New ternary water-soluble support from self-assembly of β-cyclodextrin-ionic liquid and an anionic polymer for a dialysis device.

Asmaa Bouyahya,Audrey Favrelle-Huret,Frédéric Guillen,Sébastien Balieu,Mohammed Lahcini,Valérie Mesnage,Carole Karakasyan-Dia,Didier Le Cerf,Géraldine Gouhier,Berthe-Sandra Sembo-Backonly

doi:10.1007/s11356-021-16374-0

Abstract

We developed a new hybrid material resulting from an innovative supramolecular tripartite association between an ionic liquid covalently immobilized on primary β-cyclodextrins rim and an anionic water-soluble polymer. Two hydrophilic ternary complexes based on native and permethylated β-cyclodextrins substituted with an ionic liquid and immobilized on poly(styrene sulfonate) (CD-IL+PSS- and CD(OMe)IL+PSS-) were obtained by simple dialysis with a cyclodextrin maximal grafting rate of 25% and 20% on the polymer, respectively. These polyelectrolytes are based on electrostatic interactions between the opposite charges of the imidazolium cation of the ionic liquid and the poly(styrene sulfonate) anion. The inclusion properties of the free cavities of the cyclodextrins and the synergic effect of the polymeric matrix were studied with three reference guests such as phenolphthalein, p-nitrophenol, and 2-anilinonaphthalene-6-sulfonic acid using UV-visible, fluorescent, and NMR spectroscopies. The support has been applied successfully in dialysis device to extract and concentrated aromatic model molecule. This simple and flexible synthetic strategy opens the way to new hybrid materials useful for fast and low-cost ecofriendly extraction techniques relevant for green analytical chemistry.

Highlights

Ionic liquids (ILs) are a broad class of salts with melting points below 100°C and are generally composed of an organic cation, and an organic or inorganic anion
The ring-opening of ε-caprolactone 1 by methyltrichlorosilane (MeSiCl3) in presence of NaI in ACN led to methyl 6-halohexanoate 2
The immobilization of a short ionic linker on β-cyclodextrin inhibited all intramolecular inclusion phenomena and provided certain flexibility to improve the electrostatic interactions with poly(styrene sulfonate) (PSS)

Summary

Introduction

Ionic liquids (ILs) are a broad class of salts with melting points below 100°C and are generally composed of an organic cation (such as imidazolium, pyridinium, phosphonium or ammonium cation), and an organic or inorganic anion. By avoiding any intramolecular inclusion of the ionic liquid, this new assembly will keep the cavity of the β-cyclodextrin available and improve the potential of extraction and preconcentration of molecules of interest. The experiment was carried out on CD(OMe)-IL+PSS- 12 with grafting of 1/44 CD-IL/SS and inclusion of PP varying between 16% and 26% was observed, probably due to an increase of water solubility of the complex and better accessibility to CD cavity once immobilized on the polymer backbone.

Results

Conclusion