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Molecularly Imprinted Polymer (MIP): A Promising Recognition System for Development of Optical Sensor for Textile Dyes
Available online at www.sciencedirect.com
ScienceDirect Procedia Technology 27 (2017) 299 – 300
Biosensors 2016
Molecularly imprinted polymer (MIP): a promising recognition system for development of optical sensor for textile dyes Marcos Vinicius Foguel, Natacha Thaisa Bello Pedro, Maria Valnice Boldrin Zanoni, Maria del Pilar Taboada Sotomayor* Department of Analytical Chemistry, Institute of Chemistry, Unesp-Univ Estadual Paulista, Rua Professor Francisco Degni, 55 – 14.800-060, Araraquara, SP, Brazil
Abstract An alternative for determination of dyes is the biomimetic sensors development with optical transduction, employing molecularly imprinted polymers (MIP) as recognition system. This work shows the MIP synthesis for the textile dye Acid Green 16 and the results of rebinding, selectivity and application of this MIP in textile effluent. The imprinted polymer presented rebinding of 83% and imprinted factor of 6.91, great selectivity and recovery next to 100%. Due to the excellent performance of this MIP, it can be a promising synthetic recognizer in the development of optical biomimetic sensors based on optical fibers. © 2017 2016Published The Authors. Published Elsevier Ltd.access article under the CC BY-NC-ND license © by Elsevier Ltd.by This is an open (http://creativecommons.org/licenses/by-nc-nd/4.0/). Peer-review under responsibility of the organizing committee of Biosensors 2016. Peer-review under responsibility of the organizing committee of Biosensors 2016 Keywords: molecularly imprinted polymer; synthetic recognizer; optical sensor; dye; environmental pollutant; acid green 16
1. Introduction The detection and quantification of environmental pollutants, as textile dyes, is essential [1]. A promising way to determine these compounds is development of sensors using optical transduction, using molecularly imprinted polymers (MIP) as recognition system. MIP is a technique used for creating tailor-made artificial receptor sites in a polymer and presents good affinity and selectivity [2]. MIPs are produced by growing a polymer around a template molecule [3]. This work shows the MIP synthesis for the textile dye Acid Green 16 (AG16) and the results of rebinding, selectivity and application of this MIP in textile effluent, like a viable optical sensing phase.
* Corresponding author. Tel.: +55 16 3301 9620; fax: +55 16 3322 2308. E-mail address: [email protected]
2212-0173 © 2017 Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/). Peer-review under responsibility of the organizing committee of Biosensors 2016 doi:10.1016/j.protcy.2017.04.123
300
Marcos Vinicius Foguel et al. / Procedia Technology 27 (2017) 299 – 300
2. Experimental MIP was synthetized using 0.08 mmol AG16 (template), 0.24 mmol 1-vinylimidazole (functional monomer), 6.0 mL methanol (solvent), 16 mmol ethylene glycol dimethacrylate (cross-link) and 0.024 mmol 2,2′-Azobis(2methylpropionitrile) (initiator). N2 was purged for 10 min and the polymerization was done overnight at 60 °C. AG16 was removed by washing in a Soxhlet with methanol/acetic acid. Non-imprinted polymers (NIP) were synthesized in the same way, but without the addition of AG16. For the analysis of polymer amount, 30 µmol L-1 of AG16 and 1-8 mg mL-1 polymer was added in Eppendorf tubes for 60 min. The adsorption isotherm was carried out using different AG16 concentrations (5-240 µmol L-1) incubated with 8 mg mL-1 polymer for 60 min. Then, the tubes were centrifuged and absorbance of supernatants was monitored at 642 nm. Selectivity was performed using four different dyes: Methyl Green (MG), Basic Red 9 (BR9), Acid Red 1 (AR1) and Direct Yellow 50 (DY50). 50 µmol L-1 of each dye were added with 8 mg mL-1 of polymer (MIP/NIP) for 60 min and the rebinding percentage was compared. 1.0 L of effluent sample of a textile industry was spiked with 4.5 µmol L-1 of AG16. Then, 100 mg of MIP/NIP particles was filled in an empty SPE tube. 25 mL of spiked sample was passed through the cartridges. Dye elution was performed with 10 mL of methanol. 