Ionic liquids as promising functional materials for microextraction of steroid hormones

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Prospects for the use of imidazolium ionic liquids (IL) as extractants of sex steroid hormones (estrogens and androgens) in microextraction methods (dispersive liquid-liquid microextraction, DLLME, and magnetic solid-phase microextraction, mSPME) are identified. The key parameters of DLLME using C6MImNTf2 IL, affecting the extraction efficiency, are optimized using the design of experiment method. High degrees of recovery (88–99 %) are achieved. An approach of dynamic IL immobilization on the surface of magnetic nanoparticles (MNPs) for steroid extraction under mSPME conditions is proposed. Two types of MNP pre-coating are studied: hydrophilic based on silica and hydrophobic with oleic acid. The capabilities of C8MImBF4 IL as a MNP surface modifier for efficient steroid extraction are revealed. Optimum conditions provided high degrees of recovery (83–97 %), with the exception of estriol (60 %). The detection limits are 0.26–1.29 ng/mL. Limitations of the method related to partial removal of IL from the surface of NPs are revealed, which reduces the reproducibility of the results for estriol.

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作者简介

A. Araslanova

Saint Petersburg State University

Email: Lena_pol@inbox.ru

Institute of Chemistry

俄罗斯联邦, Universitetskii pr. 26, Petrodvorets, Saint Petersburg

M. Vasilenko

Saint Petersburg State University

Email: Lena_pol@inbox.ru

Institute of Chemistry

俄罗斯联邦, Universitetskii pr. 26, Petrodvorets, Saint Petersburg

E. Bessonova

Saint Petersburg State University

编辑信件的主要联系方式.
Email: Lena_pol@inbox.ru

Institute of Chemistry

俄罗斯联邦, Universitetskii pr. 26, Petrodvorets, Saint Petersburg

L. Kartsova

Saint Petersburg State University

Email: Lena_pol@inbox.ru

Institute of Chemistry

俄罗斯联邦, Universitetskii pr. 26, Petrodvorets, Saint Petersburg

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2. Scheme 1. Structural formulas of steroid hormones.

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3. Fig. 1. Chromatogram of a mixture of steroid hormone standards (estrogens and androgens) by RP HPLC with diode array detection. Conditions: liquid chromatograph LC-40 (Shimadzu), column: Kinetex™ 5 μm Biphenyl 100 Å, 150 × 2.1 mm, 5 μm, eluent: phase A – 0.1% aqueous formic acid solution, phase B – acetonitrile, 0.1% HCOOH, gradient elution mode. Mobile phase flow rate: 0.3 ml/min, thermostat temperature: 30°C.

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4. Fig. 2. The influence of the nature of the dispersing solvent and ionic liquid on the values of the degrees of extraction of steroid hormones (estrone, estradiol, estriol, testosterone and progesterone) from aqueous solutions.

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5. Fig. 3. Pareto plot for factors influencing the extraction of (a) testosterone and (b) estriol (factors: A – pH value of the sample solution, B – volume of acetonitrile, C – mass of ionic liquid).

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6. Fig. 4. Dependence of the peak area (a) of testosterone and (b) estradiol (after extraction) on the content of acetonitrile, the mass of the ionic liquid and the pH value of the solution.

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7. Fig. 5. Effect of (a) NaCl salt concentration (0–10%, w/v) and (b) ultrasonic treatment time on the extraction efficiency of steroids.

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8. Fig. 6. Scheme of synthesis of core-shell nanoparticles.

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9. Fig. 7. Electron micrographs of nanoparticles (a) Fe3O4@OA and (b) Fe3O4@SiO2 obtained by the SEM method.

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10. Fig. 8. Magnetization curves of Fe3O4@OA nanoparticles.

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11. Fig. 9. IR spectra of Fe3O4, Fe3O4@SiO2, Fe3O4@OA nanoparticles and pure oleic acid.

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12. Fig. 10. Results of optimization of parameters affecting the extraction of analytes by mSPME: Pareto plot for (a) estradiol and (b) progesterone for factors (factor designations: A – mixing time, B – ionic liquid mass, C – nanoparticle suspension volume) and dependence of peak area (c) of estradiol and (d) testosterone on the nanoparticle suspension volume and ionic liquid mass.

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13. Fig. 11. Selection of sample volume for steroid extraction by mSPME.

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