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Preliminary Study of Molecularly Imprinted Polymer-based Potentiometric Sensor for Glucose
Available online at www.sciencedirect.com
ScienceDirect Procedia Engineering 170 (2017) 84 – 87
Engineering Physics International Conference, EPIC 2016
Preliminary Study of Molecularly Imprinted Polymer-based Potentiometric Sensor for Glucose Widayania,*, Yantia, Triati Dewi Kencana Wungua, and Suprijadib a Nuclear Physics and Biophysics Research Division, Theoretical High Energy Physics and Instrumentation Research Division, Faculty of Mathematics and Natural Sciences, Institut Teknologi Bandung, Jalan Ganesa 10, Bandung 40132, Indonesia b
Abstract Molecularly imprinted polymer (MIP) based on methacrylic acid (MAA) has been synthesized by bulk polymerization using glucose as template. Its potential application as electrode of potentiometric sensor for glucose has been studied. This study shows that potential responses of the MIP-based electrode depend on the concentration of glucose. For glucose concentration up to 7 mmol L-1, the measured potential is within the range of 72.5 to 295.8 mV. The potential response is linearly correlated to glucose concentration within the range of 0.02 mmol L-1 to 5 mmol L-1 with sensitivity of about 43.71.6 mV/mmol L-1. As a comparison, potential response of Non Imprinted Polymer (NIP) electrode of has been measured. There is a significance difference between the two electrodes, where the NIP-based electrode shows far less sensitive potential response to glucose concentration compared to that of MIP-based electrode. © 2017 The Authors. 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/). © 2016 The Authors. Published by Elsevier Ltd. Peer-review under responsibility of the organizing committee of the Engineering Physics International Conference 2016 Keywords: molecularly imprinted polymer; potentiometric sensor; glucose
1. Introduction Molecular imprinted polymers (MIPs) are synthetic polymers with specific recognition sites obtained through polymerization of a functional monomer and a crosslinking agent in the presence of a specific molecule used as a template. After polymerization the template molecules are removed, leaving recognition sites that are capable of recognizing the target molecules that are identical to the previously template molecules used. The development and application of molecularly imprinted polymers (MIPs), with highly specific recognition ability for target molecules, have attracted significant attention. During recent years, the MIPs have been successfully applied to artificial antibodies [1,2], chromatography [3,4], solid phase extraction [5,6,7], and chemical sensors [8,9,10]. Recently, much attention has been paid to the development of electrochemical sensors based on MIPs [11,12,13,14,15]. The electrochemical sensors are basically categorized into four major groups depending on the measurement principles: i.e., potentiometric, amperometric, impedemetric, and conductometric sensors. Among them, the potentiometric sensors have attracted substantial interest for practical applications. Potentiometric detection based on MIP, as a simple method, offers several advantages such as ease of preparation and procedures, simple instrumentation, wide dynamic range, reasonable selectivity, and low cost.
* Corresponding author. Tel.:+62-896-6811-7091. E-mail address: [email protected]
1877-7058 © 2017 The Authors. 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 the Engineering Physics International Conference 2016
doi:10.1016/j.proeng.2017.03.016
Widayani et al. / Procedia Engineering 170 (2017) 84 – 87
The MIPs-based potentiometric has been applied in the biological [16,17], environment [18,19], food and beverage analysis [14,20], and pharmaceutical [21,22,23]. But until now, there are only few reports on the MIPs-based potentiometric sensor which is applied to the determination of glucose. Wu (2016) had detected glucose with the MIP based-potentiometric sensor. The MIP for the recognition of glucose is synthesized by coelectropolymerizing the 3-hydroxyphenyl boronic acid and phenol. To the best of our knowledge, no potentiometric sensors have been developed for the detection of glucose based on the MAAMIP. In this paper, potentiometric sensor for the determination of glucose containing MAA-based MIP as sensitive sensing elements is studied. We present a preliminary results potentiometric sensor with imprinted polymers which is fabricated on glass tube by means of methacrylic acid as the monomer and glucose as the template molecule to realize the sensitivity sensor of glucose. 2. The object of the study This study is aimed to investigate the use of MAA-based MIP as active material of potentiometric sensor for glucose. To be used as sensor materials, it is expected that potential response of the MAA-based MIP has high sensitivity to glucose concentration. 3. Methods 3.1. Materials Glucose, methacrylic acid (MAA), ethylene glycol dimethacrylate (EGDMA), benzoyl peroxide (BPO) were purchased from Sigma-Aldrich. Methanol, acetic acid, and chloroform were acquired Merck. All of the reagents were analytical grades and used as being supplied without any further purification. 