Photo-cross-linked and pH-Switchable Soft Polymer Nanocapsules from Polyglycidyl Ethers

Macromolecules, vol. 57, pp. 707–718

Abstract

High Resolution Image Download MS PowerPoint Slide Soft polymer nanocapsules and microgels, which can adapt their shape and, at the same time, sequester and release molecular payloads in response to an external trigger, are a challenging complement to vesicular structures like polymersomes. In this work, we report the synthesis of such capsules by photo-cross-linking of coumarin-substituted polyglycidyl ethers, which we prepared by Williamson etherification of epichlorohydrin (ECH) repeating units with 7-hydroxycoumarin in copolymers with tert -butyl glycidyl ether ( t BGE). To control capsule size, we employed the prepolymers in an o/w miniemulsion, where they formed a gel layer at the interface upon irradiation at 365 nm by [2π + 2π] photodimerization of the coumarin groups. Upon irradiation at 254 nm, the reaction could be reversed and the gel wall could be repeatedly disintegrated and rebuilt. We further demonstrated (i) reversible hydrophilization of the gels by hydrolysis of the lactone rings in coumarin dimers as a mechanism to manipulate the permeability of the capsules and (ii) binding functional molecules as amides. Thus, the presented nanogels are remarkably versatile and can be further used as a carrier system.

Authors 8

1. Pascal M. Jeschenko corresponding Aachen DWI - Leibniz Institute for Interactive Materials

   DWI – Leibniz Institute for Interactive Materials · Max Planck School Matter to Life

   Affiliation as printed

   DWI─Leibniz-Institute for Interactive Materials, Forckenbeckstraße 50, D-52074 Aachen, Germany

   Max Planck School Matter to Life, Jahnstraße 29, D-69120 Heidelberg, Germany

2. Marcel van Dongen Aachen DWI - Leibniz Institute for Interactive Materials

   DWI – Leibniz Institute for Interactive Materials

   Affiliation as printed

   DWI─Leibniz-Institute for Interactive Materials, Forckenbeckstraße 50, D-52074 Aachen, Germany

3. Jonas C. Rose Aachen DWI - Leibniz Institute for Interactive Materials

   DWI – Leibniz Institute for Interactive Materials

   Affiliation as printed

   DWI─Leibniz-Institute for Interactive Materials, Forckenbeckstraße 50, D-52074 Aachen, Germany

4. Dominic Schäfer Aachen Institute of Inorganic Chemistry

   RWTH Aachen University

   Affiliation as printed

   Institute of Inorganic Chemistry (IAC), RWTH Aachen University, Landoltweg 1, D-52074 Aachen, Germany

5. Michael Brüns

   Karlsruhe Institute of Technology

   Affiliation as printed

   Institute for Applied Materials and Karlsruhe Nano Micro Facility, Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, D-76344 Eggenstein-Leopoldshafen, Germany

6. Sonja Herres‐Pawlis Aachen Institute of Inorganic Chemistry

   RWTH Aachen University

   Affiliation as printed

   Institute of Inorganic Chemistry (IAC), RWTH Aachen University, Landoltweg 1, D-52074 Aachen, Germany

7. Helmut Keul Aachen DWI - Leibniz Institute for Interactive Materials

   DWI – Leibniz Institute for Interactive Materials

   Affiliation as printed

   DWI─Leibniz-Institute for Interactive Materials, Forckenbeckstraße 50, D-52074 Aachen, Germany

8. Martin Möller corresponding Aachen DWI - Leibniz Institute for Interactive Materials Institute of Technical and Macromolecular Chemistry

   DWI – Leibniz Institute for Interactive Materials · Max Planck School Matter to Life · RWTH Aachen University

   Affiliation as printed

   DWI─Leibniz-Institute for Interactive Materials, Forckenbeckstraße 50, D-52074 Aachen, Germany

   Institute of Technical and Macromolecular Chemistry (ITMC), RWTH Aachen University, Worringerweg 2, D-52074 Aachen, Germany

   Max Planck School Matter to Life, Jahnstraße 29, D-69120 Heidelberg, Germany