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Title: Tuning crystallization pathways through sequence engineering of biomimetic polymers

Journal Article · · Nature Materials
DOI: https://doi.org/10.1038/NMAT4891 · OSTI ID:1513103
 [1]; ORCiD logo [1];  [2];  [1];  [3];  [4];  [5];  [1];  [4];  [4]; ORCiD logo [3];  [1];  [6]
  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

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
Citation Metrics:
Cited by: 85 works
Citation information provided by
Web of Science

References (31)

Free-floating ultrathin two-dimensional crystals from sequence-specific peptoid polymers journal April 2010
Thermodynamically consistent description of the work to form a nucleus of any size journal January 2003
Peptoid Polymers: A Highly Designable Bioinspired Material journal May 2013
Two-step mechanism for the nucleation of crystals from solution journal February 2005
Lack of Dependence of the Sizes of the Mesoscopic Protein Clusters on Electrostatics journal November 2015
An XPS and Scanning Polarization Force Microscopy Study of the Exchange and Mobility of Surface Ions on Mica journal September 1998
Nucleation of Crystals from Solution: Classical and Two-Step Models journal May 2009
Taking Advantage of Disorder: Amorphous Calcium Carbonate and Its Roles in Biomineralization journal June 2003
Mechanistic Studies of Two-Dimensional Covalent Organic Frameworks Rapidly Polymerized from Initially Homogenous Conditions journal June 2014
Crystallization by particle attachment in synthetic, biogenic, and geologic environments journal July 2015
Interpreting the widespread nonlinear force spectra of intermolecular bonds journal August 2012
In situ TEM imaging of CaCO3 nucleation reveals coexistence of direct and indirect pathways journal September 2014
Experimental Evidence for Two-Step Nucleation in Colloidal Crystallization journal May 2009
The effect of cation valency on DLVO and hydration forces between macroscopic sheets of muscovite mica in relation to clay swelling journal March 1984
Liquid-liquid separation in solutions of normal and sickle cell hemoglobin journal June 2002
Microscopic Evidence for Liquid-Liquid Separation in Supersaturated CaCO3 Solutions journal August 2013
Stable Prenucleation Calcium Carbonate Clusters journal December 2008
Efficient method for the preparation of peptoids [oligo(N-substituted glycines)] by submonomer solid-phase synthesis journal December 1992
Prenucleation clusters and non-classical nucleation journal December 2011
Near-Equilibrium Chemical Force Microscopy journal March 2008
Protein Conformational Flexibility Enables the Formation of Dense Liquid Clusters: Tests Using Solution Shear journal June 2016
More than one pathway journal March 2013
Calcium Ions to Remotely Control the Reversible Switching of Secondary and Quaternary Structures in Bioconjugates journal April 2011
Peptoid nanosheets exhibit a new secondary-structure motif journal October 2015
The Initial Stages of Template-Controlled CaCO3 Formation Revealed by Cryo-TEM journal March 2009
Single-Molecule Determination of the Face-Specific Adsorption of Amelogenin’s C-Terminus on Hydroxyapatite journal June 2011
Surface-Directed Assembly of Sequence-Defined Synthetic Polymers into Networks of Hexagonally Patterned Nanoribbons with Controlled Functionalities journal May 2016
A perspective on underlying crystal growth mechanisms in biomineralization: solution mediated growth versus nanosphere particle accretion journal January 2015
Self-catalyzed growth of S layers via an amorphous-to-crystalline transition limited by folding kinetics journal September 2010
Can the study of self-assembly in solution lead to a good model for the nucleation pathway? The case of tolfenamic acid. journal January 2015
Seeing crystal formation one particle at a time journal March 2020

Cited By (14)

Droplet Microfluidics XRD Identifies Effective Nucleating Agents for Calcium Carbonate journal March 2019
Nanocrystalline Precursors for the Co-Assembly of Crack-Free Metal Oxide Inverse Opals journal January 2018
Hierarchical Assembly of Peptoid‐Based Cylindrical Micelles Exhibiting Efficient Resonance Energy Transfer in Aqueous Solution journal July 2019
Solid‐phase synthesis of three‐armed star‐shaped peptoids and their hierarchical self‐assembly journal January 2019
Recent advances in crystallization and self‐assembly of polypeptoid polymers journal June 2019
A Cut‐and‐Weld Process to 3D Architectures from Multiresponsive Crosslinked Liquid Crystalline Polymers journal March 2019
Controlled synthesis of highly-branched plasmonic gold nanoparticles through peptoid engineering journal June 2018
Bioinspired neuron-like electronics journal February 2019
Controlling protein assembly on inorganic crystals through designed protein interfaces journal July 2019
Accessing crystal–crystal interaction forces with oriented nanocrystal atomic force microscopy probes journal September 2018
How crystals form: A theory of nucleation pathways journal April 2019
Impurities and Homogeneous Crystal Nucleation in Aqueous Solutions - An Overview journal December 2019
Hierarchical Assembly of Peptoid‐Based Cylindrical Micelles Exhibiting Efficient Resonance Energy Transfer in Aqueous Solution journal August 2019
PyRosetta: a script-based interface for implementing molecular modeling algorithms using Rosetta journal January 2010

Figures / Tables (1)