3.2. Synthesis of molecularly imprinted polymers The MAA-based MIP using glucose as template was synthesized by the bulk polymerization method. Simply, the powdered glucose (29.5 mg) and methacrylic acid (0.2 mL), EGDMA (0.62 mL), BPO (50 mg) were dissolved in 3.1 mL of chloroform. Thereafter, the mixture was then stirred for 20 min. Next, the mixture was uniformly dispersed with sonication for 40 min. The resulting mixture was then transferred into a glass dish of 6 mm diameter. The mixture was then cooled for 1 h in a refrigerator to remove oxygen prior starting the polymerization. The polymerization was carried out at 60°C for 21 h. The template was removed by washing the membrane successively in 0.3 mL acetonitrile for 1h, 0.2 ml of a methanol/acetic acid (1:1) for 1 h, then in 0.3 ml of methanol/aquabidest (1:1) and finally in 0.3 ml of methanol for 24 h. Recognition sites were formed after the template was removed. The scheme of glucose MIP formation can be found in Ref. [25]. The non-imprinted polymer (NIP) was synthesized by the similar procedure in the absence of template molecules. 3.3. Preparation of the potentiometric sensors In order to create a potentiometric sensor, imprinted polymer as the working electrode was conditioned for 2 h by soaking in 5.0×10−3 mmol L-1 glucose solution, HCl 30 mmol L-1 (pH 1.2), and KCl. The reference electrode was an Ag/AgCl electrode while a copper wire was employed as counter electrode. All the potential measurements were carried out with the following cell assembly: Ag–AgCl|KCl|internal testing solution|salt bridge|MIP electrode|internal solution, 5.0×10−3 mmol L-1 glucose|Cu|. The cell potential was measured at different glucose concentration in the test solution in the range 0.02 mmol L-1 to 7 mmol L-1. Metrohm 692 pH/mV-meter was used for potential measurements at 25.0 ± 1 oC.
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Widayani et al. / Procedia Engineering 170 (2017) 84 – 87
4. Results and Discussion The potential response of the MIP-based and NIP-based potentiometric sensor for glucose is shown at Fig. 1. The figures show that the potential response depend on the glucose concentration.
(a)
(b)
Fig. 1. Potential response of the MIP (a) and NIP (b) based potentiometric sensor at various glucose concentrations.
As seen from the Fig. 1 (a), the effect of glucose concentration on the response potential of the electrode was studied from 0.02 mmol L-1 to 7 mmol L-1. The response potentials of the MIP electrode increases with increasing glucose concentration. Linear relationship between the response potential and the glucose concentration of MIP-based potentiometric sensor are presented in the concentration range from 0.02 mmol L-1 to 5 mmol L-1 (R2 = 0.98) with sensitivity of 43.71.6 mV/mmol L-1 giving potential within the range of 72.51.4 mV to 286.15.7 mV. High sensitivity value means that small changes in the concentration of the glucose results in significant potential response. The potential response is sensitively respond to the glucose concentration, due to the oxidation or reduction of analytes at the MIP electrode. This MIP-based potentiometric sensor is wide linear detection range, which is wider than some of previously reported glucose sensors [26,27,28]. On the other hand, when the concentration of glucose is above 5 mmol L-1, the potential response shows saturation; it means that the MIP is no more sensitive to the change of glucose concentration. Potential response of the NIP-based is measured for glucose concentration within the range of 0.02 mmol L-1 to 7 mmol L-1. The result is shown in Fig. 1 (b). As can be seen, the plots exhibit two range of linear relation with different sensitivity: (1) from 0.02 mmol L-1 to 1.5 mmol L-1 (R2 = 0.94) with sensitivity of 37.81.3 mV/mmol L-1 giving potential are within the range of 53.61.1 mV to 114.22.3 mV and (2) from 1.5 mmol L-1 to 7 mmol L-1 (R2 = 0.98) with sensitivity of 5.10.57 mV/ mmol L-1 giving potential are within the range of 114.2 2.3 mV to 143.32.9 mV. It is noted that the NIP electrode are synthesized, washed, and conditioned like the MIP electrode but without template, thus NIP is prepared without printed cavities. As expected, the NIP electrode gave much lower potential values and lower sensitivity. This indicates that glucose also interacts with the NIP electrode but it is a very weak interaction. Different with NIP electrode, MIP electrode is prepared to have recognition sites. The sites can well recognize glucose. From the experimental results, there is noticeable differences between the MIP and NIP electrodes in response to glucose. 5. Conclusion This study demonstrates the potentiometric sensor for glucose based on MAA-based MIP electrode. The MIP is prepared by bulk polymerization using glucose as template molecule. The potentiometric sensor prepared with this MIP shows a considerable difference in potential response to glucose concentration in comparison to the corresponding NIP-based sensor. The MIP electrode exhibit linear response in wide range of glucose concentration with good sensitivity. Therefore, MIP electrode based on MAA as a functional monomer is promising to be used as active material of potentiometric sensor.
