Atomic-level engineering and imaging of polypeptoid crystal lattices

  title={Atomic-level engineering and imaging of polypeptoid crystal lattices},
  author={Sunting Xuan and Xi Jiang and Ryan K Spencer and Nan K Li and David Prendergast and Nitash P. Balsara and Ronald N. Zuckermann},
  journal={Proceedings of the National Academy of Sciences of the United States of America},
  pages={22491 - 22499}
  • Sunting Xuan, Xi Jiang, R. Zuckermann
  • Published 21 October 2019
  • Chemistry, Materials Science
  • Proceedings of the National Academy of Sciences of the United States of America
Significance A fundamental challenge in materials science is to understand the atomic-level structures of nanoarchitectures assembled from synthetic polymers. Here, we report a family of sequence-defined polypeptoids that form free-floating crystalline 2-dimensional nanosheets, in which not only individual polymer chains and their relative orientations, but also atoms in nanosheets were directly observed by cryogenic transmission electron microscopy. These atomic details are inaccessible by… 

Figures and Tables from this paper

Importance of the Positively Charged σ-Hole in Crystal Engineering of Halogenated Polypeptoids.
Crystalline nanosheets formed by amphiphilic block copolypeptoids with halogenated phenyl side chains were imaged at the atomic-scale using cryogenic transmission electron microscopy (cryo-TEM). In
Crystallization and self-assembly of shape-complementary sequence-defined peptoids
The universal pairing of complementary nucleobases in DNA found in all life forms has inspired extensive studies on selective molecular recognition between information-rich sequence-defined polymer
Hierarchical Self-Assembly Pathways of Peptoid Helices and Sheets.
A new understanding of hierarchical peptoid assembly and principles for the design of peptoid-based nanomaterials are established by identifying a thermodynamically controlled assembly mechanism by which monomers assemble into disordered aggregates that self-order into 1D chiral helical rods then 2D achiral crystalline sheets.
From Distinct Metallopeptoids to Self-Assembled Supramolecular Architectures.
It is demonstrated that changing only one non-coordinating side-chain within peptoids - sequence-specific N-substituted glycine oligomers - leads to different supramolecular structures, and the selective recognition abilities of the nano- channels towards glycerol are demonstrated.
Impact of Nanoparticle Size and Surface Chemistry on Peptoid Self-Assembly
Self-assembled organic nanomaterials can be generated by bottom-up assembly pathways where the structure is controlled by the organic sequence and altered using pH, temperature, and solvation. In
Impact of Nanoparticle Size and Surface Chemistry on Peptoid Self-Assembly.
Self-assembled organic nanomaterials can be generated by bottom-up assembly pathways where the structure is controlled by the organic sequence and altered using pH, temperature, and solvation. In
Nanoparticle-Mediated Assembly of Peptoid Nanosheets Functionalized with Solid-Binding Proteins: Designing Heterostructures for Hierarchy.
This work reports on the synthesis of 3.3-nm-thick thiol-reactive peptoid nanosheets from equimolar mixtures of unmodified and maleimide-derivatized versions of the Nbpe6Nce6 oligomer, and triggers the stacking of these 2D structures into a multilayered material composed of alternating peptoid, protein, and organic layers.
Where Biology and Traditional Polymers Meet: The Potential of Associating Sequence-Defined Polymers for Materials Science
This perspective considers the synergistic advantages that can be achieved via tailoring both precise sequence control and attributes of traditional polymers in a single system and examines sequence-defined polymers as key model systems for studying previously unresolvable questions in polymer physics.


Imaging Unstained Synthetic Polymer Crystals and Defects on Atomic Length Scales Using Cryogenic Electron Microscopy
Properties of soft crystalline materials such as synthetic polymers are governed by locations of constituent atoms. Determining atomic-scale structures in these materials is difficult because they
Design, Synthesis, Assembly, and Engineering of Peptoid Nanosheets.
It is discovered that individual peptoid polymers with a simple sequence of alternating hydrophobic and ionic monomers can self-assemble into highly ordered, free-floating nanosheets, which provide a robust platform for the discovery of new classes of nanOSheets with tunable properties and novel applications.
Conformations of peptoids in nanosheets result from the interplay of backbone energetics and intermolecular interactions
A secondary structure displayed by biomimetic peptoid polymers in which the backbone exhibits the cis conformation and alternating residues display rotational states of opposed (pseudo)chirality is reported.
Universal Relationship between Molecular Structure and Crystal Structure in Peptoid Polymers and Prevalence of the cis Backbone Conformation.
This study demonstrates that when packed into supramolecular lattices or crystals, peptoid polymers prefer to adopt a regular, extended, all-cis secondary structure.
Two-dimensional polymers: just a dream of synthetic chemists?
This analysis compares polymerizations in (initially) a homogeneous phase with those at interfaces and considers structural aspects of monomers as well as possibly preferred connection modes, and briefly touches upon how the chances for a successful structural analysis of the final product can possibly be increased.
Molecular Engineering of the Peptoid Nanosheet Hydrophobic Core.
It is demonstrated that substitution at the meta and para positions of the Npe aromatic ring are well tolerated, enabling significant opportunities to tune the functional properties of peptoid nanosheets.
Functional soft materials from metallopolymers and metallosupramolecular polymers.
Developments towards applications as emissive and photovoltaic materials; as optical limiters; in nanoelectronics, information storage, nanopatterning and sensing; as macromolecular catalysts and artificial enzymes; and as stimuli-responsive materials are illustrated.
Structure and Defects in Sanidic Liquid Crystalline Polymers. 2. Structure Analysis of Sanidic Polymers by Simulation of Diffraction Patterns from Monomeric Analogs
The diffraction patterns from sanidic polymers normally show 8-10 reflections of which only 4 or 5 are unique, so that it is impossible to solve their structure. A large number of equally probable
Self‐Repair and Patterning of 2D Membrane‐Like Peptoid Materials
Due to their unique physical and chemical properties, 2D materials have attracted intense interest for applications in filtration, sensing, nanoelectronics, and biomedical devices. Peptoids are a