¹³C Dynamic Nuclear Polarization Using a Trimeric Gd³⁺ Complex as an Additive

Dissolution dynamic nuclear polarization (DNP) is one of the most successful techniques that resolves the insensitivity problem in liquid-state nuclear magnetic resonance (NMR) spectroscopy and imaging (MRI) by amplifying the signal by several thousand-fold. One way to further improve the DNP signal is the inclusion of trace amounts of lanthanides in DNP samples doped with trityl OX063 free radical as the polarizing agent. In practice, stable monomeric gadolinium complexes such as Gd-DOTA or Gd-HP-DO3A are used as beneficial additives in DNP samples, further boosting the DNP-enhanced solid-state ¹³C polarization by a factor of 2 or 3. Herein, we report on the use of a trimeric gadolinium complex as a dopant in ¹³C DNP samples to improve the ¹³C DNP signals in the solid-state at 3.35 T and 1.2 K and consequently, in the liquid-state at 9.4 T and 298 K after dissolution. Our results have shown that doping the ¹³C DNP sample with a complex which holds three Gd³⁺ ions led to an improvement of DNP-enhanced ¹³C polarization by a factor of 3.4 in the solid-state, on par with those achieved using monomeric Gd³⁺ complexes but only requires about one-fifth of the concentration. Upon dissolution, liquid-state ¹³C NMR signal enhancements close to 20 000-fold, approximately 3-fold the enhancement of the control samples, were recorded in the nearby 9.4 T high resolution NMR magnet at room temperature. Comparable reduction of ¹³C spin-lattice T₁ relaxation time was observed in the liquid-state after dissolution for both the monomeric and trimeric Gd³⁺ complexes. Moreover, W-band electron paramagnetic resonance (EPR) data have revealed that 3-Gd doping significantly reduces the electron T₁ of the trityl OX063 free radical, but produces negligible changes in the EPR spectrum, reminiscent of the results with monomeric Gd³⁺-complex doping. Our data suggest that the trimeric Gd³⁺ complex is a highly beneficial additive in ¹³C DNP samples and that its effect on DNP efficiency can be described in the context of the thermal mixing mechanism.