Biopolym. Cell. 2014; 30(3):209-215.
Molecular and Cell Biotechnologies
Colorimetric biomimetic sensor systems based on molecularly imprinted polymer membranes for highly-selective detection of phenol in environmental samples
1Sergeyeva T. A., 1Chelyadina D. S., 2Gorbach L. A., 2Brovko O. O., 3Piletska E. V., 3Piletsky S. A., 2Sergeeva L. M., 1El’skaya A. V.
  1. Institute of Molecular Biology and Genetics, NAS of Ukraine
    150, Akademika Zabolotnoho Str., Kyiv, Ukraine, 03680
  2. Institute of Macromolecular Chemistry, NAS of Ukraine
    48, Kharkivske Shosse, Kyiv, Ukraine, 02160
  3. University of Leicester
    University Road, Leicester LE1 7RH, UK

Abstract

Aim. Development of an easy-to-use colorimetric sensor system for fast and accurate detection of phenol in envi- ronmental samples. Methods. Technique of molecular imprinting, method of in situ polymerization of molecularly imprinted polymer membranes. Results. The proposed sensor is based on free-standing molecularly imprinted polymer (MIP) membranes, synthesized by in situ polymerization, and having in their structure artificial binding sites capable of selective phenol recognition. The quantitative detection of phenol, selectively adsorbed by the MIP membranes, is based on its reaction with 4-aminoantipyrine, which gives a pink-colored product. The intensity of staining of the MIP membrane is proportional to phenol concentration in the analyzed sample. Phenol can be detected within the range 50 nM–10 mM with limit of detection 50 nM, which corresponds to the concentrations that have to be detected in natural and waste waters in accordance with environmental protection standards. Stability of the MIP-membrane-based sensors was assessed during 12 months storage at room temperature. Conclusions. The sensor system provides highly-selective and sensitive detection of phenol in both mo- del and real (drinking, natural, and waste) water samples. As compared to traditional methods of phenol detection, the proposed system is characterized by simplicity of operation and can be used in non-laboratory conditions.
Keywords: phenol, molecularly imprinted polymer membranes, sensors, test-systems, colorimetry

