Alginate-Graphene Oxide Biocomposite Sorbent for Rapid and Selective Extraction of Non-Steroidal Anti-Inflammatory Drugs Using Micro-Solid Phase Extraction

Mohammad Salim Tabish(1), Nor Suhaila Mohamad Hanapi(2*), Wan Nazihah Wan Ibrahim(3), Nor’ashikin Saim(4), Noorfatimah Yahaya(5)

(1) Faculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia
(2) Faculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia
(3) Faculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia
(4) Faculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia
(5) Integrative Medicine Cluster, Advanced Medical and Dental Institute, Universiti Sains Malaysia, No. 1-8, Persiaran, Seksyen 4/1, 13200 Bandar Putra Betam, Kepala Batas, Penang, Malaysia
(*) Corresponding Author


In this work, a bio-composite sorbent, alginate incorporated graphene oxide (Alg/GO) is prepared for the micro solid phase extraction of non-steroidal anti-inflammatory drugs (NSAIDs) from water samples. The sorbent was prepared in a suspended solution form at a ratio of 0.3:1 (w/v %) of graphene oxide (GO) and alginate (Alg). The chemical structure, morphology and surface area of the composite beads were characterized using Fourier Transform Infrared Spectroscopy (FT-IR), Scanning Electron Microscopy (SEM) and Brunauer–Emmett–Teller (BET). GO showed good miscibility and well dispersion through intermolecular hydrogen bonds and electrostatic interactions within the Alg matrix. The synthesized sorbent was applied for the determination of the selected drugs in a tap water sample using micro-solid phase extraction technique and was analyzed by high-performance liquid chromatography-ultraviolet detector (HPLC-UV). The results showed good linearity in the range of 10–1000 µg L–1 with correlation coefficients (r ≥ 0.9979), low detection limits (LOD) between 3.1–4.6 µg L–1, excellent relative recoveries in the range of 99.6–102.1% and good reproducibility (RSD ≤ 3.9%). Thus, these validated results showed that Alg/GO could be potential and useful as a bio-composite sorbent for micro-solid phase extraction for the analysis of targeted drugs from aqueous matrices.


alginate; graphene oxide; non-steroidal anti-inflammatory drugs; micro-solid phase extraction

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[1] Cha, Y.B., and Myung, S.W., 2013, Determination of non-steroidal anti-inflammatory drugs in human urine sample using HPLC/UV and three phase hollow fiber-liquid phase microextraction (HF-LPME), Bull. Korean Chem. Soc., 34 (11), 3444–3450.

[2] Hanapi, N.S.M., Sanagi, M.M., Ismail, A.K., Saim, N. A., Ibrahim, W.N.W., Wan Ibrahim, W.A.W., and Marsin, F.M., 2017, Rapid determination of non-steroidal anti-inflammatory drugs in aquatic matrices by two-phase micro-electrodriven membrane extraction combined with liquid chromatography, J. Chromatogr. Sci., 56 (2), 166–176.

[3] Asgharinezhad, A.A., Ebrahimzadeh, H., Mirbabaei, F., Mollazadeh, N., and Shekari, N., 2014, Dispersive micro-solid-phase extraction of benzodiazepines from biological fluids based on polyaniline/magnetic nanoparticles composite, Anal. Chim. Acta, 844, 80–89.

[4] Peng, T., Zhu, A.L., Zhou, Y.N., Hu, T., Yue, Z.F., Chen, D.D., Wang, G.M., Kang, J., Fan, C.l., Chen, Y., and Jiang, H.Y., 2013, Development of a simple method for simultaneous determination of nine subclasses of non-steroidal anti-inflammatory drugs in milk and dairy products by ultra-performance liquid chromatography with tandem mass spectrometry, J. Chromatogr. B, 933, 15–23.

[5] Patrolecco, L., Ademollo, N., Grenni, P., Tolomei, A., Caracciolo, A.B., and Capri, S., 2013, Simultaneous determination of human pharmaceuticals in water samples by solid phase extraction and HPLC with UV-fluorescence detection, Microchem. J., 107 (3), 165–171.

[6] Zhang, H., Du, Z., Ji, Y., and Mei, M., 2013, Simultaneous trace determination of acidic non-steroidal anti-inflammatory drugs in purified water, tap water, juice, soda and energy drink by hollow fiber-based liquid-phase microextraction and ultra-high pressure liquid chromatography coupled to tandem mass spectrometry, Talanta, 109, 177–184.

