Nuclear Magnetic Resonance studies of DNP-ready trehalose obtained by solid state mechanochemical amorphization

TL;DR

This study investigates the nuclear spin relaxation and dynamic nuclear polarization in amorphous trehalose samples doped with radicals, prepared via mechanochemical amorphization, revealing polarization efficiencies comparable to standard solutions and insights into relaxation mechanisms.

Contribution

It demonstrates that amorphous trehalose prepared by mechanochemical milling can achieve DNP performance similar to traditional solutions, supporting broader use in imaging applications.

Findings

Achieved 15% polarization at 1.6 K in amorphous trehalose with 0.50% radicals.

Found relaxation rates follow a power law with an exponent near 3.

Confirmed the presence of Thermal Mixing and effective spin contact.

Abstract

$^1$H nuclear spin-lattice relaxation and Dynamic Nuclear Polarization (DNP) have been studied in amorphous samples of trehalose sugar doped with TEMPO radicals by means of mechanical milling, in the 1.6 K $\div$ 4.2 K temperature range. The radical concentration was varied between 0.34 and 0.81 $\%$. The highest polarization of 15 \% at 1.6 K, observed in the sample with concentration $0.50 \%$, is of the same order of magnitude of that reported in standard frozen solutions with TEMPO. The temperature and concentration dependence of the spin-lattice relaxation rate $1/T_{\text{1}}$, dominated by the coupling with the electron spins, were found to follow power laws with an exponent close to $3$ in all samples. The observed proportionality between $1/T_{\text{1}}$ and the polarization rate $1/T_{\text{pol}}$, with a coefficient related to the electron polarization, is consistent with the presence of Thermal Mixing (TM) and a good contact between the nuclear and the electron spins. At high electron concentration additional relaxation channels causing a decrease in the nuclear polarization must be considered. These results provide further support for a more extensive use of amorphous DNP-ready samples, obtained by means of comilling, in dissolution DNP experiments and possibly for $\textit{in vivo}$ metabolic imaging.