Mechanism of Crystalline Self‐Assembly in Aqueous Medium: A Combined Cryo‐TEM/Kinetic Study. Issue 33 (15th July 2014)

• Record Type: Journal Article
• Authors: Tidhar, Yaron; Weissman, Haim; Tworowski, Dmitry; Rybtchinski, Boris
• Is Part Of: Chemistry. Volume 20:Issue 33(2014)
• Page Start: 10332
• Page End: 10342
• Publication Date: 2014-07-15
• Subjects: Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201402096
• Languages: English
• ISSNs: 0947-6539

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Understanding the crystallization of organic molecules is a long‐standing challenge. Herein, a mechanistic study on the self‐assembly of crystalline arrays in aqueous solution is presented. The crystalline arrays are assembled from perylene diimide (PDI) amphiphiles bearing a chiral <italic>N</italic>‐acetyltyrosine side group connected to the PDI aromatic core. A kinetic study of the crystallization process was performed using circular dichroism spectroscopy combined with time‐resolved cryogenic transmission electron microscopy (cryo‐TEM) imaging of key points along the reaction coordinate, and molecular dynamics simulation of the initial stages of the assembly. The study reveals a complex self‐assembly process starting from the formation of amorphous aggregates that are transformed into crystalline material through a nucleation–growth process. Activation parameters indicate the key role of desolvation along the assembly pathway. The insights from the kinetic study correlate well with the structural data from cryo‐TEM imaging. Overall, the study reveals four stages of crystalline self‐assembly: 1) collapse into amorphous aggregates; 2) nucleation as partial ordering; 3) crystal growth; and 4) fusion of smaller crystalline aggregates into large crystals. These studies indicate that the assembly process proceeds according to a two‐step crystallization model, whereby initially formed amorphous material is reorganized into an ordered system. This process follows Ostwald's rule of stages, evolving through a series of intermediate phases prior to forming the final structure, thus providing an insight into the crystalline self‐assembly process in aqueous medium.</p> </abstract>