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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 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.

Authors:
 [1]; ORCiD logo [1];  [2];  [1];  [3];  [4];  [5];  [1];  [4];  [4]; ORCiD logo [3];  [1];  [6]
+ Show Author Affiliations
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical Sciences Division
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical Sciences Division; East China Normal Univ. (ECNU), Shanghai (China). School of Chemistry and Molecular Engineering
  3. Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Physical and Life Sciences Directorate
  4. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical Sciences Division; Univ. of Washington, Seattle, WA (United States). Dept. of Chemical Engineering
  5. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical Sciences Division; Zhejiang University, Hangzhou, Zhejiang (China). Center for Biomaterials and Biopathways, Dept. of Chemistry
  6. Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical Sciences Division; Univ. of Washington, Seattle, WA (United States). Dept. of Materials Science and Engineering
Publication Date:
Research Org.:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1513103
Report Number(s):
LLNL-JRNL-772920
Journal ID: ISSN 1476-1122; 961673
Grant/Contract Number:  
AC52-07NA27344; AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
Nature Materials
Additional Journal Information:
Journal Volume: 16; Journal Issue: 7; Journal ID: ISSN 1476-1122
Publisher:
Springer Nature - Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE

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.
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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.
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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. https://www.osti.gov/servlets/purl/1513103.
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@article{osti_1513103,
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 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.},
doi = {10.1038/NMAT4891},
journal = {Nature Materials},
number = 7,
volume = 16,
place = {United States},
year = {2017},
month = {4}
}
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DOI:  10.1038/NMAT4891
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Cited by: 31 works
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Figures / Tables:

Table 1 Table 1: Pepb-Pepb and Pepb-mica binding free energy vs. Ca2+ concentration from DFS measurements
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