Fabrication of magnetic multi-template molecularly imprinted polymer composite for the selective and efficient removal of tetracyclines from water

Abstract

• Magnetic multi-template molecularly imprinted polymer composite was synthesized.

• MIP composite was used as the adsorbent for removal of tetracyclines from water.

• MIP composite showed excellent adsorption selectivity toward tetracyclines.

• MIP composite possessed good reusability.

Antibiotic contamination of the water environment has attracted much attention from researchers because of their potential hazards to humans and ecosystems. In this study, a multi-template molecularly imprinted polymer (MIP) modified mesoporous silica coated magnetic graphene oxide (MGO@MS@MIP) was prepared by the surface imprinting method via a sol-gel process and was used for the selective, efficient and simultaneous removal of tetracyclines (TCs), including doxycycline (DC), tetracycline (TC), chlorotetracycline (CTC) and oxytetracycline (OTC) from water. The synthesized MIP composite was characterized by Fourier transform infrared spectroscopy, transmission electron microscope and thermogravimetric analysis. The adsorption properties of MGO@MS@MIP for these TCs were characterized through adsorption kinetics, isotherms and selectivity tests. The MIP composite revealed larger adsorption quantities, excellent selectivity and rapid kinetics for these four tetracyclines. The adsorption process was spontaneous and endothermic and followed the Freundlich isotherm model and the pseudo-second-order kinetic model. The MGO@MS@MIP could specifically recognize DC, TC, CTC and OTC in the presence of some chemical analogs. In addition, the sorption capacity of the MIP composite did not decrease significantly after repeated application for at least five cycles. Thus, the prepared magnetic MIP composite has great potential to contribute to the effective separation and removal of tetracyclines from water.

Graphical abstract

Keywords

Tetracyclines / Removal / Adsorption / Molecularly imprinted polymer / Magnetic graphene oxide

References

[1] Ahmed M J (2017). Adsorption of quinolone, tetracycline, and penicillin antibiotics from aqueous solution using activated carbons. Environmental Toxicology and Pharmacology, 50: 1–10

[2] Buelke C, Alshami A, Casler J, Lin Y, Hickner M, Aljundi I H (2019). Evaluating graphene oxide and holey graphene oxide membrane performance for water purification. Journal of Membrane Science, 588: 117195 doi:10.1016/j.memsci.2019.117195

[3] Chen H Y, Liu Y D, Dong B (2018). Biodegradation of tetracycline antibiotics in A/O moving-bed biofilm reactor systems. Bioprocess and Biosystems Engineering, 41(1): 47–56

[4] Chen Y J, Wang F H, Duan L C, Yang H, Gao J (2016). Tetracycline adsorption onto rice husk ash, an agricultural waste: Its kinetic and thermodynamic studies. Journal of Molecular Liquids, 222: 487–494

[5] Cui Y, Tan F, Wang Y, Ren S, Chen J (2020). Diffusive gradients in thin films using molecularly imprinted polymer binding gels for in situ measurements of antibiotics in urban wastewaters. Frontiers of Environmental Science & Engineering, 14(6): 111

[6] Dai Y J, Zhang K X, Meng X B, Li J J, Guan X T, Sun Q Y, Sun Y, Wang W S, Lin M, Liu M, Yang S S, Chen Y J, Gao F, Zhang X, Liu Z H (2019). New use for spent coffee ground as an adsorbent for tetracycline removal in water. Chemosphere, 215: 163–172

[7] Du F Y, Sun L S, Tan W, Wei Z Y, Nie H G, Huang Z J, Ruan G H, Li J P (2019). Magnetic stir cake sorptive extraction of trace tetracycline antibiotics in food samples: preparation of metal-organic framework-embedded polyHIPE monolithic composites, validation and application. Analytical and Bioanalytical Chemistry, 411(10): 2239–2248

[8] Duman O, Ayranci E (2010). Attachment of benzo-crown ethers onto activated carbon cloth to enhance the removal of chromium, cobalt and nickel ions from aqueous solutions by adsorption. Journal of Hazardous Materials, 176(1–3): 231–238

[9] Duman O, Özcan C, Gürkan Polat T, Tunç S (2019). Carbon nanotube-based magnetic and non-magnetic adsorbents for the high-efficiency removal of diquat dibromide herbicide from water: OMWCNT, OMWCNT-Fe₃O₄ and OMWCNT-k-carrageenan-Fe₃O₄ nanocomposites. Environmental Pollution, 244: 723–732 doi:10.1016/j.envpol.2018.10.071

[10] Duman O, Tunç S, Bozoğlan B K, Polat T G (2016). Removal of triphenylmethane and reactive azo dyes from aqueous solution by magnetic carbon nanotube-k-carrageenan Fe₃O₄ nanocomposite. Journal of Alloys and Compounds, 687: 370–383

