Perspectives on DNP-enhanced NMR spectroscopy in solutions

Bentum, Jan van; Meerten, Bas van; Sharma, Manvendra; Kentgens, A.P.M.

doi:10.1016/j.jmr.2016.01.010

Cited by 41 publications

(27 citation statements)

References 77 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The development of spectrometers operating at ultrahigh fields and of ultrasensitive cryogenic probes will likely provide only a partial solution to this problem. The development of other methods, such as room temperature nuclear dynamic polarization , will be necessary to gain a sensitivity high enough to detect NAs at a level corresponding to their physiological concentrations. For all in‐cell NMR experiments, in which high intracellular concentrations (> 50 μ m ) are employed, the biological relevance of the results needs to be critically considered.…”

Section: Discussionmentioning

confidence: 99%

Advances in the cellular structural biology of nucleic acids

et al. 2018

View full text Add to dashboard Cite

Conventional biophysical and chemical biology approaches for delineating relationships between the structure and biological function of nucleic acids (NAs) abstract NAs from their native biological context. However, cumulative experimental observations have revealed that the structure, dynamics and interactions of NAs might be strongly influenced by a broad spectrum of specific and nonspecific physical-chemical environmental factors. This consideration has recently sparked interest in the development of novel tools for structural characterization of NAs in the native cellular context. Here, we review the individual methods currently being employed for structural characterization of NA structure in a native cellular environment with a focus on recent advances and developments in the emerging fields of in-cell NMR and electron paramagnetic resonance spectroscopy and in-cell single-molecule FRET of NAs.

show abstract

Section: Discussionmentioning

confidence: 99%

Advances in the cellular structural biology of nucleic acids

et al. 2018

View full text Add to dashboard Cite

show abstract

“…However, the low sensitivity of NMR spectroscopy hindered our efforts to detect minor reaction intermediates. Therefore, sensitivity enhancement techniques such as dynamic nuclear polarization (DNP) NMR methods and/or presaturation methods to increase the dynamic range of the proton spectra by pre‐saturating large water signals, are expected to be useful to detect low‐concentration species. In the future, the amount of methanol crossover will be calibrated by simultaneously analyzing anode and cathode exhausts, and the evaporation of methanol will be calibrated by measuring the time‐dependent concentration of methanol at 80°C.…”

Section: Nmr Peak Areas and Widths Of Anode Exhausts And Currents Of mentioning

confidence: 99%

Nuclear Magnetic Resonance Spectroscopic Investigation of Anode Exhaust of Direct Methanol Fuel Cells Without Isotope Enrichment

Byun

Hwang

Han

2016

Bulletin Korean Chem Soc

View full text Add to dashboard Cite

“…6,7 Solution studies have mainly focussed on water, since its small size leads to fast rotational dynamics, leading to relatively high enhancements even at high magnetic fields. [7][8][9][10][11][12] There is great potential for the study of hydration dynamics of proteins and soft materials, 13,14 as well as polarization transfer to other molecules. 15 However, since water interacts very strongly with the electric fields of microwaves, dielectric heating is a significant issue in aqueous solutions, particularly when working with temperature-sensitive biological molecules, or when the coupling factor needs to be known accurately.…”

mentioning

confidence: 99%

Optically-generated Overhauser dynamic nuclear polarization: A numerical analysis

Cheney

Wedge

2020

The Journal of Chemical Physics

View full text Add to dashboard Cite

Recently, an alternative approach to dynamic nuclear polarization (DNP) in the liquid state was introduced, using optical illumination instead of microwave pumping. By exciting a suitable dye to the triplet state which undergoes diffusive encounter with a persistent radical forming a quartet-doublet pair in the encounter complex, dynamic electron polarization (DEP) is generated via the radical-triplet pair mechanism (RTPM). Subsequent cross-relaxation generates nuclear polarization without the need for microwave saturation of the electronic transitions. Here, we present a theoretical justification for the initial experimental results, by means of numerical simulations. These allow investigation of the effects of various experimental parameters, such as radical and dye concentrations, sample geometry, and laser power, on the DNP enhancement factors, providing targets for experimental optimization. It is predicted that reducing the sample volume will result in larger enhancements, by permitting a higher concentration of triplets in a sample of increased optical density. We also explore the effects of pulsed laser rather than continuous-wave illumination, rationalising the failure to observe the optical DNP effect under illumination conditions common to DEP experiments. Examining the influence of illumination duty cycle the conditions necessary to permit use of pulsed illumination without compromising signal enhancement are determined, which may reduce undesirable laser heating effects. This first simulation of the optical DNP method therefore underpins the further development of the technology. I. INTRODUCTION Among all of the hyperpolarization techniques for overcoming the intrinsically low sensitivity of Nuclear Magnetic Resonance (NMR) spectroscopy, Dynamic Nuclear Polarization (DNP) is the most studied and widely applicable. 1 It was first proposed by Overhauser in 1953, 2 and demonstrated experimentally by Carver and Slichter, 3 that saturating Electron Paramagnetic Resonance (EPR) transitions results in an increase in NMR sensitivity. This effect, due to cross-relaxation between the electron and nuclear spins, was later extended from lithium to free radicals in solution, 4 but has never been widely applied due to technical challenges and problems with reducing Overhauser efficiency at the high magnetic fields necessary for high resolution NMR spectroscopy.

show abstract

Perspectives on DNP-enhanced NMR spectroscopy in solutions

Cited by 41 publications

References 77 publications

Advances in the cellular structural biology of nucleic acids

Advances in the cellular structural biology of nucleic acids

Nuclear Magnetic Resonance Spectroscopic Investigation of Anode Exhaust of Direct Methanol Fuel Cells Without Isotope Enrichment

Optically-generated Overhauser dynamic nuclear polarization: A numerical analysis

Contact Info

Product

Resources

About