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Challenging the Ostwald rule of stages in mechanochemical cocrystallisation.

ABSTRACT: Mechanochemistry provides an efficient, but still poorly understood route to synthesize and screen for polymorphs of organic solids. We present a hitherto unexplored effect of the milling assembly on the polymorphic outcome of mechanochemical cocrystallisation, tentatively related to the efficiency of mechanical energy transfer to the milled sample. Previous work on mechanochemical cocrystallisation has established that introducing liquid or polymer additives to milling systems can be used to direct polymorphic behavior, leading to extensive studies how the amount and nature of grinding additive affect reaction outcome and polymorphism. Here, focusing on a model pharmaceutical cocrystal of nicotinamide and adipic acid, we demonstrate that changes to the choice of milling media (i.e. number and material of milling balls) and/or the choice of milling assembly (i.e. jar material) can be used to direct polymorphism of mechanochemical cocrystallisation, enabling the selective synthesis, and even reversible and repeatable interconversion of cocrystal polymorphs. While real-time mechanistic studies of mechanochemical transformations of metal-organic materials have previously suggested that reactions follow a path described by Ostwald's rule of stages, i.e. from metastable to increasingly more stable product structures, the herein presented systematic study presents an exception to that rule, revealing that modification of energy input in the mechanochemical system, combined with a small energy difference between polymorphs, permits the selective synthesis of either the more stable room temperature form, or the new metastable high-temperature form, of the target cocrystal.

SUBMITTER: Germann LS

PROVIDER: S-EPMC8162427 | biostudies-literature |

REPOSITORIES: biostudies-literature

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Project description:Bergmann's rule is a well-established, ecogeographical principle that states that body size varies positively with latitude, reflecting the thermoregulatory benefits of larger bodies as temperatures decline. However, this principle does not seem to easily apply to migratory species that are able to avoid the extreme temperatures during winter at higher latitudes. Further, little is known about the ontogeny of this relationship across life stages or how it is influenced by ongoing global climate change. To address these knowledge gaps, we assessed the contemporary relationship between latitude and body size in a long-distance migratory species, the prothonotary warbler (Protonotaria citrea) across life stages (egg to adult) on their breeding grounds. We also measured historic eggs (1865-1961) to assess if the relationship between latitude and size during this life stage has changed over time. In accordance with Bergmann's rule, we found a positive relationship between latitude and body mass during all post-embryonic life stages, from early nestling stage through adulthood. We observed this same predicted pattern with historic eggs, but contemporary eggs exhibited the reverse (negative) relationship. We suggest that these results indicate a genetic component to this pattern and speculate that selection for larger body size in altricial nestlings as latitude increases may possibly drive the pattern in migratory species as even rare extreme cold weather events may cause mortality during early life stages. Furthermore, the opposite relationships observed in eggs, dependent on time period, may be related to the rapidly warming environments of higher latitudes that is associated with climate change. Although it is unclear what mechanism(s) would allow for this recent reversal in eggs (but still allow for its maintenance in later life stages). This evidence of a reversal suggests that anthropogenic climate change may be in the process of altering one of the longest-standing principles in ecology.

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Challenging the Ostwald rule of stages in mechanochemical cocrystallisation.

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