Articles | Volume 4, issue 2
https://doi.org/10.5194/mr-4-243-2023
© Author(s) 2023. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
https://doi.org/10.5194/mr-4-243-2023
© Author(s) 2023. This work is distributed under
the Creative Commons Attribution 4.0 License.
the Creative Commons Attribution 4.0 License.
The solid effect of dynamic nuclear polarization in liquids – accounting for g-tensor anisotropy at high magnetic fields
Institute of Physical and Theoretical Chemistry, Goethe University, 60438 Frankfurt am Main, Germany
Danhua Dai
Institute of Physical and Theoretical Chemistry, Goethe University, 60438 Frankfurt am Main, Germany
Thomas F. Prisner
Institute of Physical and Theoretical Chemistry, Goethe University, 60438 Frankfurt am Main, Germany
Related authors
Deniz Sezer
Magn. Reson., 4, 129–152, https://doi.org/10.5194/mr-4-129-2023, https://doi.org/10.5194/mr-4-129-2023, 2023
Short summary
Short summary
Since its discovery 65 years ago, the solid-state dynamic nuclear polarization effect has been rationalized in terms of mixing of the Zeeman energy levels. Before becoming aware of this explanation, Erb, Motchane and Uebersfeld proposed a dynamical equation to make sense of their experiments. Here we provide a formal justification of their phenomenological equation. The result is a different way of thinking about the solid-state effect, with novel implications for the effect in liquids.
Deniz Sezer
Magn. Reson., 4, 153–174, https://doi.org/10.5194/mr-4-153-2023, https://doi.org/10.5194/mr-4-153-2023, 2023
Short summary
Short summary
We show that the field profile of the solid effect in liquids is rich in dynamical information, including about timescales of molecular diffusion. We develop a general theoretical framework for extracting this information through quantitative fits to the experimental data. Unusual peaks in the enhancement field profile, which resemble thermal mixing but are not related to it, are demonstrated to arise in liquids under some conditions. These additionally restrict the dynamical parameters.
Paul Trenkler, Burkhard Endeward, Snorri Sigurdsson, and Thomas Prisner
Magn. Reson. Discuss., https://doi.org/10.5194/mr-2025-11, https://doi.org/10.5194/mr-2025-11, 2025
Preprint under review for MR
Short summary
Short summary
Pulse EPR techniques measure distances and orientation between paramagnetic markers attached to biomolecules. If they are rigidly anchored, advanced structural insights into structure and dynamics of the biomolecule follow. We used chirp pulses to perform real 2D EPR experiment with much shorter experimental time compared to experiments with monochromatic microwave pulses. We also present new pulse sequences and give a detailed protocol for setting up such experiments.
Deniz Sezer
Magn. Reson., 4, 129–152, https://doi.org/10.5194/mr-4-129-2023, https://doi.org/10.5194/mr-4-129-2023, 2023
Short summary
Short summary
Since its discovery 65 years ago, the solid-state dynamic nuclear polarization effect has been rationalized in terms of mixing of the Zeeman energy levels. Before becoming aware of this explanation, Erb, Motchane and Uebersfeld proposed a dynamical equation to make sense of their experiments. Here we provide a formal justification of their phenomenological equation. The result is a different way of thinking about the solid-state effect, with novel implications for the effect in liquids.
Deniz Sezer
Magn. Reson., 4, 153–174, https://doi.org/10.5194/mr-4-153-2023, https://doi.org/10.5194/mr-4-153-2023, 2023
Short summary
Short summary
We show that the field profile of the solid effect in liquids is rich in dynamical information, including about timescales of molecular diffusion. We develop a general theoretical framework for extracting this information through quantitative fits to the experimental data. Unusual peaks in the enhancement field profile, which resemble thermal mixing but are not related to it, are demonstrated to arise in liquids under some conditions. These additionally restrict the dynamical parameters.
Sarah R. Sweger, Vasyl P. Denysenkov, Lutz Maibaum, Thomas F. Prisner, and Stefan Stoll
Magn. Reson., 3, 101–110, https://doi.org/10.5194/mr-3-101-2022, https://doi.org/10.5194/mr-3-101-2022, 2022
Short summary
Short summary
This work examines the physics underlying double electron–electron resonance (DEER) spectroscopy, a magnetic-resonance method that provides nanoscale data about protein structure and conformations.
