Multilevel Manipulation of Supramolecular Structures of Giant Molecules via Macromolecular Composition and Sequence

Abstract

We have successfully synthesized a series of monodispersed chain-like giant molecules with precisely controlled macromolecular composition and sequence based on polyhedral oligomeric silsesquioxane (POSS) nanoparticles using an orthogonal “click” strategy. Their nonspherical supramolecular structures, such as lamellae, double gyroids, and hexagonal packed cylinders, are mainly determined by the composition (namely, the number of incorporated amphiphilic nanoparticles). In addition, by precisely alternating the sequence of arranged nanoparticles in the giant molecules with identical chemical compositions, the domain sizes of their supramolecular structures could be fine-tuned. This is attributed to the macromolecular conformational differences caused by collective hydrogen bonding interactions in each set of sequence isomeric giant molecules. This work has demonstrated multilevel manipulation of supramolecular structures of giant molecules: coarse tuning by composition and fine-tuning by sequence.

Macromolecular Isomerism in Giant Molecules

“…It was found that sequence does impact the phase‐separated nanostructures significantly. For example, the DB 6 , BDB 4 , and B 2 DB 3 form three distinct spherical phases, that is, body–center–cubic (BCC), sigma (σ), and A15, respectively . “Folding” of the chain and the resulting distinct interfacial curvature were believed to account for such differences.…”

Polyhedral Oligomeric Silsesquioxane Hybrid Polymers: Well‐Defined Architectural Design and Potential Functional Applications

“…Click adaptors are a class of small molecules that easily convert one click functionality to another or extend the total number of clickable sites. For instance, isomeric chain‐like giant molecules have been precisely synthesized through an orthogonal click strategy that combined SPAAC and oxime ligation reactions (Figure b) . Taking advantage of the introduction of two growing sites from the click adaptor, half as many reaction cycles are needed for a given number of POSS cages along the chain, offering new opportunities to study sequence effects of those giant molecules in nonspherical phase regions.…”

“…a) Linear sequence‐mandated giant molecules via repeated esterification reaction cycles from two different types of clickable POSS, b) sequence of isomeric chain‐like giant molecules synthesized from POSS with two clickable functionalities and “linear click adaptor” by combining SPAAC and oxime ligation, c) iterative synthetic strategy for POSS‐based sequence isomers (PS‐(APOSS)(BPOSS) 2 by SPACC from azido‐terminated PS, and two different types of clickable POSS. Reproduced with permission . Copyright 2017, Wiley‐VCH, American Chemical Society; Copyright 2016, Royal Society of Chemistry.…”

Self-Assembly and Applications of Amphiphilic Hybrid POSS Copolymers

“…Cheng and coworkers have produced a series of famous and important works starting from 2010 on POSS amphiphilic materials and their assemblies [ 26 , 81 , 82 , 83 ]. Recently, they found that difference between phase-separated nanostructures could be determined by precisely controlling the sequence and the number of incorporated POSS cages (composition), because the sequence of the symmetry could affect the cross-sectional areas of the hydrophobic/hydrophilic POSS domains [ 84 ]. In another work, they also found that both the compositional variation and specific sequences could induce unconventional phase formation from specifically designed chain-like giant molecules.…”