RESUMEN

Complexes of paramagnetic metal ions, in particular Gd3+, have been demonstrated as efficient polarising agents for magic-angle spinning (MAS) dynamic nuclear polarisation (DNP). We recently demonstrated that commercially available and inexpensive Gd(NO3)3 is suitable for use as an "off-the-shelf" MAS DNP polarising agent, providing promising sensitivity enhancements to 1H, 13C, and 15N NMR signals. Here we expand upon this approach by investigating the impact of the Gd(NO3)3 concentration and by exploring a larger range of readily available Gd3+ sources. We found that a Gd(NO3)3 concentration of 20 mM in the case of 1H and 13C, and 40 mM in the case of 15N, offers optimum signal enhancements and is rationalised as a trade-off between DNP enhancements, polarisation build-up times, and electron paramagnetic resonance (EPR) spin-spin relaxation times. We determined that a range of different gadolinium compounds (GdCl3, Gd2(SO4)3, GdBr3, and Gd(OAc)3) are also suitable for use as polarising agents and yield 1H, 13C, and 15N signal enhancements of variable values. Gd(OAc)3 yields lower signal enhancements, which is proposed to be the result of greater local asymmetry at the Gd3+ centre leading to EPR line broadening, and the methyl group in the acetate ion acting as a relaxation sink and limiting the nuclear polarisation available.

RESUMEN

Magic angle spinning nuclear magnetic resonance spectroscopy experiments are widely employed in the characterization of solid media. The approach is incredibly versatile but deleteriously suffers from low sensitivity, which may be alleviated by adopting dynamic nuclear polarization methods, resulting in large signal enhancements. Paramagnetic metal ions such as Gd3+ have recently shown promising results as polarizing agents for 1H, 13C, and 15N nuclear spins. We demonstrate that the widely available and inexpensive chemical agent Gd(NO3)3 achieves significant signal enhancements for the 13C and 15N nuclear sites of [2-13C,15N]glycine at 9.4 T and ∼105 K. Analysis of the signal enhancement profiles at two magnetic fields, in conjunction with electron paramagnetic resonance data, reveals the solid effect to be the dominant signal enhancement mechanism. The signal amplification obtained paves the way for efficient dynamic nuclear polarization without the need for challenging synthesis of Gd3+ polarizing agents.

Asunto(s)

RESUMEN

The optical dynamic nuclear polarization (DNP) method has been proposed as an alternative to microwave pumping as a hyperpolarization method for solution-state NMR studies. Using continuous laser illumination to photogenerate triplet states in the presence of a persistent radical produces chemically-induced dynamic electron polarization (CIDEP) via the radical-triplet pair mechanism (RTPM), with cross-relaxation transferring this to nuclear hyperpolarization via an Overhauser mechanism. Numerical simulations have previously indicated that reducing the sample volume while maintaining a constant optical density can significantly increase the NMR signal enhancement, due to the larger steady-state concentration of triplets obtained. Here we provide the first experimental confirmation of these effects, producing a nearly five-fold increase in the optical DNP enhancement factor just by reducing the sample volume with optimal dye and radical concentrations adjusted for each optical path length. The results are supported with an in depth analysis of volume effects in the numerical model, with which they are in good qualitative agreement. These important observations will impact on the future development of the technique, with particular significance for attempts to apply DNP methods to increase sensitivity for volume-limited biological samples.

Asunto(s)

RESUMEN

Spin hyperpolarization can dramatically increase signal intensities in magnetic resonance experiments, providing either improved bulk sensitivity or additional spectroscopic detail through selective enhancements. While typical hyperpolarization approaches have utilized microwave irradiation, one emerging route is the use of optically generated triplet states. We report an investigation into the effects of solution viscosity on radical-triplet pair interactions, propose a new standard for quantification of the hyperpolarization in EPR experiments, and demonstrate a significant increase in the optically generated 1H NMR signal enhancement upon addition of glycerol to aqueous solutions.

RESUMEN

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 a 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. 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 the pulsed laser rather than continuous-wave illumination, rationalizing the failure to observe the optical DNP effect under illumination conditions common to DEP experiments. Examining the influence of the illumination duty cycle, the conditions necessary to permit the 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.