Alexey Fedotov, Ilya Kurakin, Sebastian Fischer, Thomas Vogl, Thomas F. Prisner, and Vasyl Denysenkov
Magn. Reson., 1, 275–284, https://doi.org/10.5194/mr-1-275-2020, https://doi.org/10.5194/mr-1-275-2020, 2020
Short summary
Short summary
The sensitivity of magnetic resonance imaging can be increased by coupling of the less sensitive nuclear spins which are excited at radio frequencies to unpaired electron spins of radicals which are excited at microwave frequencies. Here we demonstrate how a Fabry–Perot-type microwave resonance structure can be used to significantly enhance the polarization transfer from electron to water proton nuclear spins under constant flow conditions for imaging applications at 1.5 T.
Cited articles
Abragam, A. and Goldman, M.: Principles of dynamic nuclear polarisation, Rep. Prog. Phys., 41, 395, https://doi.org/10.1088/0034-4885/41/3/002, 1978. a
Anderson, P. W.: A Mathematical Model for the Narrowing of Spectral Lines by Exchange or Motion, J. Phys. Soc. Jpn., 9, 316–339, https://doi.org/10.1143/JPSJ.9.316, 1954. a, b
Atsarkin, V. A.: Dynamic nuclear polarization: Yesterday, today, and tomorrow, J. Phys. Conf. Ser., 324, 012003, https://doi.org/10.1088/1742-6596/324/1/012003, 2011. a
Carver, T. R. and Slichter, C. P.: Experimental Verification of the Overhauser Nuclear Polarization Effect, Phys. Rev., 102, 975–980, https://doi.org/10.1103/PhysRev.102.975, 1956. a
Costa-Filho, A. J., Shimoyama, Y., and Freed, J. H.: A 2D-ELDOR Study of the Liquid Ordered Phase in Multilamellar Vesicle Membranes, Biophys. J., 84, 2619–2633, https://doi.org/10.1016/S0006-3495(03)75067-X, 2003. a, b
Denysenkov, V., Dai, D., and Prisner, T. F.: A triple resonance (e, 1H, 13C) probehead for liquid-state DNP experiments at 9.4 Tesla, J. Magn. Reson., 337, 107185, https://doi.org/10.1016/j.jmr.2022.107185, 2022. a, b, c
Erb, E., Motchane, J.-L., and Uebersfeld, J.: Effet de polarisation nucléaire dans les liquides et les gaz adsorbés sur les charbons, Compt. Rend., 246, 2121–2123, 1958a. a
Erb, E., Motchane, J.-L., and Uebersfeld, J.: Sur une nouvelle méthode de polarisation nucléaire dans les fluides adsorbés sur les charbons. extension aux solides et en particulier aux substances organiques irradiées., Compt. Rend., 246, 3050–3052, 1958b. a
Filippov, A., Orädd, G., and Lindblom, G.: The Effect of Cholesterol on the Lateral Diffusion of Phospholipids in Oriented Bilayers, Biophys. J., 84, 3079–3086, https://doi.org/10.1016/S0006-3495(03)70033-2, 2003. a
Freed, J. H.: Theory of Slow Tumbling ESR Spectra for Nitroxides, in: Spin Labeling: Theory and Applications, edited by: Berliner, L. J., Academic Press, Inc., 53–132, https://doi.org/10.1016/B978-0-12-092350-2.50008-4, 1976. a
Gizatullin, B., Mattea, C., and Stapf, S.: Field-cycling NMR and DNP – A friendship with benefits, J. Magn. Reson., 322, 106851, https://doi.org/10.1016/j.jmr.2020.106851, 2021a. a, b, c
Gizatullin, B., Mattea, C., and Stapf, S.: Molecular Dynamics in Ionic Liquid/Radical Systems, J. Phys. Chem. B, 125, 4850–4862, https://doi.org/10.1021/acs.jpcb.1c02118, 2021b. a, b
Gizatullin, B., Mattea, C., and Stapf, S.: Three mechanisms of room temperature dynamic nuclear polarization occur simultaneously in an ionic liquid, Phys. Chem. Chem. Phys., 24, 27004–27008, https://doi.org/10.1039/D2CP03437A, 2022. a
Greenwood, A. I., Tristram-Nagle, S., and Nagle, J. F.: Partial molecular volumes of lipids and cholesterol, Chem. Phys. Lipids, 143, 1–10, https://doi.org/10.1016/j.chemphyslip.2006.04.002, 2006. a