[7] Jiao, C., Xiong, J., Tao, J., Xu, S., Zhang, D., Lin, H., and Chen, Y., 2016, Sodium alginate/graphene oxide aerogel with enhanced strength–toughness and its heavy metal adsorption study, Int. J. Biol. Macromol., 83, 133–141.

[8] Park, S.B., Lih, E., Park, K.S., Joung, Y.K., and Han, D.K., 2017, Biopolymer-based functional composites for medical applications, Prog. Polym. Sci., 68, 77–105.

[9] Abdollahi, M., Alboofetileh, M., Rezaei, M., and Behrooz, R., 2013, Comparing physico-mechanical and thermal properties of alginate nanocomposite films reinforced with organic and/or inorganic nanofillers, Food Hydrocolloids, 32 (2), 416–424.

[10] He, Y., Zhang, N., Gong, Q., Qiu, H., Wang, W., Liu, Y., and Gao, J., 2012, Alginate/graphene oxide fibers with enhanced mechanical strength prepared by wet spinning, Carbohydr. Polym., 88 (3), 1100–1108.

[11] Zheng, H., Yang, J., and Han, S., 2016, The synthesis and characteristics of sodium alginate/graphene oxide composite films crosslinked with multivalent cations, J. Appl. Polym. Sci., 133 (27), 43616.

[12] Seo, P.W., Khan, N.A., and Jhung, S.H., 2017, Removal of nitroimidazole antibiotics from water by adsorption over metal–organic frameworks modified with urea or melamine, Chem. Eng. J., 315, 92–100.

[13] Rahim, M., and Haris, M.R.H.M., 2015, Application of biopolymer composites in arsenic removal from the aqueous medium, J. Radiat. Res. Appl. Sci., 8 (2), 255–263.

[14] Campíns-Falcó, P., Sevillano-Cabeza, A., Herráez-Hernández, R., Molins-Legua, C., Moliner-Martínez, Y., and Verdú-Andrés, J., 2006, “Solid-Phase Extraction and Clean-Up Procedures in Pharmaceutical Analysis” in Encyclopedia of Analytical Chemistry, Eds., Meyers, R.A., and Meyers, R.A., John Wiley & Sons, Ltd., 2–5.

[15] Ray, S.C., 2015, Applications of Graphene and Graphene-Oxide Based Nanomaterials, William Andrew Publishing, 2–4.

[16] Nazario, C.E.D., Fumes, B.H., da Silva, M.R., and Lanças, F.M., 2017, New materials for sample preparation techniques in bioanalysis, J. Chromatogr. B, 1043, 81–95.

[17] Karimi, B., and Ramezanzadeh, B.A, 2017, Comparative study on the effects of ultrathin luminescent graphene oxide quantum dot (GOQD) and graphene oxide (GO) nanosheets on the interfacial interactions and mechanical properties of an epoxy composite, J. Colloid Interface Sci., 493, 62–76.

[18] Xu, Y., Wu, Q., Sun, Y., Bai, H., and Shi, G., 2010, Three-dimensional self-assembly of graphene oxide and DNA into multifunctional hydrogels, ACS Nano, 4 (12), 7358–7362.

[19] Platero, E., Fernandez, M.E., Bonelli, P.R., and Cukierman, A.L., 2017, Graphene oxide/alginate beads as adsorbents: influence of the load and the drying method on their physicochemical-mechanical properties and adsorptive performance, J. Colloid Interface Sci., 491, 1–12.

[20] Fei, Y., Li, Y., Han, S., and Ma, J., 2016, Adsorptive removal of ciprofloxacin by sodium alginate/graphene oxide composite beads from aqueous solution, J. Colloid Interface Sci., 484, 196-204.

[21] Algothmi, W.M., Bandaru, N.M., Yu, Y., Shapter, J.G., and Ellis, A.V., 2013, Alginate–graphene oxide hybrid gel beads: An efficient copper adsorbent material, J. Colloid Interface Sci., 397, 32–38.

[22] Zhang, X., Wu, Y., Xiao, G., Tang, Z., Wang, M., Liu, F., and Zhu, X., 2017, Simultaneous photocatalytic and microbial degradation of dye-containing wastewater by a novel g-C3N4-P25/photosynthetic bacteria composite, PloS One, 12 (3), e0172747.

[23] Sangwichien, C., Aranovich, G.L., and Donohue, M.D., 2002, Density functional theory predictions of adsorption isotherms with hysteresis loops, Colloids Surf., A, 206 (1-3), 313–320.