Widayani et al. / Procedia Engineering 170 (2017) 84 – 87
Acknowledgements This research is supported by Institut Teknologi Bandung, Indonesia and The Ministry of Research and Higher Education, Indonesia via research grant with contract number of 583w/l1.C01/PL/ 2016. References [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] [23] [24] [25] [26] [27] [28]
N. Lavignac, C.J. Allender, K.R. Brain, Molecularly imprinted polymers as alternatives to antibodies in sorbent assays, Anal. Chim. Acta 510 (2004) 139–145. P. Manesiotis, A.J. Hall, J. Courtois, K. Irgum, B. Sellergren, An artificial riboflavin receptor prepared by a template analogue imprinting strategy, Ang. Chemie. 44 (2005) 3902–3906. Z.L. Fan, G.L. Yang, H.Y. Liu, Y. Chen, Investigation of molecularly imprinted polymer rod with aminoantipyrine as template by in situ polymerization method and their separation characteristics, Chin. J. Chromatogr. 21 (2003) 199–201. L. Qin, X.W. He, W. Zhang, W.Y. Li, Y.K. Zhang, Surface-modified polystyrene beads as photografting imprinted polymer matrix for chromatographic separation of proteins, J. Chromatogr. A 1216 (2009) 807–814. F. Qiao, H. Sun, H. Yan, K.H. Row, Molecularly imprinted polymers for solid phase extraction, Chromatogr. 64 (2006) 625–634. M.M. Ariffin, E.I. Miller, P.A.G. Cormack, R.A. Anderson, Molecularly imprinted solid-phase extraction of diazepam and its metabolites from hair samples, Anal. Chem. 79 (2007) 256–262. D. Jégourel, R. Delépée, F. Breton, A. Rolland, R. Vidal, L.A. Agrofoglio, Molecularly imprinted polymer of 5-methyluridine for solid-phase extraction of pyrimidine nucleoside cancer markers in urine, Bioorg. Med. Chem. 16 (2008) 8932–8939. Z.P. Yang, C.J. Zhang, Designing of MIP-based QCM sensor for the determination of Cu (II) ions in solution, Sens. Actuators B 142 (2009) 210–215. Y. Yang, C.L. Yi, J. Luo, R. Liu, J.K. Liu, J.Q. Jiang, X.Y. Liu, Glucose sensors based on electrodeposition of molecularly imprinted polymeric micelles: a novel strategy for MIP sensors, Biosens. Bioelectron. 26 (2011) 2607–2612. I. Royani, Widayani, M. Abdullah, Khairurrijal, An atrazine molecularly imprinted polymer synthesized using a cooling-heating method with repeated washing: its physicochemical characteristics and enhanced cavities, Int. J. Electrochem. Sci. 9 (2014) 5651-5662. T.A. Sergeyeva, S.A. Piletsky, A.A. Brovko, E.A. Slinchenko, L.M. Sergeeva, T.L. Panasyuk, A.V. El’skaya, Conductimetric sensor for atrazine detection based on molecularly imprinted polymer membranes, Analyst 124 (1999) 331–334. T. Panasyuk-Delaney, V.M. Mirsky, M. Ulbricht, O.S. Wolfbeis, Impedometric herbicide chemosensors based on molecularly imprinted polymers, Anal. Chim. Acta 435 (2001) 157–162. W.Mi. Yeha, K.Ch. Ho, Amperometric morphine sensing using a molecularly imprinted polymer-modified electrode, Anal. Chim. Acta 542 (2005) 76– 82. K.K. Tadi, R.V. Motghare, Potentiometric selective recognition of oxalic acid based on molecularly imprinted polymer, Int. J. Electrochem. Sci. 8 (2013) 3197–3211. A.H. Kamel, H.R. Galal. MIP-based biomimetic sensors for static and hydrodynamic potentiometric transduction of sitagliptin in biological fluids, Int. J. Electrochem. Sci. 9 (2014) 4361–4373. L. Li, Y. Liang, Y. Liu, Designing of molecularly imprinted polymer-based potentiometric sensor for the determination of heparin, Anal. Biochem. 