Issue 23, 2019

Self-assembly of oppositely charged polyelectrolyte block copolymers containing short thermoresponsive blocks

Abstract

The assembly of oppositely charged block copolymers, containing small thermoresponsive moieties, was investigated as a function of salt concentration and temperature. Aqueous solutions of poly-[N-isopropylacrylamide]-b-poly[dimethylaminoethyl methacrylate] (NIPAM44-b-DMAEMA216) and PNIPAM-b-poly[acrylic acid]-b-PNIPAM (NIPAM35-b-AA200-b-NIPAM35) were mixed in equal charge stoichiometry, and analysed by light scattering (LS), NMR spectroscopy and small angle X-ray scattering (SAXS). At room temperature, two different micelle morphologies were found at different salt concentrations. At NaCl concentrations below 0.75 M, complex coacervate core micelles (C3M) with a PNIPAM corona were formed as a result of interpolyelectrolyte complexation. At NaCl concentrations exceeding 0.75 M, the C3M micelles inverted into PNIPAM cored micelles (PCM), containing a water soluble polyelectrolyte corona. This behavior is ascribed to the salt concentration dependence of both the lower critical solution temperature (LCST) of PNIPAM, and the complex coacervation. Above 0.75 M NaCl, the PNIPAM blocks are insoluble in water at room temperature, while complexation between the polyelectrolytes is prevented because of charge screening by the salt. Upon increasing the temperature, both types of micelles display a cloud point temperature (Tcp), despite the small thermoresponsive blocks, and aggregate into hydrogels. These hydrogels consist of a complexed polyelectrolyte matrix with microphase separated PNIPAM domains. Controlling the morphology and aggregation of temperature sensitive polyelectrolytes can be an important tool for drug delivery systems, or the application and hardening of underwater glues.

Graphical abstract: Self-assembly of oppositely charged polyelectrolyte block copolymers containing short thermoresponsive blocks

Supplementary files

Article information

Article type
Paper
Submitted
15 feb 2019
Accepted
27 mar 2019
First published
09 apr 2019
This article is Open Access
Creative Commons BY-NC license

Polym. Chem., 2019,10, 3127-3134

Self-assembly of oppositely charged polyelectrolyte block copolymers containing short thermoresponsive blocks

I. A. van Hees, P. J. M. Swinkels, R. G. Fokkink, A. H. Velders, I. K. Voets, J. van der Gucht and M. Kamperman, Polym. Chem., 2019, 10, 3127 DOI: 10.1039/C9PY00250B

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