Amino functionalized mesoporous silica for drug adsorption

N. Benyoub, A. Benhamou, A. Debab


The main objective of this work was to synthesize hexagonal mesoporous materials such as MCM-41 from optimized protocols and to test their effectiveness in adsorption of different pharmaceutical pollutants. First, pore size and the specific surface area of the base materials have been modified by incorporation of amino groups in post-synthesis, by selective extraction of the loaded groups and finally by calcination. Subsequently, adsorbent products were characterized by their mesoscopic textures, structures and controls using different methods: X-Ray Diffraction (XRD), Specific Surface Area (BET), Fourier Transform Infrared Spectroscopy (FTIR), Thermogravimetric analyses (TGA/DTA) and Zetametry. Finally, their adsorption capacities were evaluated using several pharmaceutical residues under standard conditions (such as Diclofenac, Cefalexin ...). The results obtained during the adsorption study showed the effectiveness of these materials for the decontamination of aqueous media contaminated with pharmaceutical residues. Kinetic and adsorption isotherm studies were carried out to clarify the method of binding of the selected pharmaceutical pollutants to the tested materials.

Full Text:



Chiola, V.; Ritsko, J. E.; Van der Pool, C. D. Process for producing low-bulk density silica U. S. Patent Office 3 (1971) 556-725.

Beck, J.S.; Vartuli, J.C.; Roth, W.J.; Leonowicz, M.E.; Kresge, C.T.; Schmitt, K.D.; Chu, C. T.W.; Olson, D.H.; Sheppard, E. A new family of mesoporous molecular sieves prepared with liquid crystal templates. Journal of the American Chemical Society 114 (1992) 108, 340.

Zhao, X.S.; Lu, G.Q.M; Millar, G.J. Advances in Mesoporous Molecular Sieve MCM- 41. Industrial & Engineering Chemistry Research 35 (7) (1996).

Kresge, C.T.; Leonowcz, M.E.; Roth, J.W; Vartuli, J.C.; Beck, J.S. Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism. Narture, 359 (1992) 710-712.

Hickey, A.J.; Smyth, H.D.C. Pharmaco-Complexity, Outlines in Pharmaceutical Sciences. American Association of Pharmaceutical Scientists 2011.

Jishuai, B.; Chun, H.; Yulun, N.; Min, Y.; Jiuhui, Q. Mechanism of Catalytic Ozonation in Fe2O3/Al2O3@SBA-15 Aqueous Suspension for Destruction of Ibuprofen. Environnemental. Sciences Technology (2015) 1-32.

McCusker, L.B.; Liebau, F.; Engelhardt, G. Micoporous and Materials. Pure Applied Chemistry 73 (2001) 381-394 .

Wang, X.; Lin, K.S.K.; Sheng, J.C.C. Direct Synthesis and Catalytic Applications of Ordered Large Pore Aminopropyl-Functionalized SBA-15 Mesoporous Materials. Journal of Physical Chemistry B 109 (2005) 1763-1769.

Zhang, Y.; Wang , H.; Gao, C.; Li, X.; Li, L. Highly ordered mesoporous carbon nanomatrix as a new approach to improve the oral absorption of the water-insoluble drug, simvastatin. European Journal of Pharmaceutical Sciences 49 (2013) 864–872.

Rashi, S.; Prajapati, S.K. ; Singh, D. Mesoporous Silica Nanoparticles for Controlled Drug Delivery. World Journal of Pharmacy and Pharmaceutical Sciences 4 (6) (2013) 332-347.

Enrique, V.G; Cecilia, J.A; Moya, E.M.O; Jr Celio, L.C.; Diana, C.S.A; Enrique, R.C. Low Cost Pore Expanded SBA-15 Functionalized with Amine Groups Applied to CO2 Adsorption. Materials 8 (2015) 2495-2513.

Claudio, A.V.; Oliveira, V. Hydrophobic contribution to amoxicillin release associated with organofunctionalized mesoporous SBA-16 carriers. Materials Research Bulletin 7522 (2014) 1-35.

Javad, S.; Zohre, Z. Advanced drug delivery systems: Nanotechnology of health design A review. Journal of Saudi Chemical Society 18 (2013) 85–99.

Marie, H.J. Medicaments et environnement. Académie nationale de Pharmacie (2008), Paris, France.

Staub, P.F. Les substances émergentes dans l’environnement. Office National de l’Eau et des Milieux Aquatiques (ONEMA) (2009), Paris, France.

Melissa, B. Impacts des substances pharmaceutiques sur l’eau et les milieux aquatiques. Office International de l’Eau (OIEau) (2010), Paris, France.

Loos, R.; Locoro, G.; Comero, S.; Contini, S.; Schwesig, D.; Werres, F.; Balsaa, P.; Gans, O.; Weiss, S.; Blaha, L.; Bolchi, M.; Gawlik B.M. Pan-European survey on the occurrence of selected polar organic persistent pollutants in ground water. Water Research 44 (2010) 4115-4126.

