π–π Interlocking Effect for Designing Biodegradable Nanorods with Controlled Lateral Surface Curvature

Abstract

The morphology of nanoparticles is closely related to their various applications. However, precise control over geometric parameters such as the lateral surface curvature (K) of nanorods still remains an important challenge. To address this issue, we propose a π–π interlocking effect for fabricating biodegradable nanorods with tailored lateral surface curvature. This interlocking effect originates from π–π interactions, provides noncovalent conformational locks among poly-γ-benzyl-l-glutamate (PBLG) chains, and plays a key role in the formation of these nanorods during self-assembly. This interlocking effect can be facilely manipulated by end-group engineering; different α end groups are introduced into PBLG homopolypeptides to afford nanorods with controlled lateral surface curvature. The stronger the π–π interlocking effect, the straighter the lateral surface of nanorods. Furthermore, a co-solvent strategy can be applied to facilely control the aspect ratio (Γ) of the nanorods with a straight lateral surface. Compared with other nanorods that are either based on nonbiodegradable materials or dependent upon complicated cost-consuming processes, this work provides a versatile bottom-up strategy for preparing biodegradable nanorods with controlled lateral surface curvature and aspect ratio.

Physically and Chemically Compartmentalized Polymersomes for Programmed Delivery and Biological Applications

“…As one of the most powerful tool to prepare soft nanomaterials with precisely controlled structure and functionality, − polymer self-assembly also plays important role in the fabrication of MCPs, including polymersomes-in-polymersomes, , MVVs, − onion-like polymersomes , and LCVs . For instance, Cheng et al reported the preparation and self-assembly of amphiphilic polyurethane phosphate (PUP), which self-assembled into various morphologies including LCVs by adjusting the hydrophobic chain length and initial polymer concentration in the PU tail.…”

Homopolymer Self-Assembly: Principles, Driving Forces, and Applications

“…Furthermore, our group introduced a series of terminal groups with different π−π stacking strengths into poly-γbenzyl-L-glutamate (PBLG) homopolymers. 29 These homopolymers could self-assemble into nanorods. The lateral surface of nanorods is regulated by the strength of π−π stacking among the terminal groups.…”

Chirality-controlled polymerization-induced self-assembly

“…Additional forces that can contribute to polymer self-assembly are p-p stacking interactions from the aromatic group on the PPhe core-forming block. 66,70 It is possible that the strength of these aromatic interactions is affected by the changing secondary structure and/or that these interactions are governed by the degree of hetero-chirality. Nevertheless, more research is required to further elucidate the driving force for this intriguing PISA formulation that is aided by the structure of the peptide chain.…”