Hausser, K. H. and Stehlik, D.: Dynamic Nuclear Polarization in Liquids, in: Advances in Magnetic Resonance, edited by: Waugh, J. S., vol. 3, 79–139 pp., Academic Press, https://doi.org/10.1016/B978-1-4832-3116-7.50010-2, 1968. a, b
Kubo, R.: Note on the Stochastic Theory of Resonance Absorption, J. Phys. Soc. Jpn., 9, 935–944, https://doi.org/10.1143/JPSJ.9.935, 1954. a, b
Kubo, R.: A Stochastic Theory of Line Shape, in: Advances in Chemical Physics, edited by: Shuler, K. E., vol. XV, chap. 6, John Wiley & Sons Inc., 101–127, https://doi.org/10.1002/9780470143605.ch6, 1969. a
Kučerka, N., Nagle, J. F., Sachs, J. N., Feller, S. E., Pencer, J., Jackson, A., and Katsaras, J.: Lipid Bilayer Structure Determined by the Simultaneous Analysis of Neutron and X-Ray Scattering Data, Biophys. J., 95, 2356–2367, https://doi.org/10.1529/biophysj.108.132662, 2008. a
Küçük, S. E., Neugebauer, P., Prisner, T. F., and Sezer, D.: Molecular simulations for dynamic nuclear polarization in liquids: a case study of TEMPOL in acetone and DMSO, Phys. Chem. Chem. Phys., 17, 6618–6628, https://doi.org/10.1039/C4CP05832A, 2015. a
Kuzhelev, A. A., Dai, D., Denysenkov, V., and Prisner, T. F.: Solid-like Dynamic Nuclear Polarization Observed in the Fluid Phase of Lipid Bilayers at 9.4 T, J. Am. Chem. Soc., 144, 1164–1168, https://doi.org/10.1021/jacs.1c12837, 2022. a, b
Kuzhelev, A. A., Denysenkov, V., Ahmad, I. M., Rogozhnikova, O. Y., Trukhin, D. V., Bagryanskaya, E. G., Tormyshev, V. M., Sigurdsson, S. T., and Prisner, T. F.: Solid-Effect Dynamic Nuclear Polarization in Viscous Liquids at 9.4 T Using Narrow-Line Polarizing Agents, J. Am. Chem. Soc., 145, 10268–10274, https://doi.org/10.1021/jacs.3c01358, 2023. a, b, c
Leblond, J., Papon, P., and Korringa, J.: Stochastic Theory of Dynamic Spin Polarization in Viscous Liquids with Anisotropic Electron-Spin Relaxation, Phys. Rev. A, 4, 1539–1549, https://doi.org/10.1103/PhysRevA.4.1539, 1971a. a, b
Leblond, J., Uebersfeld, J., and Korringa, J.: Study of the Liquid-State Dynamics by Means of Magnetic Resonance and Dynamic Polarization, Phys. Rev. A, 4, 1532–1539, https://doi.org/10.1103/PhysRevA.4.1532, 1971b. a, b, c
Lipari, G. and Szabo, A.: Model-free approach to the interpretation of nuclear magnetic resonance relaxation in macromolecules. 2. Analysis of experimental results, J. Am. Chem. Soc., 104, 4559–4570, https://doi.org/10.1021/ja00381a010, 1982. a
Livshits, V. A., Kurad, D., and Marsh, D.: Simulation Studies on High-Field EPR Spectra of Lipid Spin Labels in Cholesterol-Containing Membranes, J. Phys. Chem. B, 108, 9403–9411, https://doi.org/10.1021/jp035915p, 2004. a, b
Livshits, V. A., Kurad, D., and Marsh, D.: Multifrequency simulations of the EPR spectra of lipid spin labels in membranes, J. Magn. Reson., 180, 63–71, https://doi.org/10.1016/j.jmr.2006.01.005, 2006. a
Lou, Y., Ge, M., and Freed, J. H.: A Multifrequency ESR Study of the Complex Dynamics of Membranes, J. Phys. Chem. B, 105, 11053–11056, https://doi.org/10.1021/jp013226c, 2001. a
Meirovitch, E., Nayeem, A., and Freed, J. H.: Analysis of protein-lipid interactions based on model simulations of electron spin resonance spectra, J. Phys. Chem., 88, 3454–3465, https://doi.org/10.1021/j150660a018, 1984. a, b, c
