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Title: Tuning crystallization pathways through sequence engineering of biomimetic polymers

Abstract

Two-step nucleation pathways in which disordered, amorphous, or dense liquid states precede 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 vs 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 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 design of self-assembling polymer systems.

Authors:
; ORCiD logo; ; ; ; ; ; ; ; ; ORCiD logo; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1368119
Report Number(s):
PNNL-SA-123850
Journal ID: ISSN 1476-1122; KC0203030
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
Nature Materials
Additional Journal Information:
Journal Volume: 16; Journal ID: ISSN 1476-1122
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English

Citation Formats

Ma, Xiang, Zhang, Shuai, Jiao, Fang, Newcomb, Christina J., Zhang, Yuliang, Prakash, Arushi, Liao, Zhihao, Baer, Marcel D., Mundy, Christopher J., Pfaendtner, James, Noy, Aleksandr, Chen, Chun-Long, and De Yoreo, James J. Tuning crystallization pathways through sequence engineering of biomimetic polymers. United States: N. p., 2017. Web. doi:10.1038/nmat4891.
Ma, Xiang, Zhang, Shuai, Jiao, Fang, Newcomb, Christina J., Zhang, Yuliang, Prakash, Arushi, Liao, Zhihao, Baer, Marcel D., Mundy, Christopher J., Pfaendtner, James, Noy, Aleksandr, Chen, Chun-Long, & De Yoreo, James J. Tuning crystallization pathways through sequence engineering of biomimetic polymers. United States. doi:10.1038/nmat4891.
Ma, Xiang, Zhang, Shuai, Jiao, Fang, Newcomb, Christina J., Zhang, Yuliang, Prakash, Arushi, Liao, Zhihao, Baer, Marcel D., Mundy, Christopher J., Pfaendtner, James, Noy, Aleksandr, Chen, Chun-Long, and De Yoreo, James J. Mon . "Tuning crystallization pathways through sequence engineering of biomimetic polymers". United States. doi:10.1038/nmat4891.
@article{osti_1368119,
title = {Tuning crystallization pathways through sequence engineering of biomimetic polymers},
author = {Ma, Xiang and Zhang, Shuai and Jiao, Fang and Newcomb, Christina J. and Zhang, Yuliang and Prakash, Arushi and Liao, Zhihao and Baer, Marcel D. and Mundy, Christopher J. and Pfaendtner, James and Noy, Aleksandr and Chen, Chun-Long and De Yoreo, James J.},
abstractNote = {Two-step nucleation pathways in which disordered, amorphous, or dense liquid states precede 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 vs 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 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 design of self-assembling polymer systems.},
doi = {10.1038/nmat4891},
journal = {Nature Materials},
issn = {1476-1122},
number = ,
volume = 16,
place = {United States},
year = {2017},
month = {4}
}

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