The first part of the work consisted of building up the analytical setup, which can be conceptually divided in four main blocks (Figure ): gas settings, milling, trapping of the sublimated species, and NMR analysis. In a typical run (see Section 2 of the Supporting Information for a detailed description of the apparatus and its operation), an inert carrier gas (nitrogen or argon) was first regulated in its pressure (0.3-0.4 bar) and flow (0.1-1.5 L/min) and then passed through the milling vessel at the same time as the grinding is conducted. All experiments were performed in a custom made 20 mL milling jar made of duralumin presenting an inlet and an outlet gas connection. The latter included an internal cotton pad to prevent the passage of powder particles directly in the PTFE connecting tubing. The grinding action was conducted using 4.0 g of Ø 2 mm glass beads at the frequency of 10 Hz, which allowed for a constant and uniform distribution of the powders on the high surface of the milling media without damaging the soft material of the vessel. Also, the thermal conductivity of the duralumin material of the jar in combination with the "soft" grinding conditions ensured a constant (or at least non-detectable increase of the) jar temperature during milling, which in turn could have affected the sublimation phenomena. The gas flow at the exit of the milling jar, enriched with the sublimated species, was then bubbled into dimethyl sulfoxide (DMSO), where the sublimate dissolved. Finally, the analyte in the DMSO solution was in operando monitored by circulating the liquid through a glass flow cell inside of an NMR benchtop system. This part of the apparatus, designed and developed by Magritek GmbH, specifically consisted of a software controlled peristaltic pump, which alternated phases of pumping (to refresh the analyte solution through the NMR magnet) and rest (to allow the development of the required sample pre-magnetization and its analysis) optimized according to the observed analyte.