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Nonionic Microgels Adapt to Ionic Guest Molecules: Superchaotropic Nanoions
Jasmin Simons1, Nabanita Hazra1, Alexander V Petrunin1
1Institute of Physical Chemistry, RWTH Aachen University, Landoltweg 2, DE-52074 Aachen, Germany.
Superchaotropic polyoxometalates (POMs) induce tunable swelling and deswelling in poly(N-isopropylacrylamide) (pNiPAM) microgels by altering their charge and acting as cross-links. This reveals POMs as effective agents for modifying microgel properties.
Area of Science:
- Materials Science
- Polymer Chemistry
- Soft Matter Physics
Background:
- Microgels are versatile solute carriers whose properties depend on solute interactions.
- Polyoxometalates (POMs) are ionic solutes with unique properties relevant for material modification.
Purpose of the Study:
- To investigate the impact of superchaotropic Keggin POMs (PW and SiW) on the swelling and internal structure of nonionic poly(N-isopropylacrylamide) (pNiPAM) microgels.
- To understand the mechanisms behind POM-induced swelling and deswelling in microgels.
- To explore the potential of POMs for fine-tuning microgel properties.
Main Methods:
- Light scattering techniques.
- Small-angle X-ray scattering (SAXS).
Main Results:
- POM binding induces microgel swelling at low concentrations due to counterion osmotic pressure and deswelling at higher concentrations via physical cross-linking.
- The swelling/deswelling transition is sharper for PW than SiW, attributed to PW's lower charge density and stronger binding.
- Microgel network softness and topology significantly influence the swelling response to POM binding.
- POM/pNiPAM systems exhibit both temperature and pH-responsive swelling.
Conclusions:
- POMs offer a novel method for controlling microgel swelling and internal structure, distinct from traditional salts or surfactants.
- Microgel network architecture plays a crucial role in mediating responses to external stimuli like POMs.
- These findings open avenues for designing advanced functional microgels with tunable properties for various applications.
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