Construction and micellization of a noncovalent double hydrophilic block copolymer

Abstract

The first noncovalent double hydrophilic block copolymer was constructed through inclusion complexation between beta-cyclodextrin and the adamantyl group; it can further self-assemble into two distinctly different micelles in response to pH and temperature in dilute aqueous solution.

Multi‐Responsive Supramolecular Double Hydrophilic Diblock Copolymer Driven by Host‐Guest Inclusion Complexation between β‐Cyclodextrin and Adamantyl Moieties

“…[56] In this work, we first attempted a three step approach by coupling click and ATRP techniques (Scheme 1 and 2). Monosubstituted b-CD derivative, b-CD-OTs (1), was prepared at first according to literature procedures, [60] and its azidation with NaN 3 afforded mono-6-deoxy-6-azido-bcyclodextrin (b-CD-N 3 , 2).…”

“…It should be noted that, in this study, a random copolymer of Ad-containing monomer and t-butyl acrylate was employed, thus molecular recognition moieties were arranged in a less-defined manner. Most recently, Shi et al [56] reported the construction and self-assembly of a responsive water-soluble supramolecular diblock copolymer consisting of PNIPAM and poly(4-vinyl pyridine) (P4VP) sequences. They observed the formation of two types of non-covalently connected aggregates in response to solution pH and temperature.…”

Dynamic Macromolecular Material Design—The Versatility of Cyclodextrin‐Based Host–Guest Chemistry

“…Fort he "grafting from" polymerization route,s everal examples of CD-functionalized polymerization mediators have been described in the literature that allow the polymerization to be started from the CD core, for example,f or NMP, [56] ATRP, [57] and RAFT. [58] "Grafting to" of CDs to various polymer structures after polymerization has also been reported, for example,b yC uAAc after ATRP [57] or RAFT polymerization. [59] Here,azide-monofunctionalized b-CD was conjugated to various polymers functionalized with alkyne units as the end groups or in the side chain.…”

“…[58] Since then, similar strategies have been developed with several types of supramolecular diblock copolymers. [49a,57] Supramolecular star polymers were utilized for the formation of micelles as well as,f or example, b-CD-centered four-arm POEGMA complexed with ah ydrophobic adamantyl end functionalized poly[bis(trifluoroethoxy)phosphazene] that showed critical micelle concentrations (cmcs) from 4.6 to 28.2 mg L À1 and micelle radii from 32 to 60 nm depending on the length of the b-CD-containing block.…”

“…[58] Specifically, b-CD-functionalized poly(4-vinylpyridine) (P4VP) and adamantyl-functionalized poly(N-isopropylacrylamide) (PNIPAM) were conjugated in as upramolecular fashion. Later, Jiang and co-workers also presented ad iblock copolymer based on b-CD.…”