434 (2013) 242–246. T. Alizadeh, M. Akhoundian, A novel potentiometric sensor for promethazine based on a molecularly imprinted polymer (MIP): The role of MIP structure on the sensor performance, Electrochim. Acta 55 (2010) 3477–3485. K. Prasad, K.P. Prathish, J.M. Gladis, G.R.K. Naidu, T.P. Rao, Molecularly imprinted polymer (biomimetic) based potentiometric sensor for atrazine, Sens. Actuator B 123 (2007) 65–70. V. Vishnuvardhan, Y. Kalyan, K.P. Prathish, B. Gangadhar, Y. Tharakeswar, T.P. Rao, G. R. Naidu, Imprinted polymer inclusion membrane based potentiometric sensor for determination and quantification of diethyl chlorophosphate in natural waters, Am. J. Anal.Chem. 2 (2011) 376–382. R. Liang, R. Zhang, W. Qin, Potentiometric sensor based on molecularly imprinted polymer for determination of melamine in milk, Sens. Actuator B 141 (2009) 544–550. F.T.C. Moreira, A.H. Kamel, J.R.L. Guerreiro, M.G.F. Sales, Man-tailored biomimetic sensor of molecularly imprinted materials for the potentiometric measurement of oxytetracycline, Biosens. Bioelectron. 26 (2010) 566–574. M.S. Tehrani, M.T. Vardini, P. A. Azar, S.W. Husain, Molecularly imprinted polymer based PVC-membrane-coated graphite electrode for the determination of metoprolol, Int. J. Electrochem. Sci. 5 (2010) 88–104. Helena M.V. Oliveira, Felismina T.C. Moreira, M. Goreti F. Sales, Ciprofloxacin-imprinted polymeric receptors as ionophores for potentiometric transduction, Electrochim. Acta 56 (2011) 2017–2023. Y. Wu, Q.Wang, M. Chen, C. Dong, X. Zhang, S. Wang, An Enzyme Free Potentiometric Detection of Reducing Sugars Based on a Poly(3hydroxyphenylboronic acid-co-phenol) Molecularly Imprinted Polymer Modified Electrode, Am. J. Biomed. Sci. 8(1) (2016) 82–96. Yanti, T. Nurhayati, I. Royani, Widayani, Khairurrijal, Synthesis and characterization of MAA-based molecularly imprinted polymer (MIP) with Dglucose template, J. Phys.: Conference series 739 (2016) 012143. E. Asav, E. Akyilmaz, Preparation and optimization of a bienzymic biosensor based on self-assembled monolayer modified gold electrode for alcohol and glucose detection, Biosens. Bioelectron. 25 (2010) 1014–1018. S. Aytac, F. Kuralay, I.H. Boyacı, C. Unaleroglu, A novel polypyrrolephenylboronic acid based electrochemical saccharide sensor, Sens. Actuator B, 160 (2011) 405–411. Y. Oztekin, A. Ramanaviciene, Z. Yazicigil, A.O. Solak, A. Ramanavicius, Direct electron transfer from glucose oxidase immobilized on polyphenanthrolinemodified glassy carbon electrode, Biosens. Bioelectron. 26 (2011) 2541.
