BDPA: An Efficient Polarizing Agent for Fast Dissolution Dynamic Nuclear Polarization NMR Spectroscopy

Lumata, Lloyd; Ratnakar, S. James; Jindal, Ashish; Merritt, Matthew E.; Comment, Arnaud; Malloy, Craig R.; Sherry, A. Dean; Kovács, Zoltán

doi:10.1002/chem.201102037

Cited by 80 publications

(138 citation statements)

References 18 publications

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“…17,18,20,21,31,34,49 Trityl OX063, the stable organic radical used in this work, has a very narrow EPR linewidth that makes it ideal for polarizing low-γ nuclei such as 13 C. When using this free radical to polarize low-γ nuclei such as 13 C spins, DNP data at 3.35 T and temperatures close to 1 K have shown indications of thermal mixing (TM) as the predominant DNP mechanism. 24,[50][51][52][53] Other DNP data at similar conditions suggested that the mechanism could be a combination of the solid effect (SE) and cross effect (CE).…”

Section: Resultsmentioning

confidence: 99%

“…In dissolution DNP, organic free radicals including trityls and nitroxides are most commonly used as the polarizing agents. 16,17 Other radicals such as BDPA, 18 DPPH, 19 and galvinoxyl 20 have been used with some success as well as novel methods such as photoinduced radicals 21 and paramagnetic centers within nanoparticles. 22,23 Nitroxide free radicals have relatively wide EPR linewidths, which are better suited for DNP of high-γ nuclei such as 1 H spins and also provide decent polarization levels for low-γ nuclei such as 13 C. 24 This class of free radicals maintain their popularity by being comparatively inexpensive, highly water soluble, easily scavenged, and effective for cross polarization DNP.…”

Section: Introductionmentioning

confidence: 99%

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Influence of Dy3+ and Tb3+ doping on 13C dynamic nuclear polarization

Niedbalski

Parish

Kiswandhi

et al. 2017

The Journal of Chemical Physics

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Dynamic nuclear polarization (DNP) is a technique that uses a microwave-driven transfer of high spin alignment from electrons to nuclear spins. This is most effective at low temperature and high magnetic field, and with the invention of the dissolution method, the amplified nuclear magnetic resonance (NMR) signals in the frozen state in DNP can be harnessed in the liquid-state at physiologically acceptable temperature for in vitro and in vivo metabolic studies. A current optimization practice in dissolution DNP is to dope the sample with trace amounts of lanthanides such as Gd 3+ or Ho 3+ , which further improves the polarization. While Gd 3+ and Ho 3+ have been optimized for use in dissolution DNP, other lanthanides have not been exhaustively studied for use in 13 C DNP applications. In this work, two additional lanthanides with relatively high magnetic moments, Dy 3+ and Tb 3+ , were extensively optimized and tested as doping additives for 13 C DNP at 3.35 T and 1.2 K. We have found that both of these lanthanides are also beneficial additives, to a varying degree, for 13 C DNP. The optimal concentrations of Dy 3+ (1.5 mM) and Tb 3+ (0.25 mM) for 13 C DNP were found to be less than that of Gd 3+ (2 mM). W-band electron paramagnetic resonance shows that these enhancements due to Dy 3+ and Tb 3+ doping are accompanied by shortening of electron T 1 of trityl OX063 free radical. Furthermore, when dissolution was employed, Tb 3+ -doped samples were found to have similar liquid-state 13 C NMR signal enhancements compared to samples doped with Gd 3+ , and both Tb 3+ and Dy 3+ had a negligible liquid-state nuclear T 1 shortening effect which contrasts with the significant reduction in T 1 when using Gd 3+ . Our results show that Dy 3+ doping and Tb 3+ doping have a beneficial impact on 13 C DNP both in the solid and liquid states, and that Tb 3+ in particular could be used as a potential alternative to Gd 3+ in 13 C dissolution DNP experiments. Published by AIP Publishing.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Influence of Dy3+ and Tb3+ doping on 13C dynamic nuclear polarization

