Liquid state DNP for water accessibility measurements on spin-labeled membrane proteins at physiological temperatures

Doll, Andrin; Bordignon, Enrica; Joseph, Benesh; Tschaggelar, René; Jeschke, Gunnar

doi:10.1016/j.jmr.2012.06.003

Cited by 41 publications

(41 citation statements)

References 41 publications

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“…We will find it convenient to refer to 1 − E (which is referred to in other literature as “ ε ” or “− ε ”, e.g. [24]) as the “amount of polarization transferred” [25]. Following Hausser one can solve Eq.…”

Section: Reviewmentioning

confidence: 99%

“…Thus, one can avoid both the benefits and the pitfalls alluded to earlier in this section by presenting a more qualitative parameter that describes water accessibility. Through application to select spin-labeled protein systems, they are able to empirically demonstrate that ODNP can measure the accessibility of the spin probe to the aqueous solvent in complex and important biomolecular systems, such as an ABC transporter protein embedded in lipid membranes [24]. …”

Section: Reviewmentioning

confidence: 99%

“…The Bennati group adopted a different strategy, performing X-band DNP experiments with a commercial amplifier added on to the output of an ESR spectrometer, and re-purposing commercial ENDOR probes as DNP probes [3, 30]. Most recently Doll et al [24] presented a high-quality home-built resonator, which includes a resonant NMR probe firmly mounted inside a dielectric resonator. Both the NMR and ESR performances of this device are excellent.…”

Section: Reviewmentioning

confidence: 99%

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Quantitative cw Overhauser effect dynamic nuclear polarization for the analysis of local water dynamics

Franck

Pavlova

Scott

et al. 2013

Progress in Nuclear Magnetic Resonance Spectroscopy

123

237

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Liquid state Overhauser Effect Dynamic Nuclear Polarization (ODNP) has experienced a recent resurgence of interest. The ODNP technique described here relies on the double resonance of electron spin resonance (ESR) at the most common, i.e. X-band (~ 10 GHz), frequency and 1H nuclear magnetic resonance (NMR) at ~ 15 MHz. It requires only a standard continuous wave (cw) ESR spectrometer with an NMR probe inserted or built into an X-band cavity. Our focus lies on reviewing a new and powerful manifestation of ODNP as a high frequency NMR relaxometry tool that probes dipolar cross relaxation between the electron spins and the 1H nuclear spins at X-band frequencies. This technique selectively measures the translational mobility of water within a volume extending 0.5–1.5 nm outward from a nitroxide radical spin probe that is attached to a targeted site of a macromolecule. This method has been applied to study the dynamics of water that hydrates or permeates the surface or interior of proteins, polymers, and lipid membrane vesicles. We begin by reviewing the recent advances that have helped develop ODNP into a tool for mapping the dynamic landscape of hydration water with sub-nanometer locality. In order to bind this work coherently together, and to place it in the context of the extensive body of research in the field of NMR relaxometry, we then rephrase the analytical model and extend the description of the ODNP-derived NMR signal enhancements. This extended model highlights several aspects of ODNP data analysis, including the importance of considering all possible effects of microwave sample heating, the need to consider the error associated with various relaxation rates, and the unique ability of ODNP to probe the electron–1H cross-relaxation process, which is uniquely sensitive to fast (tens of ps) dynamical processes. By implementing the relevant corrections in a stepwise fashion, this paper draws a consensus result from previous ODNP procedures, and then shows how such data can be further corrected to yield clear and reproducible saturation of the NMR hyperpolarization process. Finally, drawing on these results, we broadly survey the previous ODNP dynamics literature. We find that the vast number of published, empirical hydration dynamics data can be reproducibly classified into regimes of surface, interfacial, vs buried water dynamics.

