Core-shell polydopamine magnetic nanoparticles as sorbent in micro-dispersive solid-phase extraction for the determination of estrogenic compounds in water samples prior to high-performance liquid chromatography-mass spectrometry analysis.
In this work, core-shell Fe3O4@poly(dopamine) magnetic nanoparticles (m-NPs) were prepared and characterized in our laboratory and applied as sorbents for the magnetic-micro solid phase extraction (m-μSPE) of twelve estrogenic compounds of interest (i.e. 17α-estradiol, 17β-estradiol, estrone, hexestrol, 17α-ethynylestradiol, diethylstibestrol, dienestrol, zearalenone, α-zearalanol, β-zearalanol, α-zearalenol and β-zearalenol) from different water samples. Separation, determination and quantification were achieved by high-performance liquid chromatography coupled to ion trap mass spectrometry with electrospray ionization. NPs@poly(dopamine) were synthesized by a chemical coprecipitation procedure and characterized by different surface characterization techniques (X-ray diffraction, X-ray photoelectron spectroscopy, thermogravimetric analysis, transmission and scanning electron microscopy, infrared and Raman spectroscopy, vibrating sample magnetometry, microelectrophoresis and adsorption/desorption isotherms). Parameters affecting the extraction efficiency of m-μSPE (i.e. polymerization time, pH of the sample, extraction and elution conditions) were studied and optimized. The methodology was validated for Milli-Q, mineral, tap and wastewater using 2-methoxyestradiol as internal standard, obtaining recoveries ranging from 70 to 119% with relative standard deviation values lower than 20% and limits of quantification in the range 0.02-1.1 μg/L.
Departamento de Química, Unidad Departamental de Química Analítica, Facultad de Ciencias, Universidad de La Laguna (ULL), Avda. Astrofísico Fco. Sánchez, s/n, 38206 La Laguna, Spain. Electronic address: bsocasro@ull.es.
Bárbara
B
Socas-Rodríguez
Departamento de Química, Unidad Departamental de Química Analítica, Facultad de Ciencias, Universidad de La Laguna (ULL), Avda. Astrofísico Fco. Sánchez, s/n, 38206 La Laguna, Spain. Electronic address: jhborges@ull.edu.es.
Javier
J
Hernández-Borges
Laboratory of Nanotechnology on Surfaces, Institute of Materials Science of Seville (CSIC-Univ. Sevilla), Calle Américo Vespucio 49, 41092 Sevilla, Spain. Electronic address: psalazar@icmse.csic.es.
Pedro
P
Salazar
Neurochemistry and Neuroimaging Group, Laboratory of Sensors, Biosensors and Materials, Faculty of Medical Sciences, University of La Laguna, Campus de Ofra s/n,, 38071 La Laguna, Tenerife, Spain. Electronic address: mmartinh@ull.edu.es.
Miriam
M
Martín
Departamento de Química, Unidad Departamental de Química Analítica, Facultad de Ciencias, Universidad de La Laguna (ULL), Avda. Astrofísico Fco. Sánchez, s/n, 38206 La Laguna, Spain. Electronic address: mrguez@ull.edu.es.
Miguel Ángel
MÁ
Rodríguez-Delgado
D000327:Adsorption; D002623:Chemistry Techniques, Analytical / Q000379:methods*; D002851:Chromatography, High Pressure Liquid; D004967:Estrogens / Q000032:analysis*; D058185:Magnetite Nanoparticles / Q000737:chemistry*; D013058:Mass Spectrometry; D052616:Solid Phase Extraction; D062065:Wastewater / Q000737:chemistry; D014867:Water / Q000737:chemistry*; D014874:Water Pollutants, Chemical / Q000032:analysis*
D004967:Estrogens; D058185:Magnetite Nanoparticles; D062065:Wastewater; D014867:Water; D014874:Water Pollutants, Chemical
Estrogens; Liquid chromatography; Magnetic nanoparticles; Mass spectrometry; Microdispersive solid-phase extraction; Polydopamine