Niedbalski

Parish

Kiswandhi

et al. 2017

The Journal of Chemical Physics

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“…However, increasing the scavenger concentration above a certain threshold will also lead to increased relaxation induced by the presence of ascorbate molecules. A possible way to avoid this issue would be to use radicals such as BDPA (1,3-bisdiphenylene-2-phenylallyl), which can be easily filtered out since they precipitate in aqueous solutions (21).…”

Section: Discussionmentioning

confidence: 99%

Hyperpolarized ⁶Li as a probe for hemoglobin oxygenation level

Balzan

Mishkovsky

Simonenko

et al. 2015

Contrast Media & Molecular

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a Hyperpolarization by dissolution dynamic nuclear polarization (DNP) is a versatile technique to dramatically enhance the nuclear magnetic resonance (NMR) signal intensity of insensitive long-T 1 nuclear spins such as 6 Li. The 6 Li longitudinal relaxation of lithium ions in aqueous solutions strongly depends on the concentration of paramagnetic species, even if they are present in minute amounts. We herein demonstrate that blood oxygenation can be readily detected by taking advantage of the 6 Li signal enhancement provided by dissolution DNP, together with the more than 10% decrease in 6 Li longitudinal relaxation as a consequence of the presence of paramagnetic deoxyhemoglobin.

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“…Pyridine was hyperpolarized by BDPA radicals at ≈40 mM with an equal volume of d 6 -DMSO. Indazole was hyperpolarized in a 1:1 solution of d 6 -DMSO/sulfolane with 40 mM BDPA [24]. Approximately 4 mL of methanold 4 were used to dissolve both samples.…”

Section: Experimental Methodsmentioning

confidence: 99%

HyperSPASM NMR: A new approach to single-shot 2D correlations on DNP-enhanced samples

Donovan

Frydman

2012

Journal of Magnetic Resonance

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Dissolution DNP experiments are limited to a single or at most a few scan, before the nonBoltzmann magnetization has been. This makes it impractical to record 2D NMR data by conventional, t 1 -incremented schemes. Here a new approach termed HyperSPASM to establish 2D heteronuclear correlations in a single scan is reported, aimed at dealing with this kind of challenge. The HyperSPASM experiment relies on imposing an amplitude-modulation of the data by a single Δt 1 indirect-domain evolution time, and subsequently monitoring the imparted encoding on separate echo and the anti-echo pathway signals within a single continuous acquisition. This is implemented via the use of alternating, switching, coherence selection gradients. As a result of these manipulations the phase imparted by a heteronucleus over its indirect domain evolution can be accurately extracted, and 2D data unambiguously reconstructed with a single-shot excitation. The nature of this sequence makes the resulting experiment particularly well suited for the collecting indirectly-detected HSQC data on hyperpolarized samples. The potential of the ensuing "HyperSPASM" method is exemplified with natural-abundance hyperpolarized correlations on model systems.

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BDPA: An Efficient Polarizing Agent for Fast Dissolution Dynamic Nuclear Polarization NMR Spectroscopy

Cited by 80 publications

References 18 publications

Influence of Dy3+ and Tb3+ doping on 13C dynamic nuclear polarization

Influence of Dy3+ and Tb3+ doping on 13C dynamic nuclear polarization

Hyperpolarized ⁶Li as a probe for hemoglobin oxygenation level

HyperSPASM NMR: A new approach to single-shot 2D correlations on DNP-enhanced samples

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BDPA: An Efficient Polarizing Agent for Fast Dissolution Dynamic Nuclear Polarization NMR Spectroscopy

Cited by 80 publications

References 18 publications

Influence of Dy3+ and Tb3+ doping on 13C dynamic nuclear polarization

Influence of Dy3+ and Tb3+ doping on 13C dynamic nuclear polarization

Hyperpolarized 6Li as a probe for hemoglobin oxygenation level

HyperSPASM NMR: A new approach to single-shot 2D correlations on DNP-enhanced samples

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Hyperpolarized ⁶Li as a probe for hemoglobin oxygenation level