Tuning crystallization pathways through sequence engineering of biomimetic polymers
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical Sciences Division
- 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
- Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States). Physical and Life Sciences Directorate
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Physical Sciences Division; Univ. of Washington, Seattle, WA (United States). Dept. of Chemical Engineering
- 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
- 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
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.
- Research Organization:
- Lawrence Livermore National Laboratory (LLNL), Livermore, CA (United States)
- Sponsoring Organization:
- USDOE National Nuclear Security Administration (NNSA); USDOE Office of Science (SC), Basic Energy Sciences (BES)
- Grant/Contract Number:
- AC52-07NA27344; AC05-76RL01830
- OSTI ID:
- 1513103
- Report Number(s):
- LLNL-JRNL-772920; 961673
- Journal Information:
- Nature Materials, Vol. 16, Issue 7; ISSN 1476-1122
- Publisher:
- Springer Nature - Nature Publishing GroupCopyright Statement
- Country of Publication:
- United States
- Language:
- English
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