Loos, R.; Gawlik, B.M.; Locoro, G.; Rimaviciute, E.; Contini, S.; Bidoglio, G. EU-wide survey of polar organic persistent pollutants in European river waters. Environmental Pollution 157 (2009) 561–568.

Wantala, K.; Sthiannopkao, S.; Srinameb, B.; Grisdanurak, N.; Kim, K.W. Synthesis and characterization of Fe-MCM-41 from rice husk silica by hydrothermal technique for arsenate adsorption. Environmental Geochemistry and Health 32(4) (2010) 261–266.

Hermida, L.; Abdullah, A.Z.; Mohamed, A.R. Effects of functionalization conditions of sulfonic acid grafted SBA-15 on catalytic activity in the esterification of glycerol to monoglyceride: a factorial design approach. Journal of Porous Materials 19 (5) (2012) 835–846.

Dubois, M.; Gulik-Krzywicki, T.; Cabane, B. Growth of silica polymers in a lamellar mesophase. Langmuir 9 (3) (1993) 673-680.

Barczak, M.; Wierzbicka, M.; Borowski, P. Sorption of diclofenac onto functionalized mesoporous silicas: Experimental and theoretical investigations. Microporous and Mesoporous Materials 264 (2018) 254-264.

Nassi, M.; Sarti, E. ; Pasti, L. ; Martucci, A. ; Marchetti, N. ; Cavazzini, A. ; Galarneau, A. Removal of perfluorooctanoic acid from water by adsorption on high surface area mesoporous materials. Journal of Porous Materials 21 (4) (2014) 423–432.

Suriyanon, N.; Punyapalaku, P. ; Ngamcharussrivicha, C. Mechanistic study of diclofenac and carbamazepine adsorption on functionalized silica-based porous materials. Chemical Engineering Journal 214 (2013) 208–218.

Carniti, P.; Gervasini, A. Liquid-Solid Adsorption Properties: Measurement of the Effective Surface Acidity of Solid Catalysts. Calorimetry and Thermal Methods in Catalysis 154 (2013) 543-551.

Krasucka, P.; Goworek J. MCM-41 silica as a host material for controlled drug delivery systems. Annales Universitatis Mariae Curie-Skłodowska, sectio AA – Chemia 70 (2) (2015) 45.

Loos , R.; Carvalho, R.; Antonio, D.C.; Comero, S.; Locoro, G.; Tavazzi, S.; Paracchini, B.; Ghiani, M.; Lettieri, T.; Blaha, L.; Jarosova, B.; Voorspoels, S.; Servaes, K.; Haglund, P.; Fick, J.; Lindberg, R.H.; Schwesig, D.; Gawlik, B.M. EU-wide monitoring survey on emerging polar organic contaminants in wastewater treatment plant effluents. Water Research 47 (2013) 6475-6487.

Dahanea, S.; Galeraa, M.M.; Marchionnia, M.E.; Viciana, M.M.S.; Derdourd, A.; García, M.D.G. Mesoporous silica based MCM-41 as solid-phase extraction sorbent combined with micro-liquid chromatography-quadrupole-mass spectrometry for the analysis of pharmaceuticals in waters. Edition Talanta 152 (2016) 378-391.

Benhamou, A.; Baudu, M.; Derriche, Z.; Basly, J.P. Aqueous heavy metals removal on amine-functionalized Si-MCM-41 and Si-MCM-48. Journal Hazard Mater 171 (2009) 1001–1008.

Engineering Techniques, Measurement-Analyzes, Analytical Techniques, Thermal Methods of Analysis «article updated from P 1260 published in 2001».

Showkat, A.M.; Zhang, Y.P.; Kim, M.S.; Lyenger, A.; Karla, G.; Reddy,Ra.; Lee, K.P. Analysis of Heavy Metal Toxic Ions by Adsorption onto Amino-functionalized ordered Mesporous Silica. Bull. Kor. Chemical Society 28 (2007) 1985-1992.

Dada, A.O1.; Olalekan, A.P.; Olatunya, A.M. Langmuir, Freundlich, Temkin and Dubinin–Radushkevich Isotherms Studies of Equilibrium Sorption of Zn2+ Unto Phosphoric Acid Modified Rice Husk. IOSR Journal of Applied Chemistry (IOSRJAC) 3 (1) (2012) 38-45.

Brunauer, S.; Emmett, P.H. ; Teller, E. Adsorption of Gases in Multimolecular Layers . Journal of the American Chemical Society 60 (1938) 309 – 319.

Ariapad, A.; Zanjanchi, M.A.; Arvand, M. Efficient removal of anionic surfactant using partial template-containing MCM-41. Desalination 284 (2012) 142–149.

