Cyclodextrin-Functionalized Fiber Yarns Spun from Deep Eutectic Cellulose Solutions for Nonspecific Hormone Capture in Aqueous Matrices.

Hannes Orelma,Orlando J. Rojas,Steven Spoljaric,Jani Lehmonen,Jukka Seppälä,Tommi Virtanen,Ali Harlin

doi:10.1021/acs.biomac.7b01765

Hannes Orelma, Orlando J. Rojas + Show 5 more

Open Access

https://doi.org/10.1021/acs.biomac.7b01765

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Abstract

A wood based yarn platform for capturing pharmaceutical molecules from water was developed. Cellulose fiber yarns were modified with cyclodextrins, and the capture of 17α-ethinyl estradiol (EE2), a synthetic estrogen hormone used as contraceptive, from water was tested. The yarns were prepared by spinning a deep eutectic solution (DES) of cellulose in choline chloride-urea. Despite their high porosity and water sorption capacity (5 g/g), the spun fiber yarns displayed high wet strength, up to 60% of that recorded in dry condition (128 MPa with 17% strain at break). Cyclodextrin irreversible attachment on the yarns was achieved with adsorbed chitosan and the conjugation reactions and capture of EE2 by the cyclodextrin-modified cellulose were confirmed via online detection with Surface Plasmon Resonance (SPR). The facile synthesis of the bioactive yarns and EE2 binding capacity from aqueous matrices (as high as 2.5 mg/g) indicate excellent prospects for inexpensive platforms in disposable affinity filtration. The study presents a strategy to produce a wood fiber based yarn to be used as a platform for human and veterinary pharmaceutical hormone capture.

Highlights

Besides their advantages as far as carbon neutrality, wood-based cellulose materials have an extraordinarily large application potential due to their cost, biodegradability, and recyclability
The measurements were carried out with gold-covered surface plasmon resonance (SPR) sensors carrying spin-coated cellulose nanofibrils (CNF) that were utilized as a model for the surface of the fiber yarns
Cellulose fiber yarns carrying cyclodextrin were used for 17αethinyl estradiol (EE2) capture

Summary

■ INTRODUCTION

Besides their advantages as far as carbon neutrality, wood-based cellulose materials have an extraordinarily large application potential due to their cost, biodegradability, and recyclability. EE2 Hormone-Capturing Fiber Yarns Obtained by DES Solution Regeneration and Synthesized by First Adsorbing Chitosan Followed by Covalent Conjugation of Carboxylated Cyclodextrinsa aCyclodextrin moieties were able to bind EE2 hormones non- from water matrices. The water absorption properties of cellulose fiber yarns, their high wet strength and affinity to chitosan, were combined with the immobilization of TEMPO-oxidized cyclodextrins for the capture of 17α-ethinyl estradiol from aqueous matrices (Scheme 1). For covalent conjugation of TO-CD to the chitosan-modified fiber yarn, aqueous EDC/NHS coupling was utilized, which catalyzed the formation of amide bond between carboxyl and primary amine groups.[36] 0.025 g of TO-CD, 0.06 g of EDC, and 0.106 g of NHS were dissolved into 50 mL of 50 mM NaOAc buffer at pH 5. The measurements were carried out with gold-covered SPR sensors carrying spin-coated cellulose nanofibrils (CNF) that were utilized as a model for the surface of the fiber yarns. NMR spectra of β-cyclodextrin before and after TEMPO-oxidation. (i) nonoxidated cyclodextrin. (ii) TEMPO-oxidized cyclodextrin, neutral conditions. (iii) TEMPO-oxidized cyclodextrin, alkaline conditions

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■ CONCLUSIONS

■ ACKNOWLEDGMENTS

Findings

■ REFERENCES