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ScienceDirect Procedia Engineering 170 (2017) 84 – 87
Engineering Physics International Conference, EPIC 2016
Preliminary Study of Molecularly Imprinted Polymer-based Potentiometric Sensor for Glucose Widayania,*, Yantia, Triati Dewi Kencana Wungua, and Suprijadib a Nuclear Physics and Biophysics Research Division, Theoretical High Energy Physics and Instrumentation Research Division, Faculty of Mathematics and Natural Sciences, Institut Teknologi Bandung, Jalan Ganesa 10, Bandung 40132, Indonesia b
Abstract Molecularly imprinted polymer (MIP) based on methacrylic acid (MAA) has been synthesized by bulk polymerization using glucose as template. Its potential application as electrode of potentiometric sensor for glucose has been studied. This study shows that potential responses of the MIP-based electrode depend on the concentration of glucose. For glucose concentration up to 7 mmol L-1, the measured potential is within the range of 72.5 to 295.8 mV. The potential response is linearly correlated to glucose concentration within the range of 0.02 mmol L-1 to 5 mmol L-1 with sensitivity of about 43.71.6 mV/mmol L-1. As a comparison, potential response of Non Imprinted Polymer (NIP) electrode of has been measured. There is a significance difference between the two electrodes, where the NIP-based electrode shows far less sensitive potential response to glucose concentration compared to that of MIP-based electrode. © 2017 The Authors. 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/). © 2016 The Authors. Published by Elsevier Ltd. Peer-review under responsibility of the organizing committee of the Engineering Physics International Conference 2016 Keywords: molecularly imprinted polymer; potentiometric sensor; glucose
1. Introduction Molecular imprinted polymers (MIPs) are synthetic polymers with specific recognition sites obtained through polymerization of a functional monomer and a crosslinking agent in the presence of a specific molecule used as a template. After polymerization the template molecules are removed, leaving recognition sites that are capable of recognizing the target molecules that are identical to the previously template molecules used. The development and application of molecularly imprinted polymers (MIPs), with highly specific recognition ability for target molecules, have attracted significant attention. During recent years, the MIPs have been successfully applied to artificial antibodies [1,2], chromatography [3,4], solid phase extraction [5,6,7], and chemical sensors [8,9,10]. Recently, much attention has been paid to the development of electrochemical sensors based on MIPs [11,12,13,14,15]. The electrochemical sensors are basically categorized into four major groups depending on the measurement principles: i.e., potentiometric, amperometric, impedemetric, and conductometric sensors. Among them, the potentiometric sensors have attracted substantial interest for practical applications. Potentiometric detection based on MIP, as a simple method, offers several advantages such as ease of preparation and procedures, simple instrumentation, wide dynamic range, reasonable selectivity, and low cost.
* Corresponding author. Tel.:+62-896-6811-7091. E-mail address: [email protected]
1877-7058 © 2017 The Authors. 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 the Engineering Physics International Conference 2016
doi:10.1016/j.proeng.2017.03.016
Widayani et al. / Procedia Engineering 170 (2017) 84 – 87
The MIPs-based potentiometric has been applied in the biological [16,17], environment [18,19], food and beverage analysis [14,20], and pharmaceutical [21,22,23]. But until now, there are only few reports on the MIPs-based potentiometric sensor which is applied to the determination of glucose. Wu (2016) had detected glucose with the MIP based-potentiometric sensor. The MIP for the recognition of glucose is synthesized by coelectropolymerizing the 3-hydroxyphenyl boronic acid and phenol. To the best of our knowledge, no potentiometric sensors have been developed for the detection of glucose based on the MAAMIP. In this paper, potentiometric sensor for the determination of glucose containing MAA-based MIP as sensitive sensing elements is studied. We present a preliminary results potentiometric sensor with imprinted polymers which is fabricated on glass tube by means of methacrylic acid as the monomer and glucose as the template molecule to realize the sensitivity sensor of glucose. 2. The object of the study This study is aimed to investigate the use of MAA-based MIP as active material of potentiometric sensor for glucose. To be used as sensor materials, it is expected that potential response of the MAA-based MIP has high sensitivity to glucose concentration. 3. Methods 3.1. Materials Glucose, methacrylic acid (MAA), ethylene glycol dimethacrylate (EGDMA), benzoyl peroxide (BPO) were purchased from Sigma-Aldrich. Methanol, acetic acid, and chloroform were acquired Merck. All of the reagents were analytical grades and used as being supplied without any further purification. 