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Kinetic Trapping of Metastable Amino Acid Polymorphs
Author(s) -
Azhad U. Chowdhury,
Christopher M. Dettmar,
Shane Z. Sullivan,
Shijie Zhang,
Kevin T. Jacobs,
David J. Kissick,
Thora R. Maltais,
Hartmut G. Hedderich,
Patricia A. Bishop,
Garth J. Simpson
Publication year - 2014
Publication title -
journal of the american chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 7.115
H-Index - 612
eISSN - 1520-5126
pISSN - 0002-7863
DOI - 10.1021/ja410293p
Subject(s) - metastability , chemistry , crystallization , crystallography , polymorphism (computer science) , crystal (programming language) , kinetic energy , chemical physics , second harmonic generation , evaporation , synchrotron , organic chemistry , thermodynamics , optics , laser , biochemistry , physics , quantum mechanics , computer science , genotype , gene , programming language
Second harmonic generation (SHG) microscopy measurements indicate that inkjet-printed racemic solutions of amino acids can produce nanocrystals trapped in metastable polymorph forms upon rapid solvent evaporation. Polymorphism impacts the composition, distribution, and physico-kinetic properties of organic solids, with energetic arguments favoring the most stable polymorph. In this study, unfavored noncentrosymmetric crystal forms were observed by SHG microscopy. Polarization-dependent SHG measurement and synchrotron X-ray microdiffraction analysis of individual printed drops are consistent with formation of homochiral crystal production. Fundamentally, these results provide evidence supporting the ubiquity of Ostwald's Rule of Stages, describing the hypothesized transitioning of crystals between metastable polymorphic forms in the early stages of crystal formation. Practically, the presence of homochiral metastable forms has implications on chiral resolution and on solid form preparations relying on rapid solvent evaporation.

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