3. Results and discussion The polymers' performance was analyzed by rebinding of AG16 to the MIP's cavities varying the amount of polymers. Increasing the polymer concentration favored rebinding of the analyte to polymers. The rebinding of the dye to the MIP reached 79% when using 8 mg mL-1 of polymer, against 24% to the NIP and low variation among the measurements. The result of isotherm curve was very satisfactory. The amount of dye bound to the NIP was almost null, while to the MIP presented value of Q quite significant (20 mg g-1). Therefore, it is clear that selective cavities for the dye AG16 were formed successfully on the MIP structure. The imprinted factor of MIP presented an excellent result, 6.91. This result shows that the dye AG16 has a high capacity to bind to the selective cavities of the MIP. MIP-AG16 was quite selective compared to the DY50, AR1, MG and BR9, since approximately 86% of AG16 was bound to the MIP, while these other four dyes presented between 4 and 11% of binding. The extraction of AG16 dye in effluent was excellent, since the MIP presented recovery of 94.1%, while the NIP only 26.3%, showing that the use of this MIP for extraction of the dye in industrial effluents is entirely feasible. 4. Conclusions The molecularly imprinted polymer proposed in this work showed great efficiency in determining of the dye AG16. Therefore, its use as a recognizer element of optical sensors based on optical fiber can be a promising alternative for the determination of this pollutant in samples of environmental interest. Acknowledgements FAPESP (2008/10449-7, 2011/17552-0, 2014/07009-6 and 2014/25264-3) for providing the financial support. References [1] Bişgin, AT, Sürme, Y, Uçan, M, Narin, İ. Simultaneous spectrophotometric determination and column solid-phase extraction of two Lanaset textile dyes in environmental water samples. J Ind Eng Chem 2016;38:186-192. [2] Pietrzyk, A, Suriyanarayanan, S, Kutner, W, Chitta, R, D’Souza, F. Selective histamine piezoelectric chemosensor using a recognition film of the molecularly imprinted polymer of bis(bithiophene) derivatives. Anal Chem 2009;81:2633-2643. [3] Mahony, JO, Nolan, K, Smyth, MR, Mizaikoff, B. Molecularly imprinted polymers-potential and challenges in analytical chemistry. Anal Chim Acta 2005;534:31-39.
ScienceDirect Procedia Technology 27 (2017) 299 – 300
Biosensors 2016
Molecularly imprinted polymer (MIP): a promising recognition system for development of optical sensor for textile dyes Marcos Vinicius Foguel, Natacha Thaisa Bello Pedro, Maria Valnice Boldrin Zanoni, Maria del Pilar Taboada Sotomayor* Department of Analytical Chemistry, Institute of Chemistry, Unesp-Univ Estadual Paulista, Rua Professor Francisco Degni, 55 – 14.800-060, Araraquara, SP, Brazil
Abstract An alternative for determination of dyes is the biomimetic sensors development with optical transduction, employing molecularly imprinted polymers (MIP) as recognition system. This work shows the MIP synthesis for the textile dye Acid Green 16 and the results of rebinding, selectivity and application of this MIP in textile effluent. The imprinted polymer presented rebinding of 83% and imprinted factor of 6.91, great selectivity and recovery next to 100%. Due to the excellent performance of this MIP, it can be a promising synthetic recognizer in the development of optical biomimetic sensors based on optical fibers. © 2017 2016Published The Authors. Published Elsevier Ltd.access article under the CC BY-NC-ND license © by Elsevier Ltd.by This is an open (http://creativecommons.org/licenses/by-nc-nd/4.0/). Peer-review under responsibility of the organizing committee of Biosensors 2016. Peer-review under responsibility of the organizing committee of Biosensors 2016 Keywords: molecularly imprinted polymer; synthetic recognizer; optical sensor; dye; environmental pollutant; acid green 16
1. Introduction The detection and quantification of environmental pollutants, as textile dyes, is essential [1]. A promising way to determine these compounds is development of sensors using optical transduction, using molecularly imprinted polymers (MIP) as recognition system. MIP is a technique used for creating tailor-made artificial receptor sites in a polymer and presents good affinity and selectivity [2]. MIPs are produced by growing a polymer around a template molecule [3]. This work shows the MIP synthesis for the textile dye Acid Green 16 (AG16) and the results of rebinding, selectivity and application of this MIP in textile effluent, like a viable optical sensing phase.
