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Nat Mater. 2017 Jul;16(7):767-774. doi: 10.1038/nmat4891. Epub 2017 Apr 17.

Tuning crystallization pathways through sequence engineering of biomimetic polymers.

Author information

Physical Sciences Division, Pacific Northwest National Laboratory, Richland, Washington 99352, USA.
School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200241, China.
Physical and Life Sciences Directorate, Lawrence Livermore National Laboratory, Livermore, California 94550, USA.
Department of Chemical Engineering, University of Washington, Seattle, Washington 98195, USA.
Center for Biomaterials and Biopathways, Department of Chemistry, Zhejiang University, Hangzhou, Zhejiang 310027, China.
School of Natural Sciences University of California Merced, Merced, California 95343, USA.
Department of Materials Science and Engineering, University of Washington, Seattle, Washington 98195, USA.


Two-step nucleation pathways in which disordered, amorphous, or dense liquid states precede the appearance of crystalline phases have been reported for a wide range of materials, but the dynamics of such pathways are poorly understood. Moreover, whether these pathways are general features of crystallizing systems or a consequence of system-specific structural details that select for direct versus two-step processes is unknown. Using atomic force microscopy to directly observe crystallization of sequence-defined polymers, we show that crystallization pathways are indeed sequence dependent. When a short hydrophobic region is added to a sequence that directly forms crystalline particles, crystallization instead follows a two-step pathway that begins with the creation of disordered clusters of 10-20 molecules and is characterized by highly non-linear crystallization kinetics in which clusters transform into ordered structures that then enter the growth phase. The results shed new light on non-classical crystallization mechanisms and have implications for the design of self-assembling polymer systems.

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