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

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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.

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