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Improved microextraction of selected triazines using polymer monoliths modified with carboxylated multi-walled carbon nanotubes

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Abstract

This article reports on the enhancement of the capacity of an acrylate-based monolithic solid sorbent by anchoring carboxylated multi-walled carbon nanotubes (c-MWCNTs) in its pores and on its surface. Monolithic poly(butyl acrylate-co-ethyleneglycol dimethacrylate) [poly(BA-co-EGDMA)] was synthetized inside a fused silica capillary via free-radical polymerization, and an ethanolic dispersion of c-MWCNTs was passed through the capillary. The resulting poly(BA-co-EGDMA-c-MWCNTs) monolith was characterized by scanning electron microscopy to confirm the presence of the c-MWCNTs. The effect of using three different kinds of carbon nanoparticles and the microextraction step were studied using triazine herbicides as model compunds. The use of c-MWCNTs resulted in best performance in terms of extraction enhancement (compared to carboxylated single-walled carbon nanotubes and oxidized single-walled carbon nanohorns). The use of these carbon nanoparticles improved the extraction of triazines in any case when compared to using a bare poly(BA-co-EGDMA) monolith. The triazines were then quantified by gas chromatography with mass spectrometric detection. Detection limits ranged from 0.03 to 0.1 μg·L−1 (except for simazine; 0.6 μg·L−1), and the precision (relative standard deviation) varied between 3.0 and 11.4 %. The reproducibility between units is <14.3 % (expressed as relative standard deviation) which demonstrates the robustness of the method. The method was applied to analyze an unknown sample of orange juice and gave a value of 0.18 μg·L−1 for prometryn. Finally, the analysis of spiked samples of water and orange juices yielded recoveries ranging from 81 to 113 % and 75 to 125 %, respectively.

Immobilization of carboxylated multi-walled carbon nanotubes (c-MWCNTs) on the poly(BA-co-EGDMA) monolith prepared inside a fused silica capillary results in improved extraction of nine target triazines from water and juice samples.

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Acknowledgments

Financial support from the Spanish Ministry of Science and Innovation (grant CTQ2011-23790 and CTQ2014-52939-R) is gratefully acknowledged. B. Fresco-Cala expresses her gratitude for the predoctoral grant (ref FPU13/03896) from the Spanish Ministry of Education.

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Authors and Affiliations

  1. Department of Analytical Chemistry, Institute of Fine Chemistry and Nanotechnology, Marie Curie Building, Campus of Rabanales, University of Córdoba, 14071, Córdoba, Spain

    Beatriz Fresco-Cala, Soledad Cárdenas & Miguel Valcárcel

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  1. Beatriz Fresco-Cala
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  2. Soledad Cárdenas
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  3. Miguel Valcárcel
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Correspondence to Miguel Valcárcel.

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Fresco-Cala, B., Cárdenas, S. & Valcárcel, M. Improved microextraction of selected triazines using polymer monoliths modified with carboxylated multi-walled carbon nanotubes. Microchim Acta 183, 465–474 (2016). https://doi.org/10.1007/s00604-015-1673-7

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