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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Official URL: http://onlinelibrary.wiley.com/doi/10.1002/chem.20...

Abstract

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

Projects:

Project title	Project leader	Project code	Project type
Mehaniokemijska reaktivnost pod kontroliranim uvjetima temperature i atmosfere za čišću sintezu funkcionalnih materijala-MECHANOCONTROL	Krunoslav Užarević	UIP-2014-09-4744	HRZZ

Depositing User:

Stipe Lukin

Date Deposited:

26 Nov 2018 12:35

URI:

http://fulir.irb.hr/id/eprint/4351

DOI:

10.1002/chem.201702489