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Stoichiometric and Nonstoichiometric Hydrates of Brucine

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The complex interplay of temperature and water activity (a(w))/relative humidity (RH) on the solid form stability and transformation pathways of three hydrates (HyA, HyB, and HyC), an isostructural dehydrate (HyA(dehy)), an anhydrate (AH), and amorphous brucine has been elucidated and the transformation enthalpies quantified. The dihydrate (HyA) shows a nonstoichiometric (de)hydration behavior at RH = 55 at 25 degrees C and contains 3.65-3.85 mol equiv of water. Dehydration of HyC occurs in one step at RH < 55 at 25 degrees C or upon heating, and AH is obtained. The AH is the thermodynamically most stable phase of brucine at RH < 40 at 25 degrees C. Depending on the conditions, temperature, and a(w), each of the three hydrates becomes the thermodynamically most stable form. This study demonstrates the importance of applying complementary analytical techniques and appropriate approaches for understanding the stability ranges and transition behavior between the solid forms of compounds with multiple hydrates.

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