Thomas F. Prisner

Goethe University Frankfurt

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Vasyl Denysenkov

Goethe University Frankfurt

Burkhard Endeward

Goethe University Frankfurt

Snorri Th. Sigurdsson

University of Iceland

Olav Schiemann

University of Bonn

Sevdalina Lyubenova

Bruker (Germany)

Andrey A. Kuzhelev

Goethe University Frankfurt

Andriy Marko

Central European Institute of Technology

Marina Bennati

University of Göttingen

Philipp E. Spindler

Humboldt-Universität zu Berlin

Dominik Margraf

Goethe University Frankfurt

Cooperative Institutions

Robert Bosch (Germany)

256

Goethe University Frankfurt

178

GP Batteries (China)

117

Laboratoire de Chimie Moléculaire et Thioorganique

109

Lithium Power (United States)

Centre National de la Recherche Scientifique

Chinese Academy of Sciences

Freie Universität Berlin

Weatherford College

Max Planck Society

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PULSEDEPR SPECTROSCOPY: Biological Applications

Annual Review of Physical Chemistry (2001)

Thomas F. Prisner Martin Rohrer Fraser MacMillan

Pulsed electron paramagnetic resonance (EPR) methods such as ESEEM, PELDOR, relaxation time measurements, transient EPR, high-field/high-frequency EPR, and pulsed ENDOR, have been used successfully to investigate the local structure and dynamics of paramagnetic centers in biological samples. These methods allow different contributions to the EPR spectra to be distinguished and can help unravel complicated EPR spectra consisting of overlapping resonance lines, as are often found in disordered protein samples. The basic principles, specific potentials, technical requirements, and limitations of these advanced EPR techniques will be reviewed together with recent applications to metal centers, organic radicals, and spin labels in proteins.

Pulsed EPR

Site-directed spin labeling

10.1146/annurev.physchem.52.1.279

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Citations (188)

Comment on mr-2023-10

Deniz Sezer Danhua Dai Thomas F. Prisner

Abstract. In spite of its name, the solid effect of dynamic nuclear polarization (DNP) is operative also in viscous liquids, where the dipolar interaction between the polarized nuclear spins and the polarizing electrons is not completely averaged out by molecular diffusion. Under such slow-motional conditions, it is likely that the tumbling of the polarizing agent is similarly too slow to efficiently average the anisotropies of its magnetic tensors. Here we extend our previous analysis of the solid effect in liquids to account for the effect of g-tensor anisotropy at high magnetic fields. Building directly on the mathematical treatment of slow-tumbling in electron spin resonance (Freed et al., 1971), we calculate solid-effect DNP enhancements in the presence of both translational diffusion of the liquid molecules and rotational diffusion of the polarizing agent. To illustrate the formalism, we analyze high-field (9.4 T) DNP enhancement profiles from nitroxide-labeled lipids in fluid lipid bilayers. By properly accounting for power-broadening and motional-broadening, we successfully decompose the measured DNP enhancements into their separate contributions from the solid and Overhauser effects.

Rotational diffusion

Nuclear Overhauser effect

10.5194/mr-2023-10-rc3

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Dynamic Nuclear Polarization with a Rigid Biradical

Angewandte Chemie International Edition (2009)

Yoh Matsuki Thorsten Maly Olivier Ouari Hakim Karoui François Le Moigne

A new polarizing agent with superior performance in dynamic nuclear polarization experiments is introduced, and utilizes two TEMPO (2,2,6,6-tetramethylpiperidine-1-oxyl) moieties connected through a rigid spiro tether (see structure). The observed NMR signal intensities were enhanced by a factor of 1.4 compared to those of TOTAPOL, a previously described TEMPO-based biradical with a flexible tether.

10.1002/anie.200805940

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Citations (269)

Gemischtvalente Verbindungen als polarisierende Mittel für die dynamische Kern‐Overhauser‐Polarisation in Festkörpern**

Angewandte Chemie (2021)

Andrei Gurinov Benedikt Sieland Andrey A. Kuzhelev Hossam Elgabarty Thomas D. Kühne

Abstract Wir untersuchen eine neuartige Gruppe von Polarisationsmitteln – gemischtvalente Verbindungen – mittels theoretischer und experimenteller Methoden und demonstrieren ihre Leistungsfähigkeit in NMR‐Experimenten mit Hochfeld‐DNP (DNP=Dynamic Nuclear Polarization, dynamische Kernpolarisation) im festen Zustand. Diese gemischtvalenten Verbindungen stellen eine Gruppe von Molekülen dar, bei denen die molekulare Mobilität auch in Festkörpern erhalten bleibt. Folglich können solche Polarisationsmittel unter günstigen Bedingungen für die dynamische Kernpolarisationsbildung bei ultrahohen Magnetfeldern verwendet werden, um Overhauser‐DNP‐Experimente im Festkörper durchzuführen.

10.1002/ange.202103215

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Facing and Overcoming Sensitivity Challenges in Biomolecular NMR Spectroscopy

Angewandte Chemie International Edition (2015)

Jan Henrik Ardenkjær‐Larsen G. S. Boebinger Arnaud Comment Simon B. Duckett Arthur S. Edison

Abstract In the Spring of 2013, NMR spectroscopists convened at the Weizmann Institute in Israel to brainstorm on approaches to improve the sensitivity of NMR experiments, particularly when applied in biomolecular settings. This multi‐author interdisciplinary Review presents a state‐of‐the‐art description of the primary approaches that were considered. Topics discussed included the future of ultrahigh‐field NMR systems, emerging NMR detection technologies, new approaches to nuclear hyperpolarization, and progress in sample preparation. All of these are orthogonal efforts, whose gains could multiply and thereby enhance the sensitivity of solid‐ and liquid‐state experiments. While substantial advances have been made in all these areas, numerous challenges remain in the quest of endowing NMR spectroscopy with the sensitivity that has characterized forms of spectroscopies based on electrical or optical measurements. These challenges, and the ways by which scientists and engineers are striving to solve them, are also addressed.

