Highly stable and self-repairing membrane-mimetic 2D nanomaterials assembled from lipid-like peptoids

Abstract

An ability to develop sequence-defined synthetic polymers that both mimic lipid amphiphilicity for self-assembly of highly stable membrane-mimetic 2D nanomaterials and exhibit protein-like functionality would revolutionize the development of biomimetic membranes. Here we report the assembly of lipid-like peptoids into highly stable, crystalline, free-standing and self-repairing membrane-mimetic 2D nanomaterials through a facile crystallization process. Both experimental and molecular dynamics simulation results show that peptoids assemble into membranes through an anisotropic formation process. We further demonstrated the use of peptoid membranes as a robust platform to incorporate and pattern functional objects through large side-chain diversity and/or co-crystallization approaches. Similar to lipid membranes, peptoid membranes exhibit changes in thickness upon exposure to external stimuli; they can coat surfaces in single layers and self-repair. We anticipate that this new class of membrane-mimetic 2D nanomaterials will provide a robust matrix for development of biomimetic membranes tailored to specific applications.

Direct Observation and Manipulation of Supramolecular Polymerization by High‐Speed Atomic Force Microscopy

“…Similar self-repairing behavior was recently reported by Jin et al [30] for two-dimensional nanomaterials assembled from peptoids.Conventional AFM probed gradual self-repair on at imescale of several hundred minutes.R emarkably,t he much higher spatiotemporal resolution of high-speed AFM captured unique dynamic behavior in real time.F igure 3b shows the trajectory of the two tips of the cut 1NF as af unction of time.I nt he presence of 1NP,b oth tips propagated but fluctuated;c onsequently,w elding did not immediately occur. After some "trial and error", when the lengths and angles of the tips matched (see Figure S6), 1NF was eventually repaired and became stationary (at 51.8 si n Figure 3b).…”

Using Biomimetic Polymers in Place of Noncollagenous Proteins to Achieve Functional Remineralization of Dentin Tissues

“…Previous work showed that protons donated by Pro and Hyp residues can interact with acceptors such as electron rich aromatic groups, leading to CH⋯ π interactions 20–23 . Other studies showed that π-π interactions between peptoids leads to their self-assembly into highly ordered structures 56 . Thus the high content of both Pro and Hyp on the surface of the collagen triple helix can be expected to promote extensive interactions with the phenethyl side groups of the peptoids and enhance the inter collagen interactions that promote co-alignment 50 .…”

Design and preparation of organic nanomaterials using self‐assembled peptoids

“…A different synthetic approach to form 2D nanostructures was recently reported by the Chen group . Inspired by the diblock structure of lipids, a class of amphiphilic lipid‐like peptoids (e.g., peptoids 18–20 , Figure A) was synthesized, characterized by two blocks, one constituted of six polar Nce residues and the other of six N 4‐Cl pe residues.…”

“…B to E, Adapted from Ref. under CC BY. F, Scheme of the AFM mechanical damage and self‐healing process on the peptoid membrane.…”