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Synthesis and sequence-controlled self-assembly of amphiphilic triblock copolymers based on functional poly(ethylene glycol)

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Abstract

Given the increasing prosperity of multifunctional poly(ethylene glycol) (mf-PEG), an amphiphilic triblock copolymer, poly(ethylene glycol)-block-poly(ε-caprolactone)-block-poly(allyl glycidyl ether) (mPEG-PCL-PAGE), was synthesized by a combination of living ring-opening polymerization (ROP) and click chemistry. A post-modification of the allyl groups can be achieved via a radical mediated thiol–ene reaction to prepare copolymers bearing side-chain carboxylic or amino groups [mPEG-PCL-PAGE(R)]. The chemical structures and compositions of these polymers were systematically characterized using Fourier transform infrared spectroscopy (FT-IR), proton nuclear magnetic resonance spectroscopy (1H NMR) and gel permeation chromatography (GPC). The copolymers could readily assemble into micelles in aqueous solution as confirmed by fluorescence spectroscopy, dynamic light scattering (DLS), transmission electron microscopy (TEM) and zeta potential measurements. MTT and hemocompatibility assays indicated that the micelles showed no associated cytotoxicity and could be potentially used for nanomedicine. Intriguingly, the specific sequence of [mPEG-PCL-PAGE(R)] showed pH-induced morphology transformation, while the corresponding polymer with a middle PAGE segment [mPEG-PAGE(R)-PCL] did not, which, we propose, was attributed to the tunable hydrophilicity and distinctive folding of the molecular chain at varied pH values. This finding offers a route to regulate the self-assembly behaviors in polymer systems by controlling the block sequence.

Graphical abstract: Synthesis and sequence-controlled self-assembly of amphiphilic triblock copolymers based on functional poly(ethylene glycol)

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Publication details

The article was received on 03 Oct 2017, accepted on 23 Oct 2017 and first published on 25 Oct 2017


Article type: Paper
DOI: 10.1039/C7PY01680H
Citation: Polym. Chem., 2017, Advance Article
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    Synthesis and sequence-controlled self-assembly of amphiphilic triblock copolymers based on functional poly(ethylene glycol)

    Y. Qi, B. Li, Y. Wang and Y. Huang, Polym. Chem., 2017, Advance Article , DOI: 10.1039/C7PY01680H

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