Brainstorming

Hyperpolarization

10.1002/anie.201410653

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Citations (315)

Base-specific spin-labeling of RNA for structure determination

Nucleic Acids Research (2007)

Nelly Piton Yuguang Mu Gerhard Stock Thomas F. Prisner Olav Schiemann

To facilitate the measurement of intramolecular distances in solvated RNA systems, a combination of spin-labeling, electron paramagnetic resonance (EPR), and molecular dynamics (MD) simulation is presented. The fairly rigid spin label 2,2,5,5-tetramethyl-pyrrolin-1-yloxyl-3-acetylene (TPA) was base and site specifically introduced into RNA through a Sonogashira palladium catalyzed cross-coupling on column. For this purpose 5-iodo-uridine, 5-iodo-cytidine and 2-iodo-adenosine phosphoramidites were synthesized and incorporated into RNA-sequences. Application of the recently developed ACE® chemistry presented the main advantage to limit the reduction of the nitroxide to an amine during the oligonucleotide automated synthesis and thus to increase substantially the reliability of the synthesis and the yield of labeled oligonucleotides. 4-Pulse Electron Double Resonance (PELDOR) was then successfully used to measure the intramolecular spin–spin distances in six doubly labeled RNA-duplexes. Comparison of these results with our previous work on DNA showed that A- and B-Form can be differentiated. Using an all-atom force field with explicit solvent, MD simulations gave results in good agreement with the measured distances and indicated that the RNA A-Form was conserved despite a local destabilization effect of the nitroxide label. The applicability of the method to more complex biological systems is discussed.

Spin label

Cytidine

10.1093/nar/gkm169

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Liquid state DNP using a 260 GHz high power gyrotron

Physical Chemistry Chemical Physics (2010)

Vasyl Denysenkov Mark J. Prandolini Marat Gafurov Deniz Sezer Burkhard Endeward

Dynamic nuclear polarization (DNP) at high magnetic fields (9.2 T, 400 MHz 1H NMR frequency) requires high microwave power sources to achieve saturation of the EPR transitions. Here we describe the first high-field liquid-state DNP results using a high-power gyrotron microwave source (20 W at 260 GHz). A DNP enhancement of −29 on water protons was obtained for an aqueous solution of Fremy's Salt; in comparison the previous highest value was −10 using a solid-state microwave power source (maximum power 45 mW). The increased enhancements are partly due to larger microwave saturation and elevated sample temperature. These experimentally observed DNP enhancements, which by far exceed the predicted values extrapolated from low-field DNP experiments, demonstrate experimentally that DNP is possible in the liquid state also at high magnetic fields.

Gyrotron

Saturation (graph theory)

Microwave power

10.1039/c003697h

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Carr–Purcell Pulsed Electron Double Resonance with Shaped Inversion Pulses

The Journal of Physical Chemistry Letters (2015)

Philipp E. Spindler Izabela Waclawska Burkhard Endeward J. Plackmeyer Christine Ziegler

Pulsed electron paramagnetic resonance (EPR) spectroscopy allows the determination of distances, in the range of 1.5-8 nm, between two spin-labels attached to macromolecules containing protons. Unfortunately, for hydrophobic lipid-bound or detergent-solubilized membrane proteins, the maximum distance accessible is much lower, because of a strongly reduced coherence time of the electron spins. Here we introduce a pulse sequence, based on a Carr-Purcell decoupling scheme on the observer spin, where each π-pulse is accompanied by a shaped sech/tanh inversion pulse applied to the second spin, to overcome this limitation. This pump/probe excitation scheme efficiently recouples the dipolar interaction, allowing a substantially longer observation time window to be achieved. This increases the upper limit and accuracy of distances that can be determined in membrane protein complexes. We validated the method on a bis-nitroxide model compound and applied this technique to the trimeric betaine transporter BetP. Interprotomer distances as long as 6 nm could be reliably determined, which is impossible with the existing methods.

Pulsed EPR

Site-directed spin labeling

10.1021/acs.jpclett.5b01933

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Citations (82)

2D-REFINE spectroscopy: Separation of overlapping hyperfine spectra

Journal of Magnetic Resonance (2008)

Adrian Cernescu Thorsten Maly Thomas F. Prisner

10.1016/j.jmr.2008.02.018

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Mixed-valence compounds as polarizing agents for Overhauser dynamic nuclear polarization in solids

Andrei Gurinov Benedikt Sieland Andrey A. Kuzhelev Hossam Elgabarty Thomas D. Kühne

In this paper we investigate a novel set of polarizing agents -- mixed-valence compounds -- by theoretical and experimental methods and demonstrate their performance in high-field Dynamic Nuclear Polarization (DNP) experiments in the solid state. Mixed-valence compounds constitute a group of molecules, in which molecular mobility persists even in solids. Consequently, such polarizing agents can be used to perform Overhauser-DNP experiments in solid-state, with favorable conditions for dynamic nuclear polarization formation at ultra-high magnetic fields.

Nuclear Overhauser effect

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