[11] Duman O, Tunç S, Polat T G (2015). Determination of adsorptive properties of expanded vermiculite for the removal of C. I. Basic Red 9 from aqueous solution: Kinetic, isotherm and thermodynamic studies. Applied Clay Science, 109–110: 22–32

[12] Guardia L, Suarez-Garcia F, Paredes J I, Solis-Fernandez P, Rozada R, Fernandez-Merino M J, Martinez-Alonso A, Tascon J M D (2012). Synthesis and characterization of graphene-mesoporous silica nanoparticle hybrids. Microporous and Mesoporous Materials, 160: 18–24

[13] Guo J F, Yu M M, Wei X, Huang L H (2018). Preparation of core-shell magnetic molecularly imprinted polymer with uniform thin polymer layer for adsorption of dichlorophen. Journal of Chemical & Engineering Data, 63(8): 3068–3073

[14] Guo L H, Ma X G, Xie X W, Huang R F, Zhang M Y, Li J, Zeng G L, Fan Y M (2019). Preparation of dual-dummy-template molecularly imprinted polymers coated magnetic graphene oxide for separation and enrichment of phthalate esters in water. Chemical Engineering Journal, 361: 245–255

[15] Kallenberger P A, Froba M (2018). Water harvesting from air with a hygroscopic salt in a hydrogel-derived matrix. Communications Chemistry, 1(1): 28 doi:10.1038/s42004-018-0028-9

[16] Kang H J, Lim M Y, Kwon J H (2012). Effects of adsorption onto silica sand particles on the hydrolysis of tetracycline antibiotics. Journal of Environmental Monitoring, 14(7): 1853–1859

[17] Li X, Ma X G, Huang R F, Xie X W, Guo L H, Zhang M Y (2018). Synthesis of a molecularly imprinted polymer on mSiO₂@Fe₃O₄ for the selective adsorption of atrazine. Journal of Separation Science, 41(13): 2837–2845

[18] Lian L L, Lv J Y, Wang X Y, Lou D W (2018). Magnetic solid-phase extraction of tetracyclines using ferrous oxide coated magnetic silica microspheres from water samples. Journal of Chromatography. A, 1534: 1–9

[19] Liu H, Zhu J, Hao L, Jiang Y, Van Der Bruggen B, Sotto A, Gao C, Shen J (2019). Thermo- and pH-responsive graphene oxide membranes with tunable nanochannels for water gating and permeability of small molecules. Journal of Membrane Science, 587: 117163

[20] Liu P, Liu W J, Jiang H, Chen J J, Li W W, Yu H Q (2012). Modification of bio-char derived from fast pyrolysis of biomass and its application in removal of tetracycline from aqueous solution. Bioresource Technology, 121: 235–240

[21] Liu Q, Zhong L B, Zhao Q B, Frear C, Zheng Y M (2015). Synthesis of Fe₃O₄/polyacrylonitrile composite electrospun nanofiber mat for effective adsorption of tetracycline. ACS Applied Materials & Interfaces, 7(27): 14573–14583

[22] Ma P F, Yang W M, Fan T, Liu H, Zhou Z P, Li J H, Zhang L, Xu W Z (2015). Surface imprinted polymers for oil denitrification with the combination of computational simulation and multi-template molecular imprinting. Polymers for Advanced Technologies, 26(5): 476–486

[23] Pourjavadi A, Tehrani Z M, Salimi H, Banazadeh A, Abedini N (2015). Hydrogel nanocomposite based on chitosan-g-acrylic acid and modified nanosilica with high adsorption capacity for heavy metal ion removal. Iranian Polymer Journal, 24(9): 725–734

[24] Radjenovic J, Petrovic M (2017). Removal of sulfamethoxazole by electrochemically activated sulfate: Implications of chloride addition. Journal of Hazardous Materials, 333: 242–249

[25] Rattanachueskul N, Saning A, Kaowphong S, Chumha N, Chuenchom L (2017). Magnetic carbon composites with a hierarchical structure for adsorption of tetracycline, prepared from sugarcane bagasse via hydrothermal carbonization coupled with simple heat treatment process. Bioresource Technology, 226: 164–172

[26] Tsai W H, Huang T C, Huang J J, Hsue Y H, Chuang H Y (2009). Dispersive solid-phase microextraction method for sample extraction in the analysis of four tetracyclines in water and milk samples by high-performance liquid chromatography with diode-array detection. Journal of Chromatography. A, 1216(12): 2263–2269

[27] Van Der Voort P, Ravikovitch P I, De Jong K P, Neimark A V, Janssen A H, Benjelloun M, Van Bavel E, Cool P, Weckhuysen B M, Vansant E F (2002). Plugged hexagonal templated silica: a unique micro- and mesoporous composite material with internal silica nanocapsules. Chemical Communications, (9): 1010–1011 doi:10.1039/b201424f

[28] Wang J, Chen Z M, Chen B L (2014). Adsorption of polycyclic aromatic hydrocarbons by graphene and graphene oxide nanosheets. Environmental Science & Technology, 48(9): 4817–4825

