Development of hybrid monoliths incorporating metal–organic frameworks for stir bar sorptive extraction coupled with liquid chromatography for determination of estrogen endocrine disruptors in water and human urine samples

Abstract

A novel coating based on hybrid monolith with metal–organic framework (MOF) onto conventional Teflon-coated magnetic stir bars was developed. For this purpose, the external surface of the Teflon stir bar was firstly vinylized in order to immobilize a glycidyl methacrylate (GMA)–based polymer onto the magnet. Then, an amino-modified MOF of type MIL-101 (NH2-MIL-101(Al)) was covalently attached to the GMA-based monolith. After the synthesis process, several parameters affecting extraction of target estrogens by stir bar sorptive extraction (SBSE) including pH, ionic strength, extraction time, stirring rate, desorption solvent, and desorption time were also investigated. The resulting hybrid monolith was evaluated as SBSE sorbent for extraction of three estrogens (estrone, 17β-estradiol, estriol) and synthetic 17β-ethinylestradiol from water and human urine samples followed by HPLC with fluorescence detection (excitation and emission wavelengths, 280 and 310 nm, respectively). Under the optimal experimental conditions, the analytical figures of the method were established, achieving satisfactory limits of detection in the range of 0.015–0.58 µg L−1, recovery results ranging from 70 to 95% with RSD less than 6%, and precision values (intra- and inter-extraction units) below 6%. Graphical abstract

Aptamer-functionalized stir bar sorptive extraction for selective isolation, identification, and determination of concanavalin A in food by MALDI-TOF-MS

“…Apart from the benefit of providing higher selectivity to the extraction process, it would also be interesting to develop inexpensive and robust aptamer-functionalized SBSE coatings from different materials, as an alternative to those that can be prepared in commercial PDMS-coated stir bars (e.g., Twister SBSE Gerstel) [ 24 ]. In this context, our research group have successfully employed low-cost commercial PTFE stir bars to prepare SBSE coatings for the extraction of low levels of acidic drugs [ 4 ] and estrogens [ 25 ] from environmental water and urine samples. Inspired by these studies, PTFE stir bars were selected and properly modified prior to functionalization with the selective aptamer against the target protein Con A.…”

“…1 , the PTFE stir bar was firstly chemically etched with sodium naphthalene (Fluoroetch®) to convert the C-F bonds into C-H, C-OH, and COOH moieties. Then, the incorporated hydroxyl groups were susceptible to react with the epoxide groups of the GMA molecules, giving as a result a vinylized active surface [ 4 , 25 , 26 ], which was functionalized with the thiol-modified aptamer against Con A by a “thiol-ene” click reaction.…”

Evolution of Green Sample Preparation: Fostering a Sustainable Tomorrow in Analytical Sciences

“…Table summarizes recent contributions related to green sample preparation methods for bioanalysis. ,,− As it can be seen, there is not a clear preference for the use of liquid-based or solid-based extractions. A clear trend cannot be observed in the materials/solvents selected, with both commercial and lab-made alternatives being used.…”

Sensor technologies for the detection and monitoring of endocrine-disrupting chemicals

“…Monitoring and detection of EDCs compounds, as noted earlier, have been traditionally performed with analytical methods such as gas chromatography-mass spectrometry (GC-MS) ( Azzouz et al, 2020 ), Liquid chromatography ( Zatrochova et al, 2022 ), ultra-performance liquid chromatography-tandem mass spectrometry ( Zhou et al, 2022 ), capillary electrophoresis ( Chen et al, 2021 ) surface plasmon resonance ( Bakhshpour and Denizli, 2020 ), and solid phase extraction ( Zhang et al, 2020 ). Although conventional analytical methods are standardized, highly sensitive and selective, these approaches are time-consuming, have complex protocols, often require sample pre-treatment and sophisticated instrumentation, trained and skilled personnel.…”