Vortex assisted liquid-liquid microextraction based on in situ formation of a natural deep eutectic solvent by microwave irradiation for the determination of beta-blockers in water samples


JOURNAL OF CHROMATOGRAPHY A, vol.1642, 2021 (SCI-Expanded) identifier identifier identifier

  • Publication Type: Article / Article
  • Volume: 1642
  • Publication Date: 2021
  • Doi Number: 10.1016/j.chroma.2021.462007
  • Journal Indexes: Science Citation Index Expanded (SCI-EXPANDED), Scopus, Academic Search Premier, PASCAL, Analytical Abstracts, Aqualine, Aquatic Science & Fisheries Abstracts (ASFA), BIOSIS, CAB Abstracts, Chemical Abstracts Core, Chimica, Compendex, EMBASE, Environment Index, Food Science & Technology Abstracts, MEDLINE, Pollution Abstracts, Veterinary Science Database
  • Keywords: Hydrophobic natural deep eutectic solvent, In situ formation, Liquid-liquid microextraction, High-performance liquid chromatography, Experimental design, beta-blockers, EXTRACTION
  • Karadeniz Technical University Affiliated: Yes


In this study, a simple, green, and reliable method combining vortex-assisted liquid-liquid microextraction based on in situ formation of a novel hydrophobic natural deep eutectic solvent (NADES-VA-LLME) and high-performance liquid chromatography (HPLC) was developed for the determination of metoprolol and propranolol in water samples. The novel NADES was synthesized in situ within only 20 s by subjecting the water sample containing azelaic acid and thymol to microwave irradiation at 50 degrees C. Initial studies indicated that a 17:1 ratio of thymol to azelaic acid yielded the highest response for analytes. The influence of 7 parameters, including NADES volume, salt amount, sample pH, vortex time, centrifugation time, microwave time, and temperature, were screened using a 2(7-3) fractional factorial design. The obtained significant parameters were optimized by response surface methodology employing a Box-Behnken design. The method displayed satisfactory linearity (r=0.9996) for metoprolol and propranolol with limits of detection of 0.2 and 0.1 mu g/L, respectively. The relative standard deviation at 2.5, 40, and 80 mu g/L levels was lower than 6%, with accuracy in the range of 90.8-100.2%. Enrichment factors were 147.0 and 144.4 for metoprolol and propranolol, respectively. This study demonstrates that the developed in situ NADES-VA-LLME-HPLC technique can be considered as a fast and environmentally friendly alternative for isolation/preconcentration of beta-blockers from water samples. (C) 2021 Elsevier B.V. All rights reserved.