3.2. Synthesis of molecularly imprinted polymers The MAA-based MIP using glucose as template was synthesized by the bulk polymerization method. Simply, the powdered glucose (29.5 mg) and methacrylic acid (0.2 mL), EGDMA (0.62 mL), BPO (50 mg) were dissolved in 3.1 mL of chloroform. Thereafter, the mixture was then stirred for 20 min. Next, the mixture was uniformly dispersed with sonication for 40 min. The resulting mixture was then transferred into a glass dish of 6 mm diameter. The mixture was then cooled for 1 h in a refrigerator to remove oxygen prior starting the polymerization. The polymerization was carried out at 60°C for 21 h. The template was removed by washing the membrane successively in 0.3 mL acetonitrile for 1h, 0.2 ml of a methanol/acetic acid (1:1) for 1 h, then in 0.3 ml of methanol/aquabidest (1:1) and finally in 0.3 ml of methanol for 24 h. Recognition sites were formed after the template was removed. The scheme of glucose MIP formation can be found in Ref. [25]. The non-imprinted polymer (NIP) was synthesized by the similar procedure in the absence of template molecules. 3.3. Preparation of the potentiometric sensors In order to create a potentiometric sensor, imprinted polymer as the working electrode was conditioned for 2 h by soaking in 5.0×10−3 mmol L-1 glucose solution, HCl 30 mmol L-1 (pH 1.2), and KCl. The reference electrode was an Ag/AgCl electrode while a copper wire was employed as counter electrode. All the potential measurements were carried out with the following cell assembly: Ag–AgCl|KCl|internal testing solution|salt bridge|MIP electrode|internal solution, 5.0×10−3 mmol L-1 glucose|Cu|. The cell potential was measured at different glucose concentration in the test solution in the range 0.02 mmol L-1 to 7 mmol L-1. Metrohm 692 pH/mV-meter was used for potential measurements at 25.0 ± 1 oC.
85
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Widayani et al. / Procedia Engineering 170 (2017) 84 – 87
4. Results and Discussion The potential response of the MIP-based and NIP-based potentiometric sensor for glucose is shown at Fig. 1. The figures show that the potential response depend on the glucose concentration.
(a)
(b)
Fig. 1. Potential response of the MIP (a) and NIP (b) based potentiometric sensor at various glucose concentrations.
As seen from the Fig. 1 (a), the effect of glucose concentration on the response potential of the electrode was studied from 0.02 mmol L-1 to 7 mmol L-1. The response potentials of the MIP electrode increases with increasing glucose concentration. Linear relationship between the response potential and the glucose concentration of MIP-based potentiometric sensor are presented in the concentration range from 0.02 mmol L-1 to 5 mmol L-1 (R2 = 0.98) with sensitivity of 43.71.6 mV/mmol L-1 giving potential within the range of 72.51.4 mV to 286.15.7 mV. High sensitivity value means that small changes in the concentration of the glucose results in significant potential response. The potential response is sensitively respond to the glucose concentration, due to the oxidation or reduction of analytes at the MIP electrode. This MIP-based potentiometric sensor is wide linear detection range, which is wider than some of previously reported glucose sensors [26,27,28]. On the other hand, when the concentration of glucose is above 5 mmol L-1, the potential response shows saturation; it means that the MIP is no more sensitive to the change of glucose concentration. Potential response of the NIP-based is measured for glucose concentration within the range of 0.02 mmol L-1 to 7 mmol L-1. The result is shown in Fig. 1 (b). As can be seen, the plots exhibit two range of linear relation with different sensitivity: (1) from 0.02 mmol L-1 to 1.5 mmol L-1 (R2 = 0.94) with sensitivity of 37.81.3 mV/mmol L-1 giving potential are within the range of 53.61.1 mV to 114.22.3 mV and (2) from 1.5 mmol L-1 to 7 mmol L-1 (R2 = 0.98) with sensitivity of 5.10.57 mV/ mmol L-1 giving potential are within the range of 114.2 2.3 mV to 143.32.9 mV. It is noted that the NIP electrode are synthesized, washed, and conditioned like the MIP electrode but without template, thus NIP is prepared without printed cavities. As expected, the NIP electrode gave much lower potential values and lower sensitivity. This indicates that glucose also interacts with the NIP electrode but it is a very weak interaction. Different with NIP electrode, MIP electrode is prepared to have recognition sites. The sites can well recognize glucose. From the experimental results, there is noticeable differences between the MIP and NIP electrodes in response to glucose. 5. Conclusion This study demonstrates the potentiometric sensor for glucose based on MAA-based MIP electrode. The MIP is prepared by bulk polymerization using glucose as template molecule. The potentiometric sensor prepared with this MIP shows a considerable difference in potential response to glucose concentration in comparison to the corresponding NIP-based sensor. The MIP electrode exhibit linear response in wide range of glucose concentration with good sensitivity. Therefore, MIP electrode based on MAA as a functional monomer is promising to be used as active material of potentiometric sensor.
