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A metal-organic framework of type MIL-101(Cr) for emulsification-assisted micro-solid-phase extraction prior to UHPLC-MS/MS analysis of polar estrogens

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Abstract

A seamless two-step extraction procedure integrating ultrasound-assisted emulsification microextraction (USAEME) and vortex-assisted micro-solid-phase extraction (μ-SPE) was developed. A highly porous metal-organic framework of type MIL-101(Cr) is used as the sorbent, and ultra-high-performance liquid chromatography in combination with tandem mass spectrometry is used for detection. The steroid hormones estrone 17β-estradiol, estriol, and 17α-ethynylestradiol were extracted from water samples by using this method. These steroids are polar and do not pass through the polypropylene membrane that is conventionally used in μ-SPE. In the method presented here, 1-octanol is used in USAEME to extract and pre-concentrate the steroids. This facilitates the transfer to the MIL-101(Cr) phase retained by the membrane in the subsequent μ-SPE step. MIL-101(Cr) was characterized by various methods, and the parameters affecting the overall extraction efficiency were optimized. Under the most favorable conditions, the limits of detection are between 0.95 and 23 ng L−1. Good intra-day and inter-day precisions were obtained, with relative standard deviations of ≤ 9.9%. Enrichment factors are between 34 and 52. The method was applied to genuine environmental water samples in which estrone was detected. Relative recoveries ranged between 85.4% and 120.8%.

Schematic of the emulsification-assisted micro-solid-phase extraction (μ-SPE). By emulsifying 1-octanol in the water sample, polar estrogens dissolved in the solvent can easily pass the hydrophobic polypropylene membrane and then are adsorbed onto the unmodified MIL-101(Cr) held within the μ-SPE device.

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Acknowledgements

The authors thankfully acknowledge the National University of Singapore (NUS) for the support provided throughout the duration of this research (Grant No. 143-000-023-001). S.C. Tan is grateful to the NUS Graduate School for Integrative Sciences and Engineering for a scholarship award.

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Authors and Affiliations

  1. NUS Graduate School for Integrative Sciences and Engineering, National University of Singapore, University Hall, Tan Chin Tuan Wing #04-02, 21 Lower Kent Ridge Road, Singapore, 119077, Singapore

    Sze Chieh Tan & Hian Kee Lee

  2. Department of Chemistry, National University of Singapore, 3 Science Drive 3, Singapore, 117543, Singapore

    Sze Chieh Tan & Hian Kee Lee

  3. National University of Singapore Environmental Research Institute, T-Lab Building #02-01, 5A Engineering Drive 1, Singapore, 117411, Singapore

    Hian Kee Lee

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Tan, S.C., Lee, H.K. A metal-organic framework of type MIL-101(Cr) for emulsification-assisted micro-solid-phase extraction prior to UHPLC-MS/MS analysis of polar estrogens. Microchim Acta 186, 165 (2019). https://doi.org/10.1007/s00604-019-3289-9

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