Morsli, A,; Benhamou, A.; Basly, J.P.; Baudu, M.; Derriche, Z. Mesoporous silicas: improving the adsorption efficiency of phenolic compounds by the removal of the amino group from functionalized silicas. Journal Royal Society of Chemistry (RSC) Advances 5 (2015) 41631-41638.

Idris, S.A.; Alotaibi, K.M.; Peshkur, T.A.; Anderson, P.; Morris M.; Gibson, L.T. Adsorption kinetic study: Effect of adsorbent pore size distribution on the rate of Cr (VI) uptake. Microporous and Mesoporous Materials 165 (2013) 99–105.

Benhamou, A.; Basly, J.P.; Baudu, M.; Derriche, Z.; Hamacha, R. Amino-functionalized MCM-41 and MCM-48 for the removal of chromate and arsenate. Journal of Colloid and Interface Science 404 (2013) 135–139.

Trindade, F.J.; Rey, J.F.Q.; Brochsztain, S. Modification of molecular sieves MCM-41 and SBA-15 with covalently grafted pyromellitimide and 1,4,5,8-naphthalenediimide. Journal of Colloid and Interface Science 368 (2012) 34–40.

Yokoi, T.; Kubota, Y.; Tatsumi, T. Amino-functionalized mesoporous silica as base catalyst and adsorbent. Applied Catalysis A: General 421-422 (2012) 14–37.

CHEN, J. P.; WANG L. Characterization of metal adsorption kinetic properties in batch and fixed-bed reactors. Chemosphere 54 (3) (2004) 397-404.

Da'na, E. Adsorption of heavy metals on functionalized-mesoporous silica: A review. Microporous and Mesoporous Materials 247 (2017) 145-157.

Li,G.; Wang, B.; Sun, Q.; Xu, W.; Han, Y. Adsorption of lead ion on amino-functionalized fly-ash-based SBA-15 mesoporous molecular sieves prepared via two-step hydrothermal method. Microporous and Mesoporous Materials 252 (2017) 105-115.

Boukoussa, B.; Kibou, Z.; Abid, Z.; Ouargli, R.; Braham, N.C.; Villemin, D.; Hamacha, R. Key factor affecting the basicity of mesoporous silicas MCM-41: effect of surfactant extraction time and Si/Al ratio. Chemical Papers 72 (2) (2017) 289–299.

Albayati, T.M.; Jassam, A.A.A. Experimental Study of Drug Delivery system for Prednisolone Loaded and Released by Mesoporous Silica MCM-41. Al-Khwarizmi Engineering Journal 15 (1) (2019) 117- 124.

Albayati, T.M.; Jassam, A.A.A. Synthesis and characterization of mesoporous materials as a carrier and release of prednisolone in drug delivery system. Journal of Drug Delivery Science and Technology 53 (2019) 101-176.

Maria, G.; Stoica, A.I.; Luta, I.; Stirbet, D.; Radu, G.L. Cephalosporin release from functionalized MCM-41 supports interpreted by various models. Microporous and Mesoporous Materials 162 (2012) 80–90.

Uthappa, U.T.; Brahmkhatr, V.; Sriram, G.; Jung, H.Y; Yu, J.; Kurkuri, N.; Aminabhavi, T.M. ; Altalhi, T.; Neelgund, G.M.; Kurkuri, M.D. Nature engineered diatom biosilica as drug delivery systems. Journal of Controlled Release 281 (2018) 70-83.

Alivand, M.S; Najmi, M.; Tehran, N.H.M.H.; Kamali, A.; Tavakoli, O.; Rashid, A. ; Esrafil, M.D ; Ghasemy, I. ; Mazaheri, O. Tuning the surface chemistry and porosity of waste-derived nanoporous materials toward exceptional performance in antibiotic adsorption: Experimental and DFT studies. Chemical Engineering Journal 374 (2019) 274-291

Nairi, V.; Medda, L.; Monduzzi, M.; Salis, A. Adsorption and release of ampicillin antibiotic from ordered mesoporous silica. Journal of Colloid and Interface Science 497 (2017) 217–225.

Wolfe, D.; Schorr, M.; Hanson, M.; Nelson, C.H.; Richards, S.M. Hazard assessment for a pharmaceutical mixture detected in the upper Tennessee River using Daphnia magna. Global Journal of Environmental Science and Management 1 (2015)1-14.

Moritz, G.M.; Moritz, M. APTES-modified mesoporous silicas as the carriers for poorly water-soluble drug. Modeling of diflunisal adsorption and release. Applied Surface Science 368 (2016) 348–359.

Hebig, K.H.; Groza, L.G.; Sabourin, M.J.; Scheytt, T.J.; Ptacek, C.J. Transport behavior of the pharmaceutical compounds carbamazepine, sulfamethoxazole, gemfibrozil, ibuprofen, and naproxen, and the lifestyle drug caffeine, in saturated laboratory columns. Science of The Total Environment (590–591) (2017) 708-719.


  • There are currently no refbacks.