Tuning crystallization pathways through sequence engineering of biomimetic polymers

Xiang Ma, Shuai Zhang, Fang Jiao, Christina J. Newcomb, Yuliang Zhang, Arushi Prakash, Zhihao Liao, Marcel D. Baer, Christopher J. Mundy, James Pfaendtner, Aleksandr Noy, Chun Long Chen, James J. De Yoreo

Research output: Contribution to journalArticlepeer-review

75 Scopus citations


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.

Original languageEnglish (US)
Pages (from-to)767-774
Number of pages8
JournalNature Materials
Issue number7
StatePublished - Jul 1 2017
Externally publishedYes

ASJC Scopus subject areas

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics
  • Mechanics of Materials
  • Mechanical Engineering


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