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Section: Reviewmentioning

confidence: 99%

Section: Reviewmentioning

confidence: 99%

Section: Reviewmentioning

confidence: 99%

See 1 more Smart Citation

Quantitative cw Overhauser effect dynamic nuclear polarization for the analysis of local water dynamics

Franck

Pavlova

Scott

et al. 2013

Progress in Nuclear Magnetic Resonance Spectroscopy

123

237

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“…Overhauser DNP results for spin-labeled membrane proteins [18,19], but this has not yet been carried out. However, diffusion constants of water in the vicinity of MTSL spin labels and native amino acids have been investigated in an earlier MD study [86].…”

Section: Dynamics Of Spin Labels and Relaxationmentioning

confidence: 99%

“…Such SDSL techniques are widely applied in PRE studies. They have also been used in recent liquidstate DNP work [18,19], and may become attractive for solid-state DNP [20]. Once a protein or nucleic acid is spin labeled, further information can be obtained from CW EPR experiments [14] or distance measurements between spin labels by pulsed EPR techniques [21].…”

Section: Introductionmentioning

confidence: 99%

Conformational dynamics and distribution of nitroxide spin labels

Jeschke

2013

Progress in Nuclear Magnetic Resonance Spectroscopy

Self Cite

138

115

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Long-range distance measurements based on paramagnetic relaxation enhancement (PRE) in NMR, quantification of surface water dynamics near biomacromolecules by Overhauser dynamic nuclear polarization (DNP) and sensitivity enhancement by solid-state DNP all depend on introducing paramagnetic species into an otherwise diamagnetic NMR sample. The species can be introduced by site-directed spin labeling, which offers precise control for positioning the label in the sequence of a biopolymer. However, internal flexibility of the spin label gives rise to dynamic processes that potentially influence PRE and DNP behavior and leads to a spatial distribution of the electron spin even in solid samples. Internal dynamics of spin labels and their static conformational distributions have been studied mainly by electron paramagnetic resonance spectroscopy and molecular dynamics simulations, with a large body of results for the most widely applied methanethiosulfonate spin label MTSL. These results are critically discussed in a unifying picture based on rotameric states of the group that carries the spin label. Deficiencies in our current understanding of dynamics and conformations of spin labeled groups and of their influence on NMR observables are highlighted and directions for further research suggested.

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Electron Paramagnetic Resonance Spectroscopy

Jeschke¹

2013

Ullmann's Encyclopedia of Industrial Chemistry

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The article contains sections titled: 1. Introduction 2. Principles of EPR 2.1. Electron and Nuclear Spins 2.2. High‐Field Approximation and Forbidden Transitions 2.3. Relaxation and Linewidths 3. The EPR Experiment 3.1. Continuous‐Wave EPR 3.1.1. Continuous‐Wave ENDOR and Triple Resonance 3.1.2. Progressive Saturation 3.1.3. Saturation‐Transfer EPR 3.2. Pulse EPR 3.2.1. Fourier‐Transform EPR 3.2.2. Echo‐Detected EPR 3.2.3. Relaxation Measurements 3.2.4. ESEEM and HYSCORE 3.2.5. Pulse ENDOR 3.2.6. Pulse ELDOR and Double‐Quantum EPR 3.3. EPR Imaging 4. Spectral Parameters 4.1. g ‐Factor 4.2. Hyperfine Interaction 4.3. Zero‐Field Splitting 4.4. Exchange Interaction 4.5. Dipole–Dipole Interaction 4.6. Spin Concentration 5. EPR in the Liquid State and in Soft Matter 5.1. Slow Molecular Tumbling and Local Order 5.2. Heisenberg Spin Exchange 6. Computation of Parameters and Spectra 6.1. Parameter Prediction 6.2. Data Analysis and Spectrum Simulation 7. Specialist Techniques 7.1. Spin Trapping 7.2. Spin Probing and Labeling 7.3. EPR Oxymetry 7.4. EPR Dosimetry and Dating

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Liquid state DNP for water accessibility measurements on spin-labeled membrane proteins at physiological temperatures

Cited by 41 publications

References 41 publications

Quantitative cw Overhauser effect dynamic nuclear polarization for the analysis of local water dynamics

Quantitative cw Overhauser effect dynamic nuclear polarization for the analysis of local water dynamics

Conformational dynamics and distribution of nitroxide spin labels

Electron Paramagnetic Resonance Spectroscopy

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