Müller-Warmuth, W. and Meise-Gresch, K.: Molecular Motions and Interactions as Studied by Dynamic Nuclear Polarization (DNP) in Free Radical Solutions, in: Advances in Magnetic Resonance, edited by: Waugh, J. S., vol. 11, 1–45, Academic Press, https://doi.org/10.1016/B978-0-12-025511-5.50007-4, 1983. a, b
Neudert, O., Mattea, C., and Stapf, S.: A compact X-Band resonator for DNP-enhanced Fast-Field-Cycling NMR, J. Magn. Reson., 271, 7–14, https://doi.org/10.1016/j.jmr.2016.08.002, 2016. a
Oruç, T., Küçük, S. E., and Sezer, D.: Lipid bilayer permeation of aliphatic amine and carboxylic acid drugs: rates of insertion, translocation and dissociation from MD simulations, Phys. Chem. Chem. Phys., 18, 24511–24525, https://doi.org/10.1039/C6CP05278A, 2016. a
Papon, P., Motchane, J. L., and Korringa, J.: Unitary Theory of Dynamic Polarization of Nuclear Spins in Liquids and Solids, Phys. Rev., 175, 641–649, https://doi.org/10.1103/PhysRev.175.641, 1968. a
Polimeno, A. and Freed, J. H.: Slow Motional ESR in Complex Fluids: The Slowly Relaxing Local Structure Model of Solvent Cage Effects, J. Phys. Chem., 99, 10995–11006, https://doi.org/10.1021/j100027a047, 1995. a, b, c
Prisner, T., Denysenkov, V., and Sezer, D.: Liquid state DNP at high magnetic fields: Instrumentation, experimental results and atomistic modelling by molecular dynamics simulations, J. Magn. Reson., 264, 68–77, https://doi.org/10.1016/j.jmr.2015.11.004, 2016. a
Redfield, A. G.: On the Theory of Relaxation Processes, IBM J. Res. Dev., 1, 19–31, https://doi.org/10.1147/rd.11.0019, 1957. a
Schneider, D. J. and Freed, J. H.: Calculating Slow Motional Magnetic Resonance Spectra, in: Spin Labeling: Theory and Applications, edited by: Berliner, L. J. and Reuben, J., Springer US, Boston, MA, 1–76, https://doi.org/10.1007/978-1-4613-0743-3_1, 1989. a
Sezer, D.: Computation of DNP coupling factors of a nitroxide radical in toluene: seamless combination of MD simulations and analytical calculations, Phys. Chem. Chem. Phys., 15, 526–540, https://doi.org/10.1039/C2CP42430D, 2013. a
Sezer, D.: dzsezer/solidDNPliquids_g-tensor: v1.0.0 (v1.0.0), Zenodo [code and data set], https://doi.org/10.5281/zenodo.8360325, 2023c. a
Sezer, D., Gafurov, M., Prandolini, M. J., Denysenkov, V. P., and Prisner, T. F.: Dynamic nuclear polarization of water by a nitroxide radical: rigorous treatment of the electron spin saturation and comparison with experiments at 9.2 Tesla, Phys. Chem. Chem. Phys., 11, 6638–6653, https://doi.org/10.1039/B906719C, 2009. a
Solomon, I.: Relaxation Processes in a System of Two Spins, Phys. Rev., 99, 559–565, https://doi.org/10.1103/PhysRev.99.559, 1955. a
Stoll, S. and Schweiger, A.: EasySpin, a comprehensive software package for spectral simulation and analysis in EPR, J. Magn. Reson., 178, 42–55, https://doi.org/10.1016/j.jmr.2005.08.013, 2006. a, b
Wenckebach, T.: Essentials of Dynamic Nuclear Polarization, Spindrift Publications, the Netherlands, ISBN 9789075541182, 2016. a
Short summary
We recently liberated the solid effect of dynamic nuclear polarization (DNP) from its perturbative treatment by describing the relevant spin dynamics in a time domain. This allows us to easily account for dynamical processes that modulate the spin interactions in liquids, like the translational diffusion of spins. Here we additionally model the slow rotational diffusion of the polarizing agent and analyze DNP data from nitroxide spin labels in lipid bilayers at 9.4 T.
We recently liberated the solid effect of dynamic nuclear polarization (DNP) from its...