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Tandem in situ monitoring for quantitative assessment of mechanochemical reactions involving structurally unknown phases

Lukin, Stipe; Stolar, Tomislav; Tireli, Martina; Blanco, Maria; Babić, Darko; Friščić, Tomislav; Užarević, Krunoslav; Halasz, Ivan (2017) Tandem in situ monitoring for quantitative assessment of mechanochemical reactions involving structurally unknown phases. Chemistry - A European Journal, 23 . pp. 13941-13949. ISSN 0947-6539

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Despite recent advances in real-time and in situ monitoring techniques, a thorough mechanistic understanding of mechanochemical milling reactions is often hindered by the inability of their quantitative evaluation. Here, a tandem approach combining in situ powder X-ray diffraction and Raman spectroscopy enabled quantitative assessment and kinetic analysis of mechanochemical reaction, even when involving new phases of unknown crystal structures, and short-lived intermediates. We also introduce in situ Raman monitoring as a standalone laboratory technique for quantitative assessment of mechanochemical reactions. Our approach is demonstrated on a complex and multi-step mechanochemical cocrystallization of benzoic acid and the model active pharmaceutical ingredient nicotinamide under neat and liquid-assisted grinding, which resulted in complex transformations between four polymorphs. Reaction pathways and polymorph selectivity can be tuned by both the choice of a liquid additive and its amount. Our results provide an important step toward a complete and high-throughput quantitative approach to mechanochemical reaction kinetics and mechanisms, necessary for the development of the mechanistic framework of milling reactions.

Item Type: Article
Uncontrolled Keywords: quantitative in situ monitoring; monitoring; mechanochemistry; Raman spectroscopy; synchrotron XRD; pharmaceutical cocrystals
Subjects: NATURAL SCIENCES > Chemistry
Divisions: Division of Physical Chemistry
Project titleProject leaderProject codeProject type
Mehaniokemijska reaktivnost pod kontroliranim uvjetima temperature i atmosfere za čišću sintezu funkcionalnih materijala-MECHANOCONTROLKrunoslav UžarevićUIP-2014-09-4744HRZZ
Depositing User: Stipe Lukin
Date Deposited: 26 Nov 2018 12:35
DOI: 10.1002/chem.201702489

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