* Corresponding author. Tel.: +55 16 3301 9620; fax: +55 16 3322 2308. E-mail address: [email protected]
2212-0173 © 2017 Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/). Peer-review under responsibility of the organizing committee of Biosensors 2016 doi:10.1016/j.protcy.2017.04.123
300
Marcos Vinicius Foguel et al. / Procedia Technology 27 (2017) 299 – 300
2. Experimental MIP was synthetized using 0.08 mmol AG16 (template), 0.24 mmol 1-vinylimidazole (functional monomer), 6.0 mL methanol (solvent), 16 mmol ethylene glycol dimethacrylate (cross-link) and 0.024 mmol 2,2′-Azobis(2methylpropionitrile) (initiator). N2 was purged for 10 min and the polymerization was done overnight at 60 °C. AG16 was removed by washing in a Soxhlet with methanol/acetic acid. Non-imprinted polymers (NIP) were synthesized in the same way, but without the addition of AG16. For the analysis of polymer amount, 30 µmol L-1 of AG16 and 1-8 mg mL-1 polymer was added in Eppendorf tubes for 60 min. The adsorption isotherm was carried out using different AG16 concentrations (5-240 µmol L-1) incubated with 8 mg mL-1 polymer for 60 min. Then, the tubes were centrifuged and absorbance of supernatants was monitored at 642 nm. Selectivity was performed using four different dyes: Methyl Green (MG), Basic Red 9 (BR9), Acid Red 1 (AR1) and Direct Yellow 50 (DY50). 50 µmol L-1 of each dye were added with 8 mg mL-1 of polymer (MIP/NIP) for 60 min and the rebinding percentage was compared. 1.0 L of effluent sample of a textile industry was spiked with 4.5 µmol L-1 of AG16. Then, 100 mg of MIP/NIP particles was filled in an empty SPE tube. 25 mL of spiked sample was passed through the cartridges. Dye elution was performed with 10 mL of methanol. 3. Results and discussion The polymers' performance was analyzed by rebinding of AG16 to the MIP's cavities varying the amount of polymers. Increasing the polymer concentration favored rebinding of the analyte to polymers. The rebinding of the dye to the MIP reached 79% when using 8 mg mL-1 of polymer, against 24% to the NIP and low variation among the measurements. The result of isotherm curve was very satisfactory. The amount of dye bound to the NIP was almost null, while to the MIP presented value of Q quite significant (20 mg g-1). Therefore, it is clear that selective cavities for the dye AG16 were formed successfully on the MIP structure. The imprinted factor of MIP presented an excellent result, 6.91. This result shows that the dye AG16 has a high capacity to bind to the selective cavities of the MIP. MIP-AG16 was quite selective compared to the DY50, AR1, MG and BR9, since approximately 86% of AG16 was bound to the MIP, while these other four dyes presented between 4 and 11% of binding. The extraction of AG16 dye in effluent was excellent, since the MIP presented recovery of 94.1%, while the NIP only 26.3%, showing that the use of this MIP for extraction of the dye in industrial effluents is entirely feasible. 4. Conclusions The molecularly imprinted polymer proposed in this work showed great efficiency in determining of the dye AG16. Therefore, its use as a recognizer element of optical sensors based on optical fiber can be a promising alternative for the determination of this pollutant in samples of environmental interest. Acknowledgements FAPESP (2008/10449-7, 2011/17552-0, 2014/07009-6 and 2014/25264-3) for providing the financial support. References [1] Bişgin, AT, Sürme, Y, Uçan, M, Narin, İ. Simultaneous spectrophotometric determination and column solid-phase extraction of two Lanaset textile dyes in environmental water samples. J Ind Eng Chem 2016;38:186-192. [2] Pietrzyk, A, Suriyanarayanan, S, Kutner, W, Chitta, R, D’Souza, F. Selective histamine piezoelectric chemosensor using a recognition film of the molecularly imprinted polymer of bis(bithiophene) derivatives. Anal Chem 2009;81:2633-2643. [3] Mahony, JO, Nolan, K, Smyth, MR, Mizaikoff, B. Molecularly imprinted polymers-potential and challenges in analytical chemistry. Anal Chim Acta 2005;534:31-39.