References

[1] Fink JK. Reactive polymers fundamentals and applications. 2nd ed. NY, William Andrew publ, 2013; 576 p.
[2] Skinner MK, Manikkam M, Guerrero-Bosagna C. Epigenetic transgenerational actions of endocrine disruptors. Reprod Toxicol. 2011;31(3):337-43.
[3] Zakeri-Milani P, Barzegar-Jalali M, Tajerzadeh H, Azarmi Y, Valizadeh H. Simultaneous determination of naproxen, ketoprofen and phenol red in samples from rat intestinal permeability studies: HPLC method development and validation. J Pharm Biomed Anal. 2005;39(3-4):624-30.
[4] Kim KR, Kim H. Gas chromatographic profiling and screening for phenols as isobutoxycarbonyl derivatives in aqueous samples. J Chromatogr A. 2000;866(1):87-96.
[5] Jakopic J, Petkovsek MM, Likozar A, Solar A, Stampar F, Vebe- ric R. HPLC–MS identification of phenols in hazelnut (Corylus avellana L.) kernels. Food Chem. 2011;124(3):1100–6.
[6] Sim?es NG, Cardoso VV, Ferreira E, Benoliel MJ, Almeida CM. Experimental and statistical validation of SPME-GC-MS analysis of phenol and chlorophenols in raw and treated water. Chemosphere. 2007;68(3):501-10.
[7] Lavilla I, Gil S, Costas M, Bendicho C. Dispersive liquid-liquid microextraction combined with microvolume spectrophotometry to turn green the 5530 APHA standard method for determining phenols in water and wastewater. Talanta. 2012;98:197–202.
[8] Zhou X-H, Liu L-H, Bai X, Shi H-C. A reduced graphene oxide based biosensor for high-sensitive detection of phenols in water samples. Sens Actuators B Chem. 2013;181:661–7.
[9] Cevik E, Senel M, Baykal A, Abasiyan MF. A novel amperometric phenol biosensor based on immobilized HRP on poly(glycidylmethacrylate)-grafted iron oxide nanoparticles for the determination of phenol derivatives. Sens Actuators B Chem. 2012;173:396–405.
[10] Fuchs Y, Soppera O, Haupt K. Photopolymerization and photostructuring of molecularly imprinted polymers for sensor applications--a review. Anal Chim Acta. 2012;717:7-20.
[11] Sharma PS, Dabrowski M, D’Souza F, Kutner W. Surface development of molecularly imprinted polymer films to enhance sensing signals. Trends Analyt Chem. 2013;51:146–57.
[12] Sergeyeva TA, Gorbach LA, Piletska EV, Piletsky SA, Brovko OO, Honcharova LA, Lutsyk OD, Sergeeva LM, Zinchenko OA, El'skaya AV. Colorimetric test-systems for creatinine detection based on composite molecularly imprinted polymer membranes. Anal Chim Acta. 2013;770:161-8.
[13] Serheieva TA, Pilets'ka OV, Honcharova LA, Brovko OO, Pilets'ky? SA, Iel's'ka HV. Sensor system based on molecular-imprinted polymer membranes for the selective recognition of aflatoxin B1. Ukr Biokhim Zh. 2008;80(3):84-93.
[14] Sergeyeva TA, Slinchenko OA, Gorbach LA, Matyushov VF, Brovko OO, Piletsky SA, Sergeeva LM, Elska GV. Catalytic molecularly imprinted polymer membranes: development of the biomimetic sensor for phenols detection. Anal Chim Acta. 2010;659(1-2):274-9.
[15] Sergeyeva TA, Piletsky SA, Brovko AA, Slinchenko EA, Sergeeva LM, El’skaya AV. Selective recognition of atrazine by molecularly imprinted polymer membranes. Development of conductometric sensor for herbicides detection. Anal Chim Acta. 1999; 392(2–3):105–11.
[16] Sergeyeva T.A, Gorbach LA, Slinchenko OA, Goncharova LA, Piletska OV, Brovko OO, Sergeeva LM, El’ska GV. Towards development of colorimetric test-systems for phenols detection based on computationally-designed molecularly imprinted polymer membranes. Mater Sci Eng C. 2010;30(3):431–6.
[17] Spirin YuL, Lipatov YuS, Magdinets VV, Sergeeva LM, Kercha YuYu, Savchenko TT, Vilenskaya LN. Polymers based on polyoxypropyleneglycol, diisocyanate, and monomethacrylic ester of ethyleneglycol. Vysokomolekulyarnyje Sojedineniya A. 1968; 10(9):2116–21.
[18] Fiamegos Y, Stalikas C, Pilidis G. 4-Aminoantipyrine spectro- photometric method of phenol analysis: Study of the reaction products via liquid chromatography with diode-array and mass spectrometric detection. Anal Chim Acta. 2002;467(1–2): 105–14.
[19] Sergeyeva TA, Piletsky SA, Piletskaya EV, Brovko OO, Karabanova LV, Sergeeva LM, El’skaya AV, Turner A.PF. In situ formation of porous molecularly imprinted polymer membranes. Macromolecules. 2003; 36(19):7352–7.
[20] Subrahmanyam S, Piletsky SA, Piletska EV, Chen B, Karim K, Turner AP. "Bite-and-Switch" approach using computationally designed molecularly imprinted polymers for sensing of creatinine. Biosens Bioelectron. 2001;16(9-12):631-7.
[21] Sergeyeva T.A, Piletska EV, Piletsky SA, Sergeyeva LM, Brovko OO, El’ska GV. Data on the structure and recognition properties of the template-selective binding sites in semi-IPN-based molecularly imprinted polymer membranes. Mater Sci Eng C. 2008;28(8):1472–9.