Optimisation of dynamic nuclear polarisation of [1-13C] pyruvate by addition of gadolinium-based contrast agents

Friesen-Waldner, Lanette; Chen, Albert; Mander, Will; Scholl, Timothy J.; McKenzie, Charles A.

doi:10.1016/j.jmr.2012.07.010

Cited by 27 publications

(80 citation statements)

References 13 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…41 While a variety of Ln(iii) complexes have numerous biomedical applications, particularly in contrast-enhanced MRI, 45 only Gd 3+ and Ho 3+ have been studied extensively as beneficial doping agents in 13 C dissolution DNP. [35][36][37][38] This in part takes precedent from a previous preliminary study which has shown that only Gd 3+ and Ho 3+ ions have beneficial effects on 13 C DNP, while the other Ln(iii) ions appear to have no apparent effect on 13 C DNP enhancements for trityldoped samples. 37 We would like to note that the measurements in the aforementioned previous DNP study on using lanthanide ions 37 were not really extensively optimized in terms of concentration dependence and the fact that the optimum DNP microwave frequency could shift with lanthanide doping.…”

Section: Introductionmentioning

confidence: 78%

“…The EPR experiments were performed prior to DNP experiments, and as such optimal concentrations had not yet been determined. Previous work has shown that the optimal concentration for both gadolinium and holmium is 2 mM, 34,35,38 so this was chosen to be the concentration of terbium and dysprosium studied in order to compare their electron T 1 under the same conditions. Measurements were performed at the National High Magnetic Field Laboratory (NHMFL) in Tallahassee, FL in the W-band (94 GHz) on a Bruker E680 EPR spectrometer (Bruker Biospin, Billerica, MA) using a Bruker TE 011 cylindrical cavity.…”

Section: B Epr Measurementsmentioning

confidence: 99%

“…This is in line with previous studies which have used the same method to compare DNP performance. 32,[35][36][37][38] Build-up curves were recorded and fit with single exponential equations, and using the fit, the relative polarization at 10 000 s was extrapolated.…”

Section: Hyperpolarization and Nmr Measurementsmentioning

confidence: 99%

“…[31][32][33] Meanwhile, the trityls, particularly OX063, which have some of the narrowest EPR linewidths among free radicals, were found to be excellent polarizing agents for low-γ nuclei like 13 C. 16,34 When using these radicals, DNP enhancements may be improved further by the addition of trace amounts of gadolinium. [34][35][36][37] Recently, it was found that the addition of holmium to a trityl-doped sample results in liquid state enhancement similar to that achieved by using gadolinium. 38 While the use of these lanthanides may lead to significant polarization gains, the free ion form of these lanthanides may lead to greater toxicity of the DNP sample, which must be considered prior to in vivo biomedical application.…”

Section: Introductionmentioning

confidence: 96%

See 3 more Smart Citations

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

Niedbalski

Parish

Kiswandhi

et al. 2017

The Journal of Chemical Physics

View full text Add to dashboard Cite

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.

show abstract

Section: Introductionmentioning

confidence: 78%

Section: B Epr Measurementsmentioning

confidence: 99%

Section: Hyperpolarization and Nmr Measurementsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 96%

See 2 more Smart Citations

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

Niedbalski

Parish

Kiswandhi

et al. 2017

The Journal of Chemical Physics

View full text Add to dashboard Cite

show abstract

“…Current trends suggest that the narrow ESR linewidth free radicals trityl OX063 and BDPA yielded generally higher 13 C polarization levels than the broad linewidth free radicals galvinoxyl, DPPH and 4-oxo-TEMPO. Sample preparation optimization via addition of trace amounts of gadolinium and other lanthanides in the sample [27, 29, 36, 37] or deuteration of the glassing matrix [13, 14]. On the instrumentation side, lowering the operating temperature and increasing the magnetic field of the polarizer [10, 11] may be explored in the future to further amplify the DNP-enhanced nuclear polarization.…”

Section: Resultsmentioning

confidence: 99%

Development and performance of a 129-GHz dynamic nuclear polarizer in an ultra-wide bore superconducting magnet