[29] Wang J J, Wei J (2017). Selective and simultaneous removal of dibenzothiophene and 4-methyldibenzothiophene using double-template molecularly imprinted polymers on the surface of magnetic mesoporous silica. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 5(9): 4651–4659

[30] Wang R, Ma X G, Zhang X J, Li X, Li D P, Dang Y F (2019). C8-modified magnetic graphene oxide based solid-phase extraction coupled with dispersive liquid-liquid microextraction for detection of trace phthalate acid esters in water samples. Ecotoxicology and Environmental Safety, 170: 789–795 doi:10.1016/j.ecoenv.2018.12.051

[31] Wang Z M, Wang W D, Coombs N, Soheilnia N, Ozin G A (2010). Graphene oxide-periodic mesoporous silica sandwich nanocomposites with vertically oriented channels. ACS Nano, 4(12): 7437–7450

[32] Wei D, Li M T, Wang X D, Han F, Li L S, Guo J, Ai L J, Fang L L, Liu L, Du B, Wei Q (2016). Extracellular polymeric substances for Zn(II) binding during its sorption process onto aerobic granular sludge. Journal of Hazardous Materials, 301: 407–415

[33] Wu H J, Zhang H L, Zhang W J, Yang X F, Zhou H, Pan Z Q, Wang D S (2019). Preparation of magnetic polyimide@ Mg-Fe layered double hydroxides core-shell composite for effective removal of various organic contaminants from aqueous solution. Chemosphere, 219: 66–75

[34] Xie L W, Guo J F, Zhang Y P, Hu Y C, You Q P, Shi S Y (2015). Novel molecular imprinted polymers over magnetic mesoporous silica microspheres for selective and efficient determination of protocatechuic acid in Syzygium aromaticum. Food Chemistry, 178: 18–25

[35] Xie X W, Ma X G, Guo L H, Fan Y M, Zeng G L, Zhang M Y, Li J (2019). Novel magnetic multi-templates molecularly imprinted polymer for selective and rapid removal and detection of alkylphenols in water. Chemical Engineering Journal, 357: 56–65

[36] Xu S N, Ding J, Chen L G (2018). A fluorescent material for the detection of chlortetracycline based on molecularly imprinted silica-graphitic carbon nitride composite. Analytical and Bioanalytical Chemistry, 410(27): 7103–7112

[37] Xu W Z, Zhou W, Xu P P, Pan J M, Wu X Y, Yan Y S (2011). A molecularly imprinted polymer based on TiO₂ as a sacrificial support for selective recognition of dibenzothiophene. Chemical Engineering Journal, 172(1): 191–198

[38] Yang X Q, Yang C X, Yan X P (2013). Zeolite imidazolate framework-8 as sorbent for on-line solid-phase extraction coupled with high-performance liquid chromatography for the determination of tetracyclines in water and milk samples. Journal of Chromatography. A, 1304: 28–33

[39] Ye B, Chen Z, Li X, Liu J, Wu Q, Yang C, Hu H, Wang R (2019). Inhibition of bromate formation by reduced graphene oxide supported cerium dioxide during ozonation of bromide-containing water. Frontiers of Environmental Science & Engineering, 13(6): 86

[40] Zhang M Y, Ma X G, Li J, Huang R F, Guo L H, Zhang X F, Fan Y M, Xie X W, Zeng G L (2019). Enhanced removal of As(III) and As(V) from aqueous solution using ionic liquid-modified magnetic graphene oxide. Chemosphere, 234: 196–203

[41] Zhang Y, Cheng X, Jiang X, Urban J J, Lau C H, Liu S, Shao L (2020). Robust natural nanocomposites realizing unprecedented ultrafast precise molecular separations. Materials Today, 36: 40–47

[42] Zhang Z Y, Lan H C, Liu H J, Qu J H (2015). Removal of tetracycline antibiotics from aqueous solution by amino-Fe (III) functionalized SBA15. Colloids and Surfaces a-Physicochemical and Engineering Aspects, 471: 133–138

[43] Zhou Q, Li Z Q, Shuang C D, Li A M, Zhang M C, Wang M Q (2012). Efficient removal of tetracycline by reusable magnetic microspheres with a high surface area. Chemical Engineering Journal, 210: 350–356

[44] Zhu Y W, Murali S, Cai W W, Li X S, Suk J W, Potts J R, Ruoff R S (2010). Graphene and graphene oxide: Synthesis, properties, and applications. Advanced Materials, 22(35): 3906–3924

[45] Zyoud A H, Zubi A, Zyoud S H, Hilal M H, Zyoud S, Qamhieh N, Hajamohideen A, Hilal H S (2019). Kaolin-supported ZnO nanoparticle catalysts in self-sensitized tetracycline photodegradation: Zero-point charge and pH effects. Applied Clay Science, 182: 105294

RIGHTS & PERMISSIONS

Higher Education Press