Precision synthesis of macrocyclic giant surfactants tethered with two different polyhedral oligomeric silsesquioxanes at distinct ring locations via four consecutive “click” reactions

Abstract

The combined utilization of chemoselective "click" chemistry allows for the preparation of well-defined macromolecules with complex compositions and architectures. In this article, we employed the sequential "click" strategy to further expand the scope of synthetically available giant molecules by precisely constructing new giant surfactants based on polyhedral oligomeric silsesquioxane (POSS) tethered cyclic polymers. The general synthetic approach involves sequentially performed strain-promoted azide-alkyne cycloaddition (SPAAC) as a method for bimolecular homobifunctional ring closure, copper-catalyzed azide-alkyne cycloaddition (CuAAC) for POSS-polymer conjugation, and thiol-Michael/thiol-ene reactions for POSS surface functionalization. Specifically, a cyclic polymer tethered with two POSS cages of distinct surface chemistry at different locations of the chain has been prepared. This work promises to afford numerous cyclic polymers-based giant surfactants with diverse structural variations for further investigation on unexpected physical properties.

Preparation of self-healing organic–inorganic nanocomposites with the reactions between methacrylated polyhedral oligomeric silsesquioxanes and furfurylamine

“…The concept of using nanomaterials as building units (nanoatoms) in preparation of polymer hybrid materials has been explored [12,13]. Polyhedral oligomeric silsesquioxane (POSS), which is an organiceinorganic hybrid nanoblock possessing 8e12 organic moieties which are either chemically nonreactive or reactive, is one of the promising building units.…”

Phase Behaviors of Multi‐tailed B2AB2‐Type Regio‐isomeric Giant Surfactants at the Columnar‐Spherical Boundary†

“…Giant surfactants are generally constructed by attaching polymer tails onto molecular nanoparticles, such as POSS, [ 24 ] fullerenes, [ 25‐26 ] proteins, [ 27‐28 ] among others. [ 29‐30 ] As a new type of precise macromolecules, [ 31‐32 ] they are easier to prepare than dendrimers or discrete oligomers and much more versatile in molecular design than block copolymers, [ 33 ] including “one‐head, one‐tail”, [ 34‐35 ] “one‐head, multi‐tail”, [ 36‐37 ] “multi‐head, one‐tail”, [ 38 ] “gemini‐type”, [ 39‐40 ] “ring‐type”, [ 41‐42 ] “bola‐form‐type”, [ 43‐44 ] etc . They assemble in solution to form various micellar structures such as spheres, cylinders, vesicles, [45‐46] unique grana‐like superstructures, [47] and large aggregates with exquisite inner structures.…”

Fast functionalization of ultrasound microbubbles using strain promoted click chemistry

“…Strain-promoted alkyne-azide cycloaddition is a type of metal-free click chemistry owning high conversion efficiency, orthogonality, and biocompatible properties. 11–14 The reaction has received intense interests in recent years and been widely applied in cell imaging, 15–17 tissue engineering, 18 hydrogel fabrication, 19 surfactant development, 20–22 drug release 23, 24 and preclinical applications. 25 For example, dibenzocyclooctyne (DIBO) was reported for DNA ligation and the reaction was essentially completed within 1 min.…”