• International Journal of Technology (IJTech)
  • Vol 10, No 6 (2019)

Advanced Materials as Adsorbents in Microextractions for the Determination of Contaminants: A Mini Review

Advanced Materials as Adsorbents in Microextractions for the Determination of Contaminants: A Mini Review

Title: Advanced Materials as Adsorbents in Microextractions for the Determination of Contaminants: A Mini Review
Muhammad Nur' Hafiz Rozaini, Bahruddin Saad, Muggundha Raoov Ramachandran, Evizal Abdul Kadir

Corresponding email:

Cite this article as:
Rozaini, M.N.H., Saad, B.Ramachandran, M.R., Abdul Kadir, E., 2019. Advanced Materials as Adsorbents in Microextractions for the Determination of Contaminants: A Mini Review. International Journal of Technology. Volume 10(6), pp. 1157-1165

Muhammad Nur' Hafiz Rozaini Department of Fundamental and Applied Sciences, Universiti Teknologi PETRONAS, 32610 Seri Iskandar, Perak Darul Ridzuan, Malaysia
Bahruddin Saad Department of Fundamental and Applied Sciences, Universiti Teknologi PETRONAS, 32610 Seri Iskandar, Perak Darul Ridzuan, Malaysia
Muggundha Raoov Ramachandran Department of Chemistry, Faculty of Science, University of Malaya, 50603 Kuala Lumpur, Malaysia
Evizal Abdul Kadir Faculty of Engineering, Universitas Islam Riau, Kota Pekanbaru, Riau 28284, Indonesia
Email to Corresponding Author

Advanced Materials as Adsorbents in Microextractions for the Determination of Contaminants: A Mini Review

The widespread presence of contaminants in water demands reliable and practical analytical methods to monitor them. However, before their determination, a sample pretreatment step is necessary. This has conventionally been performed using liquid-liquid extraction (LLE) or solid-phase extraction (SPE). Advances in material sciences have since been capitalized on, with new adsorbents used in conjunction with new sample pretreatment techniques based on microextractions. In this mini-review, we showcase some of our previously reported work that demonstrates how advanced materials such as graphene, molecularly imprinted polymers (MIPs), and polymeric cyclodextrins can be used as adsorbents for the determination of contaminants such as bisphenol A, steroids, sulfonamide antibiotics, and antimicrobial agents. These adsorbents formed an important component in the micro-solid phase extraction that was used for the pretreatment of the sample. A brief introduction to the adsorbents studied and evolution of extractions is provided. The distinctive features of the analytical methods used in the real sample analysis of the stated contaminants are highlighted.

Advanced materials; Analytical determination; Contaminants; Sample pretreatment


The presence of environmental pollutants such as herbicides, pharmaceutical waste, heavy metals (Kusumaningsih et al., 2012), and dyes (Mamat et al., 2018; Anuar et al., 2019) at trace levels has been the cause of much concern among the public and authorities. This has provided motivation for researchers to explore new materials that can be used for their removal. In analytical determination protocols, the use of these materials as adsorbents in sample preparation techniques has been keenly studied. Sample preparation is an important step in selectively isolating the analyte of interest from the sample before the analytical determination (normally using chromatographic methods). It also helps to preconcentrate the analytes, which is important in trace determinations. To achieve these objectives, extraction of the targeted analyte can be conducted using extractions (see section 3), and extractions using solid adsorbents have been  viewed as the way forward. The prime objective is to introduce new materials that are more selective and easily prepared, which can improve on the conventional methods. Advanced materials have been used in numerous applications such as the determination of parabens (Fumes & Lanças, 2016), sulfonamides (Rozaini et al., 2019), bisphenol A (Rozaini et al., 2017), triclosan (Alshishani et al., 2019), and endogenous steroids (Manaf et al., 2018) in both environmental waters and human urine. Another important objective is to reduce the consumption of organic solvents, which are used in large amounts in conventional liquid-liquid extraction (LLE). In this report, the use of graphene, molecularly imprinted polymers (MIPs), and polymers containing immobilized cyclodextrin (CD) are provided as examples of how these advanced materials can be used as adsorbents in sample microextractions before their analytical determination.


