Selected Publications
Amorphous quininium aspirinate from neat mechanochemistry: diffracting nanocrystalline domains and quick recrystallization upon exposure to solvent vapours
Quininium aspirinate is mechanochemically prepared as a crystalline solid by liquid-assisted grinding, or as an amorphous phase (as determined by X-ray powder diffraction), by neat grinding or neat ball milling. Our previous work demonstrated using FT-IR spectroscopy that a mechanochemical reaction had occurred in the mechanically treated neat mixtures. Herein is reported that microcrystal electron diffraction (microED) afforded the discovery of two diffracting micron-size particles in the amorphous powder synthesized by manual grinding, among a majority of non-diffracting particles. Remarkably, microED data of one of them led to the known lattice parameters of quininium aspirinate. Furthermore, this so-called ‘X-ray amorphous’ phase quickly recrystallizes upon exposure to vapors of N,N-dimethylformamide, or hexane vapours (at a lower rate); but it remains amorphous for longer than 20 months when stored at ambient conditions in a closed container. The lattice parameters and the degrees of crystallinity of both recrystallized materials are identical within the experimental error. However, slightly more intense and better-resolved X-ray powder diffraction peaks are observed in the material recrystallized from N,N-dimethylformamide vapours than in the analogous phase recovered from hexane. As expected, Williamson–Hall graphs lead to a larger average crystalline domain size for the former solid. These results illustrate the use of microED for the investigation of structural features in amorphous phases, and the generic role of the solvent vapours in promoting their recrystallization.
Outstanding Advantages, Current Drawbacks, and Significant Recent Developments in Mechanochemistry: A Perspective View
Although known since antiquity, mechanochemistry has remained dormant for centuries. Nowadays, mechanochemistry is a flourishing research field at the simultaneous stages of gathering data and (often astonishing) observations, and scientific argumentation toward their analysis, for which the combination of interdisciplinary expertise is necessary. Mechanochemistry’s implementation as a synthetic method is constantly increasing, although it remains far from being fully exploited, or understood on the basis of fundamental principles. This review starts by describing many remarkable
advantages of mechanochemical reactions, simplifying and “greening” chemistry in solutions. This description is followed by an overview of the current main weaknesses to be addressed in the near future toward the systematic study of its energetics and chemical mechanisms. This review finishes by describing recent breakthrough experimental advances, such as in situ kinetics monitoring using synchrotron X-ray powder diffraction and Raman spectroscopy, plus equally significant computational chemistry approaches, such as quantum mechanochemistry, used for the understanding of covalent or hydrogen bond ruptures in biomolecules or mechanophores in polymers at the single-molecule level. Combined with new technologies to control temperature and pressure in ball
mills, these appealing new methods are promising tools for establishing the fundamental knowledge necessary for the understanding of mechanochemical reactivity and mechanisms.