DOI: 10.17586/2226-1494-2015-15-4-568-577


N. Lopes, F. Sekeira, M. S. Gomes, N. Rogerio Nogueira, L. Bilro, O. . Zadorozhnaia, A. M. Rudnitskaya

Read the full article 
Article in Russian

For citation: Lopes N., Sequeira F., Gomes M.T.S.R., Nogueira R., Bilro L., Zadorozhnaya O.A., Rudnitskaya A.M. Fiber optic sensor modified by grafting of the molecularly imprinted polymer for the detection of ammonium in aqueous media. Scientific and Technical Journal of Information Technologies, Mechanics and Optics, 2015, vol.15, no. 4, pp. 568–577.

Subject of Research.The paper deals with novel chemical sensors based on the polymeric optical fibers modified by grafting of the molecularly imprinted polymer for the detection of ammonium in aqueous solutions. Elevated concentrations of ammonium in surface waters lead to their eutrophication, that’s why, monitoring of the content of this ion is very important for the evaluation of surface water quality. However, currently in situ monitoring of relevant parameters in surface waters is constrained by the availability and cost of commercial sensors. Attractive approach to the development of chemical sensors for remote controls is the use of polymeric optical fibers. Polymer optical fibers have high mechanical resistance and low cost, and give the possibility for multiplexing and remote sensing. Method. Polymeric layer imprinted with ammonium ions was grafted on the surface of the methylmethacrylate fiber. Methacrylic acid was used as a monomer, ethylene glycol dimethacylate as a cross-linker, 2.2'-Azobis (2-ethylpropionamidine) dihydrochloride as a radical initiator, ammonium as a template and water:ethanol 4:1 mixture as a solvent. Optimization of the imprinted polymer synthesis conditions was carried out using intensity of transmitted light, uniformity of the grafted polymeric layer and response in the aqueous ammonium solutions as optimization criteria. Main Results. Chemical sensors based on the polymeric optical fibers modified by grafting of the molecularly imprinted polymer for the detection of ammonium in aqueous solutions have been developed. New method of the grafting of the molecularly imprinted polymer on the surface of the methylmethacrylate optical fiber has been developed. It was found out, that high concentrations of the monomer and cross-linker in the polymerization solutions cause optical fiber damage while longer polymerization times result in the decrease of the intensity of transmitted light. Optical sensor demonstrating response to ammonium in the aqueous solutions was obtained using the following experimental conditions: methacrylic acid – 2.1 mmolL-1, ethylene glycol dimethacylate – 7.7 mmolL-1 and NH4Cl – 0.3 mmolL-1 and polymerization time equal to15 minutes. Practical Relevance. Results obtained in this work are applicable in the ecological monitoring of ammonium in the surface waters, in particular, as a part of remote in situ sensing systems. Furthermore, developed optimized method of the grafting of molecularly imprinted polymer on the surface of the polymeric optical fiber is usable for the development of fiber optic sensors for detection of other compounds.

Keywords: polymer optical fiber sensor, molecular imprinting, grafting, ammonium detection.

Acknowledgements. F. Sequeira and L. Bilro gratefully acknowledge the financial support received from Portuguese Foundation for Science and Technology (FCT) through fellowships SFRH/BD/88899/2012 and SFRH/BPD/78205/2011, respectively, and UID/EEA/50008/2013 and PEst-OE/EEI/LA0008/2013 (sWAT). Teresa Gomes and Alisa Rudnitskaya wish to acknowledge financial support from FCT through UID/AMB/50017/2013. This work was partially financially supported by the Government of the Russian Federation, project 074-U01.

