A new automated flow-through adsorption/desorption procedure using a multiwalled carbon nanotube immobilised mixed matrix membrane is described. The membrane consisted of 25% (w/w) multiwall carbon nanotube loading in a cellulose triacetate polymer matrix as support and was cast and embedded in a flow-through cell with a channel of an approximate length of 20 mm, a width of 2 mm, and a depth of 1.5 mm. The membrane immobilised with nanoparticles was activated using 1-octanol as a conditioning solvent. For the analyte adsorption process, 6 mL of the sample was passed through the cell at a flow rate of 0.2 mL min−1. The entrapped target analytes were then desorbed dynamically with 60 µL of 2-propanal at a flow rate of 5 µL min−1 prior to HPLC/UV analysis. The performance of the system was demonstrated for the determination of chlorinated phenoxyacetic acid herbicides in sewage water samples. Under the optimum conditions, the linearity of this method ranged from 50 to 1000 ng mL−1, with a correlation coefficient (r) ≥ 0.993 and a detection limit varying from 15 to 20 ng mL−1. Enrichment factors of up to 55 were achieved with relative recoveries of 95–99% and precision values of 6.1–7.5%.
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He Y, Lee HK (1997) Liquid phase microextraction in a single drop of organic solvent by using a conventional microsyringe. Anal Chem 69(22):4634–4640. https://doi.org/10.1021/ac970242q
Liu HH, Dasgupta PK (1996) Analytical chemistry in a drop. Solvent extraction in a microdrop. Anal Chem 68(11):1817–1821. https://doi.org/10.1021/ac960145h
Thi Thanh Thuy P, See HH, Morand R, Kraehenbuehl S, Hauser PC (2012) Determination of free and total valproic acid in human plasma by capillary electrophoresis with contactless conductivity detection. J Chromatogr B 907:74–78. https://doi.org/10.1016/j.jchromb.2012.08.037
Ojeda CB, Rojas FS (2018) Vortex-assisted liquid–liquid microextraction (VALLME): the latest applications. Chromatographia 81(1):89–103. https://doi.org/10.1007/s10337-017-3403-2
Arthur CL, Pawliszyn J (1990) Solid-phase microextraction with thermal-desorption using fused-silica optical fibers. Anal Chem 62(19):2145–2148. https://doi.org/10.1021/ac00218a019
Bojko B, Cudjoe E, Wasowicz M, Pawliszyn J (2011) Solid-phase microextraction. How far are we from clinical practice? Trac-Trend Anal Chem 30(9):1505–1512. https://doi.org/10.1016/j.trac.2011.07.008
Ziegler M, Schmarr H-G (2019) Comparison of solid-phase microextraction using classical fibers versus mini-arrows applying multiple headspace extraction and various agitation techniques. Chromatographia 82(2):635–640. https://doi.org/10.1007/s10337-018-3659-1
Basheer C, Ainedhary AA, Rao BSM, Valliyaveettil S, Lee HK (2006) Development and application of porous membrane-protected carbon nanotube micro-solid-phase extraction combined with gas chromatography/mass spectrometry. Anal Chem 78(8):2853–2858. https://doi.org/10.1021/ac060240i
Faraji M, Yamini Y, Gholami M (2019) Recent advances and trends in applications of solid-phase extraction techniques in food and environmental analysis. Chromatographia 82(8):1207–1249. https://doi.org/10.1007/s10337-019-03726-9
See HH, Sanagi MM, Ibrahim WAW, Naim AA (2010) Determination of triazine herbicides using membrane-protected carbon nanotubes solid phase membrane tip extraction prior to micro-liquid chromatography. J Chromatogr A 1217(11):1767–1772. https://doi.org/10.1016/j.chroma.2010.01.053
Bruheim I, Liu XC, Pawliszyn J (2003) Thin-film microextraction. Anal Chem 75(4):1002–1010. https://doi.org/10.1021/ac026162q
Mirnaghi FS, Hein D, Pawliszyn J (2013) Thin-film microextraction coupled with mass spectrometry and liquid chromatography-mass spectrometry. Chromatographia 76(19–20):1215–1223. https://doi.org/10.1007/s10337-013-2443-5
