Molecularly Imprinted Stir Bar Sorptive Extraction Coupled with High-Performance Liquid Chromatography for Trace Analysis of Diclofenac in Different Real Samples

Document Type: Research Article


Department of Marine Chemistry, Faculty of Marine Science, Chabahar Maritime University, P.O. Box 98617-85553 Chabahar, I.R. IRAN


A novel molecularly imprinted polymer-coated stir bar has been used to selectively extract diclofenac (DFC) directly from real samples. DFC was used as template molecule for preparation of MIP coating. The effect of different parameters on the extraction efficiency were studied and the optimum conditions were established as: the absorption and desorption times were fixed at 10 min, stirring speed was 600 rpm, pH was adjusted to 5.1, the amount of NaCl was 0.35 mol/L and extraction process was performed at a temperature of 45 °C. Under the optimum conditions, the linear range of method was 0.5- 500.0 µg/L for DFC and the detection limit was calculated to be 0.15 µg/L with an enrichment factor of 242 folds. The technique was successfully applied for the analysis of trace amounts of DFC in seawater and commercial tablet samples. The mean recoveries of spiking real samples with DFC at 10.0 µg/L level were between 94.2-100.0 % with a mean RSD of 0.7-4.6%.


Main Subjects

[1] Perisic D.J., Gilja V., Stankov M.N., Katancic Z., Kusic H., Bozic A.L., Stangar U.L., Dionysiou D.D., Removal of Diclofenac from Water by Zeolite-Assisted Advanced Oxidation Processes, J. Photochem. Photobiol., 321: 238-247(2016).

[2] Pebdani A.A., Shabani A.M.H., Dadfarnia S., Selective Separation and Determination of Diclofenac via Magnetic Molecularly Imprinted Polymer and Spectrophotometry, J. Iran. Chem. Soc., 13: 155-164 (2015).

[3] Dai C.M., Geissen S.U., Zhang Y.L., Zhang Y.J., Zhou X.F., Selective Removal of Diclofenac from Contaminated Water Using Molecularly Imprinted Polymer Microspheres, Environ. Pollut., 159: 1660-1666 (2011).

[4] Dai C.M., Zhou X.F., Zhang Y.L., Liu S.G., Zhang J., Synthesis by Precipitation Polymerization of Molecularly Imprinted Polymer for the Selective Extraction of Diclofenac from Water Samples, J. Hazard. Mater., 198: 175-181 (2011).

[5] Aurora-Prado M.S., Steppe M., Tavares M.F.M., Kedor- Hackmann E.R.M., Santoro M.I.R.M., Comparison Between Capillary Electrophoresis and Liquid Chromatography for the Determination of Diclofenac Sodium in a Pharmaceutical Tablet, J. Aoac. Int., 85: 333-340 (2002).

[7] Payan M.R., Lopez M.A.B., Torres R.F., Bernal J.L.P., Mochon M.C., HPLC Determination of Ibuprofen and Diclofenac and Salicylic Acid Using Hollow Fiber-Based Liquid Phase Micro Extraction, Anal. Chim. Acta, 653: 184-190 (2009).

[9] Pimenta A.M., Araújo A.N., Montenegro M.C.B.S.M., Simultaneous Potentiometric and Fluorimetric Determination of Diclofenac in a Sequential Injection Analysis System, Anal. Chim. Acta, 470: 185-194 (2002).

[10] Carreira L.A., Rizk M., Shabrawy Y.E., Zakhair N.A., Tonbar S.S., Europium (III) Ion Probe Spectrofluorometric Determination of Diclofenac Sodium, J. Pharm. Biomed. Anal., 13: 1331-1337 (1995).

[11] Souza R.L.D., Tubino M., Spectrophotometric Determination of Diclofenac in Pharmaceutical Preparations, J. Braz. Chem. Soc., 16: 1068-1073 (2005).

[12] Nassiri M., Kaykhaii M., Hashemi S.H., Sepahi M., Spectrophotometric Determination of Formaldehyde in Seawater Samples after in-situ Derivatization and Dispersive Liquid-Liquid Microextraction, Iran. J. Chem. Chem. Eng. (IJCCE), Articles in Press.  

[13] Sun Z., Schussler W., Sengl M., Niessner R., Knopp D., Selective Trace Analysis of Diclofenac in Surface and Wastewater Samples using Solid-Phase Extraction with New Molecularly Imprinted Polymer, Anal. Chim. Acta, 620: 73-81 (2008).

[14] Larous S., Meniai A.H., Adsorption of Diclofenac from Aqueous Solution Using Activated Carbon Prepared from Olive Stones, Int. J. Hydrogen Energy, 41: 10380–10390 (2016).

[15] Kaykhaii M., Dicinoski G.W., Haddad P.R., Solid-Phase Microextraction for the Determination of Inorganic Ions: Applications and Possibilities, Anal. Lett., 43: 1546-1555 (2010).

[16] Mullett W.M., Martin P., Pawliszyn J., In-Tube Moleculary Imprinted Polymer Solid-Phase Microextraction for the Selective Determination of Propranolol, Anal. Chem., 73: 2383-2389 (2001).

[17] Hashemi S.H., Kaykhaii M., Tabehzar F., Spectrophotometric Determination of Four Naphthalene Sulfonates in Seawater after Their Molecularly Imprinted Stir Bar Sorptive Extraction, J. Chil. Chem. Soc.,Accepted for publication.

[21] David F., Sandra P., Stir Bar Sorptive Extraction for Trace Analysis, J. Chromatogr. A, 1152: 54-59 (2007).

[22] Lei Y., Xu G., Wei F., Yang J., Hu Q., Preparation of a Stir Bar Coated with Molecularly Imprinted Polymer and its Application in Analysis of Dopamine in Urine, J. Pharm. Biomedical Analysis, 94: 118-124 (2014).

[24] Hashemi S.H., Kaykhaii M., Khajeh M., Molecularly Imprinted Polymers for Stir Bar Sorptive Extraction: Synthesis, Characterization, and Application, Anal. Lett., 48: 1815-1829 (2015).

[25] Khajeh M., Bohlooli M., Hashemi H., Imprinted Polymer Particles for Aluminum Uptake: Synthesis and Analytical Applications, J. Macromol. Sci., 46: 1-7 (2009).

[27] Amiri A., Ramazani A., Jahanshahi M., Moghadamnia A.A., Synthesis and Evaluating of Nanoporous Molecularly Imprinted Polymers for Extraction of Quercetin as a Bioactive Component of Medicinal Plants, Iran. J. Chem. Chem. Eng. (IJCCE), 35: 11-19 (2016).

[28] Khajeh M., Kaykhaii M., Mirmoghaddam M., Hashemi H., Separation of Zinc from Aqueous Samples Using a Molecular Imprinting Technique, J. Environ. Anal. Chem., 89: 981-992 (2009).

[31] Khajeh M., Kaykhaii M., Hashemi H., Mirmoghaddam M., Imprinted Polymer Particles for Iron Uptake: Synthesis and Analytical Applications, Polym. Sci. Ser. B, 51: 344-351 (2009).

[35] Rezaei F., Yamini Y., Moradi M., Ebrahimpour B., Solid Phase Extraction as a Cleanup Step Before Microextraction of Diclofenac and Mefenamic Acid Using Nanostructured Solvent, Talanta, 105: 173-178 (2013).

[38] Hashemi S.H., Kaykhaii M., Developments in Methods of Analysis for Naphthalene Sulfonates, Crit. Rev. Anal. Chem., 47: 127-137 (2016).