Combination of in situ metathesis reaction with a novel “magnetic effervescent tablet-assisted ionic liquid dispersive microextraction” for the determination of endogenous steroids in human fluids
Herein, a novel magnetic effervescence tablet-assisted microextraction coupled to in situ metathesis reaction of ionic liquid (IS-META-ILDM) is presented for the determination of four endogenous steroids in human urine, pregnant women’s blood, and fetal umbilical cord blood. The magnetic effervescent tablets, which were composed of Fe3O4 nanoparticles, sodium carbonate (alkaline source), and tartaric acid (acidic source), were used to disperse the extractant and for convenient magnetic separation. After the effervescent reaction, in situ reaction between NH4PF6 and [C6MIM]BF4 was adopted to change hydrophilic ionic liquid to hydrophobic liquid, which could be separated from the aqueous phase. The newly developed method has three obvious advantages: (1) combination of effervescent dispersion and magnetic nanoparticles’ retrieval is cost-effective and the dispersion and collection of the extractant can be completed almost simultaneously; (2) as compared to temperature-controlled ionic liquid dispersive microextraction and cold-induced solidified microextraction, this method avoids a heating and cooling process which significantly reduces the extraction time and energy cost; and (3) the combination of adsorption by magnetic nanoparticles with extraction by in situ metathesis reaction easily produces high recoveries for target analytes. The optimized composition of effervescent tablet and experimental parameters are as follows: 0.64 g mixture of sodium carbonate and tartaric acid, 7 mg of Fe3O4 (20 nm) as magnetic sorbents, 40 μL of [C6MIM]BF4 as the extraction solvent, 0.15 g NH4PF6, and 300 μL of elution solvent. Under the optimized conditions, the newly developed method provided high extraction recoveries (90.0–118.5%) and low LODs (0.14–0.17 μg L−1) in urine and blood samples. In total, this IS-META-ILDM method provided high extraction efficiency, fast and convenient separation, and underutilization of any organic solvent, and thus it has great potential for the determination of trace endogenous steroids in complex human fluids.
KeywordsEndogenous steroid hormones Magnetic effervescent tablet In situ metathesis reaction Effervescence-assisted microextraction Magnetic nanoparticles Human urine and blood
This work was jointly supported by the Natural Science Foundation of Zhejiang Provincial (LQ17H260005), the National Natural Science Foundation of China (21577107), and the Wenzhou Municipal Science and Technology Bureau (Y20160181).
Compliance with ethical standards
Conflict of interest
The authors declare that they have no conflict of interest.
All individual participants received a complete description of the study and gave written informed consent before providing the urine (healthy male) and blood samples (pregnant women’s blood and fetal umbilical cord blood). The studies were approved by The Ethics Committee of the Wenzhou People’s Hospital and performed in accordance with the ethical standards.
- 3.Gervasoni J, Schiattarella A, Primiano A, D'Addurno I, Cocci A, Zuppi C, et al. Simultaneous quantification of 17-hydroxyprogesterone, androstenedione, testosterone and cortisol in human serum by LC-MS/MS using TurboFlow online sample extraction. Clin Biochem. 2016;49:998–1003.CrossRefGoogle Scholar
- 4.Shibayama Y, Higashi T, Shimada K, Kashimada K, Onishi T, Ono M, et al. Liquid chromatography-tandem mass spectrometric method for determination of salivary 17α-hydroxyprogesterone: a noninvasive tool for evaluating efficacy of hormone replacement therapy in congenital adrenal hyperplasia. J Chromatogr B. 2008;867:49–56.CrossRefGoogle Scholar
- 8.Xu W, Li H, Guan Q, Shen Y, Cheng L. A rapid and simple liquid chromatography-tandem mass spectrometry method for the measurement of testosterone, androstenedione, and dehydroepiandrosterone in human serum. J Clin Lab Anal. 2016:1–7.Google Scholar
- 15.Wan J, Cai W, Meng X, Liu E. Monodisperse water-soluble magnetite nanoparticles prepared by polyol process for high-performance magnetic resonance imaging. Chem Commun. 2007;0:5004–5006.Google Scholar
- 23.Liu Y, Li H, Lin J-M. Magnetic solid-phase extraction based on octadecyl functionalization of monodisperse magnetic ferrite microspheres for the determination of polycyclic aromatic hydrocarbons in aqueous samples coupled with gas chromatography-mass spectrometry. Talanta. 2009;77:1037–42.CrossRefGoogle Scholar
- 26.Arain M-S, Arain S-A, Kazi T-G, Afridi H-I, Ali J, Naeemulllah, et al. Temperature controlled ionic liquid-based dispersive micro-extraction using two ligands, for determination of aluminium in scalp hair samples of Alzheimer's patients: a multivariate study. Spectrochim Acta A Mol Biomol Spectrosc. 2015;137:877–85.CrossRefGoogle Scholar
- 29.Stopforth A, Burger B-V, Crouch A-M, Sandra P. The analysis of estrone and 17β-estradiol by stir bar sorptive extraction-thermal desorption-gas chromatography/mass spectrometry: application to urine samples after oral administration of conjugated equine estrogens. J Chromatogr B. 2007;856:156–64.CrossRefGoogle Scholar
- 30.Guo T-D, Chan Y-M, Soldin S-J. Steroid profiles using liquid chromatography tandem mass spectrometry with atmospheric pressure photoionization source. Arch Pathol Lab Med. 2004;128:469–75.Google Scholar
- 32.Sippell W-G, Bidlingmaier F, Becker H, Brunig T, Dorr H, Hahn, et al. Simultaneous radioimmunoassay of plasma aldosterone, corticosterone, 11-deoxycorticosterone, progesterone, 17-hydroxyprogesterone, 11-deoxycortisol, cortisol and cortisone. J Steroid Biochem. 1978;9(1):63–74.CrossRefGoogle Scholar
- 33.Sippell W, Becker H, Versmold H, Bidlingnaier F, Knorr D. Longitudinal studies of plasma aldosterone, corticosterone, deoxycorticosterone, progesterone, 17-hydroxyprogesterone, cortisol, and cortisone determined simultaneously in mother and child at birth and during the early neonatal period. I. Spontaneous delivery. J Clin Endocrinol Metab. 1978;46:971–85.CrossRefGoogle Scholar