The Journal of Chemical Physics, Vol. 137, Issue 8 https://doi.org/10.1063/1.4747449	journal	August 2012
Perturbation of nuclear spin polarizations in solid state NMR of nitroxide-doped samples by magic-angle spinning without microwaves Thurber, Kent R.; Tycko, Robert The Journal of Chemical Physics, Vol. 140, Issue 18 https://doi.org/10.1063/1.4874341	journal	May 2014
Overhauser effects in insulating solids Can, T. V.; Caporini, M. A.; Mentink-Vigier, F. The Journal of Chemical Physics, Vol. 141, Issue 6 https://doi.org/10.1063/1.4891866	journal	August 2014
The magnetic field dependence of cross-effect dynamic nuclear polarization under magic angle spinning Mance, Deni; Gast, Peter; Huber, Martina The Journal of Chemical Physics, Vol. 142, Issue 23 https://doi.org/10.1063/1.4922219	journal	June 2015
Increase in signal-to-noise ratio of > 10,000 times in liquid-state NMR Ardenkjaer-Larsen, J. H.; Fridlund, B.; Gram, A. Proceedings of the National Academy of Sciences, Vol. 100, Issue 18 https://doi.org/10.1073/pnas.1733835100	journal	August 2003
Polarization of Nuclear Spins in Metals Carver, T. R.; Slichter, C. P. Physical Review, Vol. 92, Issue 1 https://doi.org/10.1103/PhysRev.92.212.2	journal	October 1953
Polarization of Nuclei in Metals Overhauser, Albert W. Physical Review, Vol. 92, Issue 2 https://doi.org/10.1103/PhysRev.92.411	journal	October 1953
Dynamic nuclear polarization with a cyclotron resonance maser at 5 T Becerra, Lino R.; Gerfen, Gary J.; Temkin, Richard J. Physical Review Letters, Vol. 71, Issue 21 https://doi.org/10.1103/PhysRevLett.71.3561	journal	November 1993

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Continuous wave electron paramagnetic resonance of nitroxide biradicals in fluid solution Eaton, Sandra S.; Woodcock, Lukas B.; Eaton, Gareth R. Concepts in Magnetic Resonance Part A, Vol. 47A, Issue 2 https://doi.org/10.1002/cmr.a.21426	journal	March 2018
Conformation of bis-nitroxide polarizing agents by multi-frequency EPR spectroscopy Soetbeer, Janne; Gast, Peter; Walish, Joseph J. Physical Chemistry Chemical Physics, Vol. 20, Issue 39 https://doi.org/10.1039/c8cp05236k	journal	January 2018
Optimizing nitroxide biradicals for cross-effect MAS-DNP: the role of g -tensors’ distance Mentink-Vigier, Frédéric Physical Chemistry Chemical Physics, Vol. 22, Issue 6 https://doi.org/10.1039/c9cp06201g	journal	January 2020
Large-scale ab initio simulations of MAS DNP enhancements using a Monte Carlo optimization strategy Perras, Frédéric A.; Pruski, Marek The Journal of Chemical Physics, Vol. 149, Issue 15 https://doi.org/10.1063/1.5042651	journal	October 2018
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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
MAS-DN
dinitroxides
dynamic nuclear polarization
simulations
solid-state NMR

In Silico Design of DNP Polarizing Agents: Can Current Dinitroxides Be Improved?

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References (62)

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