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Issue 38, 2018
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Effect of organic and inorganic ions on the lower critical solution transition and aggregation of PNIPAM

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Abstract

We have studied the effect of different ions belonging to the extended Hofmeister series on the thermosensitive polymer poly(N-isopropylacrylamide) (PNIPAM), by combining Differential Scanning Calorimetry (DSC) and Dynamic Light Scattering (DLS). The variations in the lower critical solution temperature (TLCS) and enthalpy change during PNIPAM phase separation evidence the importance of considering both hydration and hydrophobicity to explain the interaction of ions with interfaces. The results obtained in the presence of inorganic ions can be explained by the tendency of water molecules to preferentially hydrate the PNIPAM chains or the ions, depending on the kosmotropic (highly hydrated) or chaotropic (poorly hydrated) character of the ions. On the contrary, tetraphenyl organic ions (Ph4B and Ph4As+) interact with the hydrophobic moieties of PNIPAM chains, inducing a significant reduction of the TLCS. DLS results show that the aggregation state of PNIPAM above the TLCS is also strongly influenced by the presence of ions. While macroscopic phase separation (formation of a polymer-rich phase insoluble in water) was apparent in the presence of inorganic ions, we observed the formation of submicron PNIPAM aggregates at temperatures above the TLCS in the presence of the hydrophobic ions. Kinetically arrested monodisperse PNIPAM nanoparticles were formed in the presence of the Ph4B anion, while a rather polydisperse distribution of particle sizes was observed in the presence of Ph4As+. These results show that ionic specificity influences both the static (thermodynamic) and dynamic (kinetically controlled aggregation) states of PNIPAM in an aqueous environment.

Graphical abstract: Effect of organic and inorganic ions on the lower critical solution transition and aggregation of PNIPAM

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Publication details

The article was received on 15 Aug 2018, accepted on 17 Sep 2018 and first published on 26 Sep 2018


Article type: Paper
DOI: 10.1039/C8SM01679H
Citation: Soft Matter, 2018,14, 7818-7828
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    Effect of organic and inorganic ions on the lower critical solution transition and aggregation of PNIPAM

    L. Pérez-Fuentes, D. Bastos-González, J. Faraudo and C. Drummond, Soft Matter, 2018, 14, 7818
    DOI: 10.1039/C8SM01679H

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