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Open AccessArticle

pH-Responsive Host–Guest Complexation in Pillar[6]arene-Containing Polyelectrolyte Multilayer Films

University of Muenster, Institute of Physical Chemistry, Correnstraße 28/30, 48149 Münster, Germany
Key Laboratory of Organic Optoelectronics & Molecular Engineering, Department of Chemistry, Tsinghua University, Beijing 100084, China
Author to whom correspondence should be addressed.
Polymers 2017, 9(12), 719;
Received: 28 November 2017 / Revised: 12 December 2017 / Accepted: 13 December 2017 / Published: 16 December 2017
(This article belongs to the Special Issue Host-Guest Polymer Complexes)
A water-soluble, anionic pillar[6]arene derivative (WP6) is applied as monomeric building block for the layer-by-layer self-assembly of thin polyelectrolyte multilayer films, and its pH-dependent host–guest properties are employed for the reversible binding and release of a methylviologen guest molecule. The alternating assembly of anionic WP6 and cationic diazo resin (DAR) is monitored in-situ by a dissipative quartz crystal microbalance (QCM-D). In solution, the formation of a stoichiometric inclusion complex of WP6 and cationic methylviologen (MV) as guest molecule is investigated by isothermal titration calorimetry and UV-vis spectroscopy, respectively, and attributed to electrostatic interactions as primary driving force of the host–guest complexation. Exposure of WP6-containing multilayers to MV solution reveals a significant decrease of the resonance frequency, confirming MV binding. Subsequent release is achieved by pH lowering, decreasing the host–guest interactions. The dissociation of the host–guest complex, release of the guest from the film, as well as full reversibility of the binding event are identified by QCM-D. In addition, UV-vis data quantify the surface coverage of the guest molecule in the film after loading and release, respectively. These findings establish the pH-responsiveness of WP6 as a novel external stimulus for the reversible guest molecule recognition in thin films. View Full-Text
Keywords: host-guest chemistry; layer-by-layer self-assembly; pillar[6]arene; pH-responsiveness host-guest chemistry; layer-by-layer self-assembly; pillar[6]arene; pH-responsiveness
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MDPI and ACS Style

Nicolas, H.; Yuan, B.; Xu, J.; Zhang, X.; Schönhoff, M. pH-Responsive Host–Guest Complexation in Pillar[6]arene-Containing Polyelectrolyte Multilayer Films. Polymers 2017, 9, 719.

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