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Hybrid monoliths with metal-organic frameworks in spin columns for extraction of non-steroidal drugs prior to their quantitation by reversed-phase HPLC

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Abstract

A (glycidyl methacrylate)-co-(ethylene glycol dimethacrylate) polymer (poly(GMA-co-EDMA)) was functionalized with metal-organic frameworks (MOF) and used as a sorbent for solid-phase extraction (SPE). The polymeric sorbent was prepared in-situ by photopolymerization in a previously wall-modified spin column, and then modified with an amino-modified MOF of type NH2-MIL-101(Cr). The sorbents were used for the extraction of nonsteroidal anti-inflammatory drugs (NSAIDs) from human urine samples. The sorbent was compared with the parent monolith and embedded approach, where the MOF particles are admixed in the polymerization mixture before the in-situ polymerization in the modified spin column. SPE is performed by percolating the sample solutions in a centrifuge, which streamlines the SPE steps. The hybrid composites were characterized by scanning electron microscopy and nitrogen intrusion porosimetry. Three NSAIDs (ketoprofen, flurbiprofen, and ibuprofen) were tested. They were eluted from the sorbent with acidified water-acetonitrile mixtures and subsequently analyzed by reversed-phase HPLC with UV detection. The detection limits varied in the range from 0.1 to 7 μg·L−1, and the precisions (relative standard deviation) were <14% in all the cases. The recoveries were between 71.0 and 78.0% in spiked urine samples.

A hybrid monolith modified with amino-modified MOF [named NH2-MIL-101(Cr)] in wall-modified spin columns was prepared. The resulting micro-extraction device was applied to the extraction and preconcentration of non-steroidal anti-inflammatory drugs.

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Acknowledgments

Financial support from PROMETEO/2016/145 (Conselleria de Educación, Investigación, Cultura y Deporte, Generalitat Valenciana, Spain) and RTI2018-095536-B-I00 (Ministry of Science, Innovation and Universities, Spain) is gratefully acknowledged. E. J. C.-C. thanks the Generalitat Valenciana for a VALi+D postdoctoral research contract.

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Correspondence to Enrique Javier Carrasco-Correa or José Manuel Herrero-Martínez.

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Giesbers, M., Carrasco-Correa, E.J., Simó-Alfonso, E.F. et al. Hybrid monoliths with metal-organic frameworks in spin columns for extraction of non-steroidal drugs prior to their quantitation by reversed-phase HPLC. Microchim Acta 186, 759 (2019). https://doi.org/10.1007/s00604-019-3923-6

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Keywords

  • Sample preparation
  • Solid-phase (micro)extraction
  • Polymer organic monoliths
  • Surface modification
  • Embedded approach
  • In-situ polymerization
  • Microporous crystalline materials
  • Centrifuge extraction procedure
  • Polypropylene wall modification
  • Photografting