Widayani et al. / Procedia Engineering 170 (2017) 84 – 87
Acknowledgements This research is supported by Institut Teknologi Bandung, Indonesia and The Ministry of Research and Higher Education, Indonesia via research grant with contract number of 583w/l1.C01/PL/ 2016. References [1] [2] [3] [4] [5] [6] [7] [8] [9] [10] [11] [12] [13] [14] [15] [16] [17] [18] [19] [20] [21] [22] [23] [24] [25] [26] [27] [28]
N. Lavignac, C.J. Allender, K.R. Brain, Molecularly imprinted polymers as alternatives to antibodies in sorbent assays, Anal. Chim. Acta 510 (2004) 139–145. P. Manesiotis, A.J. Hall, J. Courtois, K. Irgum, B. Sellergren, An artificial riboflavin receptor prepared by a template analogue imprinting strategy, Ang. Chemie. 44 (2005) 3902–3906. Z.L. Fan, G.L. Yang, H.Y. Liu, Y. Chen, Investigation of molecularly imprinted polymer rod with aminoantipyrine as template by in situ polymerization method and their separation characteristics, Chin. J. Chromatogr. 21 (2003) 199–201. L. Qin, X.W. He, W. Zhang, W.Y. Li, Y.K. Zhang, Surface-modified polystyrene beads as photografting imprinted polymer matrix for chromatographic separation of proteins, J. Chromatogr. A 1216 (2009) 807–814. F. Qiao, H. Sun, H. Yan, K.H. Row, Molecularly imprinted polymers for solid phase extraction, Chromatogr. 64 (2006) 625–634. M.M. Ariffin, E.I. Miller, P.A.G. Cormack, R.A. Anderson, Molecularly imprinted solid-phase extraction of diazepam and its metabolites from hair samples, Anal. Chem. 79 (2007) 256–262. D. Jégourel, R. Delépée, F. Breton, A. Rolland, R. Vidal, L.A. Agrofoglio, Molecularly imprinted polymer of 5-methyluridine for solid-phase extraction of pyrimidine nucleoside cancer markers in urine, Bioorg. Med. Chem. 16 (2008) 8932–8939. Z.P. Yang, C.J. Zhang, Designing of MIP-based QCM sensor for the determination of Cu (II) ions in solution, Sens. Actuators B 142 (2009) 210–215. Y. Yang, C.L. Yi, J. Luo, R. Liu, J.K. Liu, J.Q. Jiang, X.Y. Liu, Glucose sensors based on electrodeposition of molecularly imprinted polymeric micelles: a novel strategy for MIP sensors, Biosens. Bioelectron. 26 (2011) 2607–2612. I. Royani, Widayani, M. Abdullah, Khairurrijal, An atrazine molecularly imprinted polymer synthesized using a cooling-heating method with repeated washing: its physicochemical characteristics and enhanced cavities, Int. J. Electrochem. Sci. 9 (2014) 5651-5662. T.A. Sergeyeva, S.A. Piletsky, A.A. Brovko, E.A. Slinchenko, L.M. Sergeeva, T.L. Panasyuk, A.V. El’skaya, Conductimetric sensor for atrazine detection based on molecularly imprinted polymer membranes, Analyst 124 (1999) 331–334. T. Panasyuk-Delaney, V.M. Mirsky, M. Ulbricht, O.S. Wolfbeis, Impedometric herbicide chemosensors based on molecularly imprinted polymers, Anal. Chim. Acta 435 (2001) 157–162. W.Mi. Yeha, K.Ch. Ho, Amperometric morphine sensing using a molecularly imprinted polymer-modified electrode, Anal. Chim. Acta 542 (2005) 76– 82. K.K. Tadi, R.V. Motghare, Potentiometric selective recognition of oxalic acid based on molecularly imprinted polymer, Int. J. Electrochem. Sci. 8 (2013) 3197–3211. A.H. Kamel, H.R. Galal. MIP-based biomimetic sensors for static and hydrodynamic potentiometric transduction of sitagliptin in biological fluids, Int. J. Electrochem. Sci. 9 (2014) 4361–4373. L. Li, Y. Liang, Y. 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