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Coupled Orientational Disorder and Hydrogen-Bond Destabilization Drive Anisotropic Surface Melting in Curcumin
Artem Shagurin1,2,3, Michael G Kiselev3, Pal Jedlovszky4
1University of Lille, CNRS UMR 8516 -LASIRe - Laboratoire Avancé de Spectroscopie pour les Interactions la Réactivité et l'environnement, 59000 Lille, France.
Molecular crystal surface stability is polymorph-dependent. This study reveals anisotropic interfacial softening in curcumin polymorphs, driven by face-specific molecular rearrangements and intermolecular forces.
Area of Science:
- Materials Science
- Crystallography
- Computational Chemistry
Background:
- Polymorph-dependent surface stability is crucial for molecular crystal performance.
- Microscopic origins of anisotropic interfacial softening are not well understood.
Purpose of the Study:
- Investigate temperature-dependent surface behavior of curcumin polymorphs.
- Elucidate the molecular mechanisms behind anisotropic interfacial softening.
Main Methods:
- Layer-resolved molecular dynamics simulations.
- Analysis of low-index crystallographic faces of three curcumin polymorphs.
Main Results:
- Structural rearrangements and interfacial softening observed below bulk melting temperature.
- Softening onset and magnitude are face-dependent.
- Early softening linked to loss of orientational order, π-π stacking, and hydrogen bonding.
Conclusions:
- Anisotropic interfacial softening in curcumin is governed by face-dependent coupling.
- Molecular orientation, intermolecular packing, hydrogen bonding, and conformational flexibility play key roles.
- Surface structure dictates thermal stability and softening behavior.
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