Advanced materials, due to their unique properties, have proven to be useful in numerous applications. We demonstrated how MIP, graphene, and CD were used as adsorbents for the microextraction of model antimicrobials, steroids, and veterinary drugs. The analytical techniques that resulted from these innovations were simple, effective, conserve solvents and materials, which support the green analytical chemistry initiatives.


The authors acknowledge the support received from the Ministry of Education Malaysia (Fundamental Research Grant Scheme – 015MA0-017), Universiti Teknologi PETRONAS (Yayasan Universiti Teknologi PETRONAS Research Grant Scheme – 015LC0-071), and Universitas Islam Riau (UIR matching grant-015ME0-038).

Supplementary Material
R1-CE-3282-20191023172634.png figure 1
R1-CE-3282-20191023172700.png figure 2
R1-CE-3282-20191023172718.png figure 3
R1-CE-3282-20191023172733.docx table 1

Alshishani, A., Saaid, M., Basheer, C., Saad, B., 2019. High Performance Liquid Chromatographic Determination of Triclosan, Triclocarban and Methyl-triclosan in Wastewater using Mini-bar Micro-solid Phase Extraction. Microchemical Journal, Volume 147, pp. 339–348­­

Andrade-Eiroa, A., Canle, M., Leroy-Cancellieri, V., Cerdà, V., 2016. Solid-phase Extraction of Organic Compounds: A Critical Review - Part II. TrAC - Trends in Analytical Chemistry, Volume 80, pp. 655–667

Anuar, F.I., Hadibarata, T., Muryanto, M., Yuniarto, A., Priyandoko, D., Sari, A.A., 2019. Innovative Chemically Modified Biosorbent for Removal of Procion Red. International Journal of Technology, Volume 10(4), pp. 776–786­

Ashley, J., Shahbazi, M.-A., Kant, K., Chidambara, V.A., Wolff, A., Bang, D.D., Sun, Y., 2017. Molecularly Imprinted Polymers for Sample Preparation and Biosensing in Food Analysis: Progress and Perspectives. Biosensors and Bioelectronics, Volume 91, pp. 606–615

Basheer, C., Ali Alnedhary, A., Rao, B.S.M., Valliyaveettil, S., Lee, H.K., 2006. Development and Application of Porous Membrane-protected Carbon Nanotube Micro-solid-phase Extraction Combined with Gas Chromatography/Mass Spectrometry. Analytical Chemistry, Volume 78(8), pp. 2853–2858

Costi, E.M., Sicilia, M.D., Rubio, S., 2010. Multiresidue Analysis of Sulfonamides in Meat by Supramolecular Solvent Microextraction, Liquid Chromatography and Fluorescence Detection and Method Validation According to the 2002/657/EC Decision. Journal of Chromatography A, Volume 1217(40), pp. 6250–6257

Crini, G., 2014. Review?: A History of Cyclodextrins Gre g. Chemical Reviews, Volume 114(21), pp. 10940–10975

Cserháti, T., Forgacs, E., 2003. Cyclodextrins in Chromatography. 1st Edition. Royal Society of Chemistry

de Toffoli, A.L., Maciel, E.V.S., Fumes, B.H., Lanças, F.M., 2018. The Role of Graphene-based Sorbents in Modern Sample Preparation Techniques. Journal of Separation Science, Volume 41(1), pp. 288–302

Del Valle, E.M.M., 2004. Cyclodextrins and Their Uses: A Review. Process Biochemistry, Volume 39(9), pp. 1033–1046

Duan, Y.P., Dai, C.M., Zhang, Y.L., Ling-Chen., 2013. Selective Trace Enrichment of Acidic Pharmaceuticals in Real Water and Sediment Samples based on Solid-phase Extraction using Multi-templates Molecularly Imprinted Polymers. Analytica Chimica Acta, Volume 758, pp. 93–100