1. Camargo J.A., Alonso A. Ecological and toxicological effects of inorganic nitrogen pollution in aquatic ecosystems: a global assessment. Environment International, 2006, vol. 32, no. 6, pp. 831–849. doi: 10.1016/j.envint.2006.05.002
2. Molins-Legua M., Meseguer-Lloret S., Moliner-Martinez Y., Campins-Falco P. A guide for selecting the most appropriate method for ammonium determination in water analysis. Trends in Analitical Chemistry, 2006, vol. 25, no. 3, pp. 282–290. doi: 10.1016/j.trac.2005.12.002
3. Zadorojny C., Saxton S., Finger R. Spectrophotometric determination of ammonia. Journal of the Water Pollution Control Federation, 1973, vol. 45, no. 5, pp. 905–912.
4. Kuo C.-T., Wang P.-Y., Wu C.-H. Fluorometric determination of ammonium ion by ion chromatography using postcolumn derivatization with o-phthaldialdehyde. Journal of Chromatography A, 2005, vol. 1085, no. 1, pp. 91–97. doi: 10.1016/j.chroma.2005.05.042
5. Thomas D.H., Rey M., Jackson P.E. Determination of inorganic cations and ammonium in environmental waters by ion chromatography with a high-capacity cation-exchange column. Journal of Chromatography A, 2002, vol. 956, no. 1–2, pp. 181–186. doi: 10.1016/S0021-9673(02)00141-3
6. McDonagh C., Burke C.S., MacCraith B.D. Optical chemical sensors. Chemical Review, 2008, vol. 108, no. 2, pp. 400–422. doi: 10.1021/cr068102g
7. Polishuk P. Plastic optical fibers branch out. IEEE Communications Magazine, 2006, vol. 44, no. 9, pp. 140–148. doi: 10.1109/MCOM.2006.1705991
8. Cennamo N., Zeni L. Bio and chemical sensors based on surface plasmon resonance in a plastic optical fiber, in Optical Sensors - New Developments and Practical Applications. Eds. M. Yasin, S. Wadi Harun, H. Arof. InTech, 2014, 230 p. doi: 10.5772/57077
9. Cennamo N., D'Agostino G., Galatus R., Bibbo L., Pesavento M., Zeni L. Sensors based on surface plasmon resonance in a plastic optical fiber for the detection of trinitrotoluene. Sensors and Actuators B, 2013, vol. 188, pp. 221–226. doi: 10.1016/j.snb.2013.07.005
10. Chen L., Xu S., Li J. Recent advances in molecular imprinting technology: current status, challenges and highlighted applications. Chemical Society Reviews, 2011, vol. 40, no. 5, pp. 2922–2942. doi:10.1039/c0cs00084a
11. Bossi A., Bonini F., Turner A.P.F., Piletsky S.A. Molecularly imprinted polymers for the recognition of proteins: the state of the art. Biosensors and Bioelectronics, 2007, vol. 22, no. 6, pp. 1131–1137. doi: 10.1016/j.bios.2006.06.023
12. Pasparakis G., Alexander C. Synthetic polymers for capture and detection of microorganisms. Analyst, 2007, vol. 132, no. 11, pp. 1075–1082. doi: 10.1039/b705097f
13. Lanza F., Hall A.J., Sellergren B., Bereczki A., Horvai G., Bayoudh S., Cormack P.A.G., Sherrington D.C. Development of a semiautomated procedure for the synthesis and evaluation of molecularly imprinted polymers applied to the search for functional monomers for phenytoin and nifedipine. Analytica Chimica Acta, 2001, vol. 435, no. 1, pp. 91–106. doi: 10.1016/S0003-2670(01)00905-9
14. Kim H., Spivak D.A. New insight into modeling non-covalently imprinted polymers. Journal of the American Chemical Society, 2003, vol. 125, no. 37, pp. 11269–11275. doi: 10.1021/ja0361502
15. Piletska E.V., Guerreiro A.R., Whitcombe M.J., Piletsky S.A. Influence of the polymerization conditions on the performance of molecularly imprinted polymers. Macromolecules, 2009, vol. 42, no. 14, pp. 4921–4928. doi: 10.1021/ma900432z
16. Lu Y., Li C., Wang X., Sun P., Xing X. Influence of polymerization temperature on the molecular recognition of imprinted polymers. Journal of Chromatography B, 2004, vol. 804, no. 1, pp. 53–59. doi: 10.1016/j.jchromb.2003.10.013
17. Piletsky S.A., Piletska E.V., Karim K., Freebairn K.W., Legge C.H., Turner A.P.F. Polymer cookery: influence of polymerization conditions on the performance of molecularly imprinted polymers. Macromolecules, 2002, vol. 35, no. 19, pp. 7499–7504. doi: 10.1021/ma0205562
18. Sellergren B., Dauwe C., Schneider T. Pressure-induced binding sites in molecularly imprinted network polymers. Macromolecules, 1997, vol. 30, no. 8, pp. 2454–2459.
19. Hattori K., Hiwatari M., Iiyama C., Yoshimi Y., Kohori F., Sakai K., Piletsky S.A. Gate effect of theophylline-imprinted polymers grafted to the cellulose by living radical polymerization. Journal of Membrane Science, 2004, vol. 233, no. 1–2, pp. 169–173. doi: 10.1016/j.memsci.2003.12.013
20. Sulitzky C., Ruckert B., Hall A.J., Lanza F., Unger K., Sellergren B. Grafting of molecularly imprinted polymer films on silica supports containing surface-bound free radical initiators. Macromolecules, 2002, vol. 35, no. 1, pp. 79–91. doi: 10.1021/ma011303w
21. Evchuk I.Yu., Musii R.I., Makitra R.G., Pristanskii R.E. Solubility of polymethyl methacrylate in organic solvents. Russian Journal of Applied Chemistry, 2005, vol. 78, no. 10, pp. 1576–1580. doi/s11167-005-0564-9: 10.1007
22. Yoshimatsu K., Yamazaki T., Chronakis I.S., Ye L. Influence of template/functional monomer/cross-linking monomer ratio on particle size and binding properties of molecularly imprinted nanoparticles. Journal of
Applied Polymer Science, 2012, vol. 124, no. 2, pp. 1249–1255. doi: 10.1002/app.35150
23. Zhu Q.-Z., Haupt K., Knopp D., Niessner R. Molecularly imprinted polymer for metsulfuron-methyl and its binding characteristics for sulfonylurea herbicides. Analytica Chimica Acta, 2002, vol. 468, no. 2, pp. 217–227. doi: 10.1016/S0003-2670(01)01437-4
Copyright 2001-2018 ©
Scientific and Technical Journal
of Information Technologies, Mechanics and Optics.
All rights reserved.