[24] Saraf, S., 2008, NSAIDs Non-Steroidal Anti-Inflammatory Drugs: An Overview, PharmaMed Press, 3–6.

[25] Li, Y., Du, Q., Liu, T., Peng, X., Wang, J., Sun, J., Wang, Y., Wu, S., Wang, Z., Xia, Y., and Xia, L., 2013, Comparative study of methylene blue dye adsorption onto activated carbon, graphene oxide, and carbon nanotubes, Chem. Eng. Res. Des., 91 (2), 361–368.

[26] Kamaruzaman, S., Sanagi, M.M., Endud, S., Ibrahim, W.A.W., and Yahaya, N., 2013, MCM-41 solid phase membrane tip extraction combined with liquid chromatography for the determination of non-steroidal anti-inflammatory drugs in human urine, J. Chromatogr. B, 940, 59–65.

[27] Sanagi, M.M., Hanapi, N.S.M., Ismail, A.K., Ibrahim, W.A.W., Saim, N., and Yahaya, N., 2014, Two-phase electro-driven membrane extraction combined with liquid chromatography for the determination of tricyclic antidepressants in aqueous matrices, Anal. Methods, 6 (21), 8802–8809.

[28] Hanapi, N.S.M., Sanagi, M.M., Ismail, A.K., Ibrahim, W.A.W., Saim, N., and Ibrahim, W.N.W., 2017, Ionic liquid-impregnated agarose film two-phase micro-electro-driven membrane extraction (IL-AF-μ-EME) for the analysis of antidepressants in water samples, J. Chromatogr. B, 1046, 73-80.

[29] Sajid, M., Basheer, C., and Mansha, M., 2016, Membrane protected micro-solid-phase extraction of organochlorine pesticides in milk samples using zinc oxide incorporated carbon foam as a sorbent, J. Chromatogr. A, 1475, 110-115.

[30] Sun, M., Wu, Q., Wang, C., and Wang, Z., 2014, Thin-film microextraction for the preconcentration of some endocrine disrupting chemicals in aqueous samples before chromatographic analysis, Anal. Methods, 6 (16), 6316–6321.

[31] Abidin, N.N.Z., Sanagi, M.M., Ibrahim, W.A.W., Endud, S., and Md Shukri, D.S., 2014, Portable micro-solid phase extraction for the determination of polycyclic aromatic hydrocarbons in water samples, Anal. Methods-UK., 6 (15), 5512–5518.

[32] Yahaya, N., Sanagi, M.M., Nur, H., Ibrahim, W.A.W., Kamaruzaman, S., and Aboul-Enein, H.Y., 2014, Solid-phase membrane tip extraction combined with liquid chromatography for the determination of azole antifungal drugs in human plasma, Anal. Methods, 6 (10), 3375–3381.

[33] Rozaini, M.N.H., Yahaya, N., Saad, B., Kamaruzaman, S., and Hanapi, N.S.M., 2017, Rapid ultrasound-assisted emulsification micro-solid phase extraction based on molecularly imprinted polymer for HPLC-DAD determination of bisphenol A in aqueous matrices, Talanta, 171, 242–249.

[34] Mao, X., He, M., Chen, B., and Hu, B., 2016, Membrane protected C18 coated stir bar sorptive extraction combined with high-performance liquid chromatography-ultraviolet detection for the determination of non-steroidal anti-inflammatory drugs in water samples, J. Chromatogr. A, 1472, 27–34.

[35] Manzo, V., Honda, L., Navarro, O., Ascar, L., and Richter, P., 2014, Microextraction of non-steroidal anti-inflammatory drugs from wastewater samples by rotating-disk sorptive extraction, Talanta, 128, 486–492.

[36] Aguilar-Arteaga, K., Rodriguez, J.A., Miranda, J.M., Medina, J., and Barrado, E., 2010, Determination of non-steroidal anti-inflammatory drugs in wastewaters by magnetic matrix solid-phase dispersion–HPLC, Talanta, 80 (3), 1152–1157.

[37] Asgharinezhad, A.A., Mollazadeh, N., Ebrahimzadeh, H., Mirbabaei, F., and Shekari, N., 2014, Magnetic nanoparticles based dispersive micro-solid-phase extraction as a novel technique for coextraction of acidic and basic drugs from biological fluids and wastewater, J. Chromatogr. A, 1338, 1-8.


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