Fumes, B.H., Lanças, F.M., 2016. Use of Graphene Supported on Aminopropyl Silica for Microextraction of Parabens from Water Samples. Journal of Chromatography, Volume 1487, pp. 64–71

Hummers, W.S., Offeman, R.E., 1958. Preparation of Graphitic Oxide. Journal of the American Chemical Society, Volume 80(6), pp. 1339–1339

Junjie, L., Mei, Y., Danqun, H., Changjun, H., Xianliang, L., Guomin, W., Dan, F., 2013. Molecularly Imprinted Polymers on the Surface of Silica Microspheres via Sol-gel Method for the Selective Extraction of Streptomycin in Aqueous Samples. Journal of Separation Science, Volume 36(6), pp. 1142–1148

Kamaruzaman, S., Hauser, P.C., Sanagi, M.M., Ibrahim, W.A.W., Endud, S., See, H.H., 2013. A Simple Microextraction and Preconcentration Approach based on a Mixed Matrix Membrane. Analytica Chimica Acta, Volume 783, pp. 24–30

Kusumaningsih, T., Jumina, Siswanta, D., Mustofa, Ohto, K., Kawakita, H., 2012. Synthesis of Poly Tetra-P-Allylcalix[4]Arene Tetra Acetic Acid Adsorbent for Cr(III) and Pb(II) Metal Ions. International Journal of Technology, Volume 3(2), pp. 93–102

Mahpishanian, S., Sereshti, H., 2017. One-step Green Synthesis of ?-Cyclodextrin/Iron Oxide-Reduced Graphene Oxide Nanocomposite with High Supramolecular Recognition Capability: Application for Vortex-assisted Magnetic Solid Phase Extraction of Organochlorine Pesticides Residue from Honey Sam. Journal of Chromatography A, Volume 1485, pp. 32–43

Mamat, M., Abdullah, M.A.A., Kadir, M.A., Jaafar, A.M., Kusrini, E., 2018. Preparation of Layered Double Hydroxides with Different Divalent Metals for the Adsorption of Methyl Orange Dye from Aqueous Solutions. International Journal of Technology, Volume 9(6), pp. 1103–1111

Manaf, N.A., Saad, B., Mohamed, M.H., Wilson, L.D., Latiff, A.A., 2018. Cyclodextrin Based Polymer Sorbents for Micro-solid Phase Extraction Followed by Liquid Chromatography Tandem Mass Spectrometry in Determination of Endogenous Steroids. Journal of Chromatography A, Volume 1543, pp. 23–33

Müller, E., Berger, R., Blass, E., Sluyts, D., Pfennig, A., 2008. Liquid-Liquid Extraction. In: Major Reference Works. Ullmann’s Encyclopedia of Industrial Chemistry.

Rozaini, M.N.H., Semail, N.-f., Saad, B., Kamaruzaman, S., Abdullah, W.N., Rahim, N.A., Miskam, M., Loh, S.H., Yahaya, N., 2019. Molecularly Imprinted Silica Gel Incorporated with Agarose Polymer Matrix as Mixed Matrix Membrane for Separation and Preconcentration of Sulfonamide Antibiotics in Water Samples. Talanta, Volume 199, pp. 522–531

Rozaini, M.N.H., Yahaya, N., Saad, B., Kamaruzaman, S., 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, Volume 171, pp. 242–249

Sajid, M., 2017. Porous Membrane Protected Micro-solid-phase Extraction: A Review of Features, Advancements and Applications. Analytica Chimica Acta, Volume 965, pp. 36–53

Tian, T., Qiu, F., Dong, K., Yang, D., 2012. Application of an Inclusion Complex for Determination of Dithianon Residues in Water and Fruits. Toxicological and Environmental Chemistry, Volume 94(6),  pp. 1034–1042

Zhang, D., Lv, P., Zhou, C., Zhao, Y., Liao, X., Yang, B., 2019. Cyclodextrin-based Delivery Systems for Cancer Treatment. Materials Science and Engineering C, Volume 96, pp. 872–886