Lumata

Martin

Jindal

et al. 2014

Magn Reson Mater Phy

View full text Add to dashboard Cite

Objective We sought to build a dynamic nuclear polarization system for operation at 4.6 T (129 GHz) and evaluate its efficiency in terms of 13C polarization levels using free radicals that span a range of ESR linewidths. Materials and methods A liquid helium cryostat was placed in a 4.6 T superconducting magnet with a 150-mm warm bore diameter. A 129-GHz microwave source was used to irradiate 13C enriched samples. Temperatures close to 1 K were achieved using a vacuum pump with a 453-m3/h roots blower. A hyperpolarized 13C nuclear magnetic resonance (NMR) signal was detected using a saddle coil and a Varian VNMRS console operating at 49.208 MHz. Samples doped with free radicals BDPA (1,3-bisdipheny-lene-2-phenylallyl), trityl OX063 (tris{8-carboxyl-2,2,6,6-benzo(1,2-d:4,5-d)-bis(1,3)dithiole-4-yl}methyl sodium salt), galvinoxyl ((2,6-di-tert-butyl-α-(3,5-di-tert-butyl-4-oxo-2,5-cyclohexadien-1-ylidene)-p-tolyloxy), 2,2-diphenylpicrylhydrazyl (DPPH) and 4-oxo-TEMPO (4-Oxo-2,2,6,6-tetramethyl-1-piperidinyloxy) were assayed. Microwave dynamic nuclear polarization (DNP) spectra and solid-state 13C polarization levels for these samples were determined. Results 13C polarization levels close to 50 % were achieved for [1-13C]pyruvic acid at 1.15 K using the narrow electron spin resonance (ESR) linewidth free radicals trityl OX063 and BDPA, while 10–20 % 13C polarizations were achieved using galvinoxyl, DPPH and 4-oxo-TEMPO. Conclusion At this field strength free radicals with smaller ESR linewidths are still superior for DNP of 13C as opposed to those with linewidths that exceed that of the 1H Larmor frequency.

show abstract

Quantitation of a spin polarization‐induced nuclear Overhauser effect (SPINOE) between a hyperpolarized ¹³C‐labeled cell metabolite and water protons

Marco‐Rius

Bohndiek

Kettunen

et al. 2014

Contrast Media & Molecular

View full text Add to dashboard Cite

The spin polarization-induced nuclear Overhauser effect (SPINOE) describes the enhancement of spin polarization of solvent nuclei by the hyperpolarized spins of a solute. In this communication we demonstrate that SPINOEs can be observed between [1,4-13C2]fumarate, hyperpolarized using the dissolution dynamic nuclear polarization technique, and solvent water protons. We derive a theoretical expression for the expected enhancement and demonstrate that this fits well with experimental measurements. Although the magnitude of the effect is relatively small (around 2% measured here), the SPINOE increases at lower field strengths, so that at clinically relevant magnetic fields (1.5–3 T) it may be possible to track the passage through the circulation of a bolus containing a hyperpolarized 13C-labeled substrate through the increase in solvent water 1H signal. © 2014 The Authors. Contrast Media & Molecular Imaging published by John Wiley and Sons, Ltd.

show abstract

Optimisation of dynamic nuclear polarisation of [1-13C] pyruvate by addition of gadolinium-based contrast agents

Cited by 27 publications

References 13 publications

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

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

Development and performance of a 129-GHz dynamic nuclear polarizer in an ultra-wide bore superconducting magnet

Quantitation of a spin polarization‐induced nuclear Overhauser effect (SPINOE) between a hyperpolarized ¹³C‐labeled cell metabolite and water protons

Contact Info

Product

Resources

About

Optimisation of dynamic nuclear polarisation of [1-13C] pyruvate by addition of gadolinium-based contrast agents

Cited by 27 publications

References 13 publications

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

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

Development and performance of a 129-GHz dynamic nuclear polarizer in an ultra-wide bore superconducting magnet

Quantitation of a spin polarization‐induced nuclear Overhauser effect (SPINOE) between a hyperpolarized 13C‐labeled cell metabolite and water protons

Contact Info

Product

Resources

About

Quantitation of a spin polarization‐induced nuclear Overhauser effect (SPINOE) between a hyperpolarized ¹³C‐labeled cell metabolite and water protons