Kamaruzaman S, Hauser PC, Sanagi MM, Ibrahim WAW, Endud S, See HH (2013) A simple microextraction and preconcentration approach based on a mixed matrix membrane. Anal Chim Acta 783:24–30. https://doi.org/10.1016/j.aca.2013.04.042
Mukhtar NH, See HH (2016) Carbonaceous nanomaterials immobilised mixed matrix membrane microextraction for the determination of polycyclic aromatic hydrocarbons in sewage pond water samples. Anal Chim Acta 931:57–63. https://doi.org/10.1016/j.aca.2016.04.032
Schmidt-Marzinkowski J, See HH, Hauser PC (2013) Electric field driven extraction of inorganic anions across a polymer inclusion membrane. Electroanalysis 25(8):1879–1886. https://doi.org/10.1002/elan.201300176
See HH, Hauser PC (2014) Automated electric-field-driven membrane extraction system coupled to liquid chromatography–mass spectrometry. Anal Chem 86(17):8665–8670. https://doi.org/10.1021/ac5015589
See HH, Hauser PC (2014) Electro-driven extraction of low levels of lipophilic organic anions and cations across plasticized cellulose triacetate membranes: effect of the membrane composition. J Membr Sci 450:147–152. https://doi.org/10.1016/j.memsci.2013.08.043
Hyotylainen T, Riekkola M-L (2008) Sorbent- and liquid-phase microextraction techniques and membrane-assisted extraction in combination with gas chromatographic analysis: a review. Anal Chim Acta 614(1):27–37. https://doi.org/10.1016/j.aca.2008.03.003
Ebrahimi R, Feizbakhsh A, Es’haghi A (2016) Extraction and derivatization of chlorophenoxy acid pesticides: performing two DLLME with one extracting phase. Chromatographia 79(7):515–520. https://doi.org/10.1007/s10337-016-3042-z
Song X-Y, Shi Y-P, Chen J (2012) A novel extraction technique based on carbon nanotubes reinforced hollow fiber solid/liquid microextraction for the measurement of piroxicam and diclofenac combined with high performance liquid chromatography. Talanta 100:153–161. https://doi.org/10.1016/j.talanta.2012.08.042
Yang Y, Chen J, Shi Y-P (2012) Determination of diethylstilbestrol in milk using carbon nanotube-reinforced hollow fiber solid-phase microextraction combined with high-performance liquid chromatography. Talanta 97:222–228. https://doi.org/10.1016/j.talanta.2012.04.021
Ji Z, Cheng J, Song C, Hu N, Zhou W, Suo Y, Sun Z, You J (2019) A highly sensitive and selective method for determination of phenoxy carboxylic acids from environmental water samples by dispersive solid-phase extraction coupled with ultra high performance liquid chromatography–tandem mass spectrometry. Talanta 191:313–323. https://doi.org/10.1016/j.talanta.2018.08.055
Ji W-H, Guo Y-S, Wang X, Lu X-F, Guo D-S (2019) Amino-modified covalent organic framework as solid phase extraction absorbent for determination of carboxylic acid pesticides in environmental water samples. J Chromatogr A 1595:11–18. https://doi.org/10.1016/j.chroma.2019.02.048
Tabani H, Fakhari AR, Shahsavani A, Behbahani M, Salarian M, Bagheri A, Nojavan S (2013) Combination of graphene oxide-based solid phase extraction and electro membrane extraction for the preconcentration of chlorophenoxy acid herbicides in environmental samples. J Chromatogr A 1300:227–235. https://doi.org/10.1016/j.chroma.2013.04.026
The authors would like to thank the Universit Teknologi Malaysia for financial support through UTM IIIG grant (Q.J130000.3054.01M19) and UTM Shine Signature Grant (Q.J130000.2454.07G73).
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Ganesan, T., Lim, H.N. & See, H.H. Automated Mixed Matrix Membrane Microextraction Prior to Liquid Chromatography for the Determination of Chlorophenoxy Acid Herbicides in Sewage Water Samples. Chromatographia (2020). https://doi.org/10.1007/s10337-020-03865-4
- Sample preparation
- Mixed matrix membrane
- System automation