A nuclear magnetic resonance spectrometer concept for hermetically sealed magic angle spinning investigations on highly toxic, radiotoxic, or air sensitive materials

Abstract

A concept to integrate a commercial high-resolution, magic angle spinning nuclear magnetic resonance (MAS-NMR) probe capable of very rapid rotation rates (70 kHz) in a hermetically sealed enclosure for the study of highly radiotoxic materials has been developed and successfully demonstrated. The concept centres on a conventional wide bore (89 mm) solid-state NMR magnet operating with industry standard 54 mm diameter probes designed for narrow bore magnets. Rotor insertion and probe tuning take place within a hermetically enclosed glovebox, which extends into the bore of the magnet, in the space between the probe and the magnet shim system. Oxygen-17 MAS-NMR measurements demonstrate the possibility of obtaining high quality spectra from small sample masses (∼10 mg) of highly radiotoxic material and the need for high spinning speeds to improve the spectral resolution when working with actinides. The large paramagnetic susceptibility arising from actinide paramagnetism in (Th 1−x U x )O 2 solid solutions gives rise to extensive spinning sidebands and poor resolution at 15 kHz, which is dramatically improved at 55 kHz. The first 17 O MAS-NMR measurements on NpO 2+x samples spinning at 55 kHz are also reported. The glovebox approach developed here for radiotoxic materials can be easily adapted to work with other hazardous or even air sensitive materials.

Local Structure and Magnetism of La1–xMxPO4 (M = Sm, 239Pu, 241Am) Explained by Experimental and Computational Analyses

“…All experiments were performed on a Bruker AVANCE III 9.4 T spectrometer with an NMR probe embedded in a nuclear glovebox . The spectra were recorded at 50 kHz at a 31 P Larmor frequency of 161.976 MHz.…”

Self-healing capacity of nuclear glass observed by NMR spectroscopy

“…Here, an alternative approach was deployed, as adopted by Martel et al . 25 . At JRC-ITU a glove-box was designed to confine the whole MAS NMR probe inside the magnet bore so that the former could be employed at its nominal performance.…”

“…In this work, MAS NMR housed in a glove-box (see Martel et al . 25 ) enabled very high sample spinning-frequency (40–50 kHz) using standard MAS NMR containers (1.3 mm outer diameter). 29 Si, 23 Na, 11 B and 27 Al could then be probed in old 244 Cm doped glasses, enabling the investigation of the nature of the coupling effect between AP and RN in nuclear glass by comparison of these results with those obtained using heavy ion irradiation of glasses (Xe and Au ions with respective energies of 92 MeV and 1 to 7 MeV, see 6 7 ).…”

Magic Angle Spinning NMR Spectroscopy: A Versatile Technique for Structural and Dynamic Analysis of Solid-Phase Systems

“…64–66 A recent highly exciting breakthrough is the announcement of room temperature and cold cryo-MAS probes from Doty Scientific 67 , which deliver 3 and 12 fold gain in sensitivity, respectively, compared to the conventional probes.…”