Responsive Supramolecular Microgels with Redox-Triggered Cleavable Crosslinks

Macromolecules, vol. 53, pp. 1043–1053

Abstract

We demonstrate a novel method to synthesize aqueous microgels with supramolecular redox-cleavable crosslinks. The redox-cleavable crosslinker was synthesized on the basis of host–guest interactions using methacrylate-modified β-cyclodextrin (host) and vinylferrocene (guest). A series of microgels with variable contents of a redox-cleavable crosslinker were synthesized via precipitation polymerization. Synthesized supramolecular microgels exhibit hydrodynamic radii in the size range 100–200 nm in the swollen state at 20 °C. The increase of the temperature induces a volume-phase transition, leading to the deswelling of microgels. This temperature-induced swelling/deswelling is completely reversible and does not lead to the degradation of microgels. Using the combination of characterization methods such as light scattering and electron microscopy, we demonstrate that the obtained microgels can be degraded using chemical oxidants (FeCl 3 or H 2 O 2 ) or oxidation during bulk electrolysis. The degradation rate was studied by tracing the hydrodynamic radius, scattering intensity, and turbidity as a function of time. Furthermore, we could also demonstrate efficient loading and release of anticancer drug (doxorubicin) with UV–vis spectroscopy.

Authors 4

1. Se‐Hyeong Jung Aachen DWI-Leibniz-Institute for Interactive Materials e.V Functional and Interactive Polymers Institute of Technical and Macromolecular Chemistry

   DWI – Leibniz Institute for Interactive Materials · RWTH Aachen University

   Affiliation as printed

   DWI-Leibniz Institute for Interactive Materials e.V., 52074 Aachen, Germany

   Functional and Interactive Polymers, Institute of Technical and Macromolecular Chemistry, RWTH Aachen University, 52074 Aachen, Germany

   DWI-Leibniz Institute for Interactive Materials e.V., 52074 Aachen, Germany

   Functional and Interactive Polymers, Institute of Technical and Macromolecular Chemistry, RWTH Aachen University, 52074 Aachen, Germany

2. Sabine Schneider Aachen Institute of Physical Chemistry

   RWTH Aachen University

   Affiliation as printed

   Institute of Physical Chemistry, RWTH Aachen University, 52074 Aachen, Germany

3. Felix A. Plamper Aachen Institute of Physical Chemistry

   TU Bergakademie Freiberg · RWTH Aachen University

   Affiliation as printed

   Institute of Physical Chemistry, RWTH Aachen University, 52074 Aachen, Germany

   Institute of Physical Chemistry, TU Bergakademie Freiberg, 09599 Freiberg, Germany

4. Andrij Pich corresponding Aachen DWI-Leibniz-Institute for Interactive Materials e.V Functional and Interactive Polymers Institute of Technical and Macromolecular Chemistry

   Maastricht University · DWI – Leibniz Institute for Interactive Materials · RWTH Aachen University

   Affiliation as printed

   Aachen Maastricht Institute for Biobased Materials (AMIBM), Maastricht University, Brightlands Chemelot Campus, 6167 RD Geleen, The Netherlands

   DWI-Leibniz Institute for Interactive Materials e.V., 52074 Aachen, Germany

   Functional and Interactive Polymers, Institute of Technical and Macromolecular Chemistry, RWTH Aachen University, 52074 Aachen, Germany

   Aachen Maastricht Institute for Biobased Materials (AMIBM), Maastricht University, Brightlands Chemelot Campus, 6167 RD Geleen, The Netherlands

   DWI-Leibniz Institute for Interactive Materials e.V., 52074 Aachen, Germany

   Functional and Interactive Polymers, Institute of Technical and Macromolecular Chemistry, RWTH Aachen University, 52074 Aachen, Germany