40 2012 3 FENXI HUAXUE Chinese Journal of Analytical Chemistry 3 354 ~ 358 DOI 10. 3724 /SP. J. 1096. 2012. 10890 1 1 2 * 1 1 264003 2 100049 7. 0 10 "8 mol /L 1. 0 10 "7 ~ 1. 0 10 "4 mol /L 55. 7 mv /decade 98% ~ 107% 3 min 1 1 2011 HPLC 2 - GC-MS 3 4 ELISA 5 HPLC GC-MS ELISA 6 ~ 8 9 MIPs 10 MIPs MIPs MIPs 2 2. 1 PXSJ-216 DU-800 / Beckman S-4800 MAA MMA TRIM 80 DVB 80 PVC o-npoe 3 5- NaTFPB THF Sig- 2011-08-10 2011-09-22 No. 20977073 No. JQ200814 * E-mail wqin@ yic. ac. cn
3 355 ma-aldrich AIBN MAA TRIM DVB 80 THF AIBN Pall Cascada 18. 2 MΩ cm 0. 1 mmol /L pk a = 9. 6 5 mmol /L Tris-HCl ph 7. 4 2. 2 11 0. 4 mmol 2. 5 mmol MAA 0. 83 mmol MMA 40 ml 1 h 1 mmol TRIM 0. 4 mmol DVB 0. 5 mmol AIBN 10 min 70 24 h - 9 1 V /V λ = 245 nm NIP MAA MMA 2. 3 MIP NIP NaTFPB o-npoe PVC 5. 0% w /w MIP NIP 1. 0% w /w NaTFPB 62. 6% w /w o-npoe 31. 4% w /w PVC360. 0 mg 3. 5 ml THF 2 h 3. 6 cm 12 h 9 mm THF 1. 0 10 "4 mol /L 5 mmol /L Tris-HCl ph 7. 4 24 h 0. 01 mol /L NaCl 24 h 2. 4 Ag /AgCl PXSJ-216 Hg 2 Cl 2 Hg KCl PVC Ag AgCl 3 mol /L KCl Henderson Debye-Hückel 3 3. 1 MIP NIP MIP NIP 1a 12 MIP 0. 5 ~ 1. 0!m MIP PVC MIP 1b NIP MIP 3. 2 MIP NaTFPB PVC MIP MIP MAA MMA NaTFPB PVC
356 40 1 Fig. 1 SEM images of obtained a clenbuterol-mip and b NIP beads 1 1% MIP MIP MIP 5% MIP o-npoe ε r = 24. 0 DOS ε r = 4. 8 DOP ε r = 5. 0 31. 3% w /w PVC 62. 7% w /w NPOE 1% w /w NaTFPB 5% w /w MIP 1 Table 1 Influence of membrane composition on electrode response PVC Plasticizer NPOE DOS DOP NaTFPB MIP Linear range mol /L Slope a mv /decade 31. 7 63. 3 - - 0 5 1 10 "6 ~ 1 10 "5 32. 2 ± 1. 0 31. 3 62. 7 - - 1 5 1 10 "7 ~ 1 10 "4 55. 7 ± 0. 5 31. 2 62. 3 - - 1. 5 5 5 10 "7 ~ 1 10 "4 54. 4 ± 0. 5 33. 0 66. 0 - - 1 0 1 10 "6 ~ 1 10 "4 55. 8 ± 0. 8 30. 2 60. 3 - - 1 8. 5 1 10 "6 ~ 1 10 "4 51. 0 ± 0. 4 31. 3-62. 7-1 5 5 10 "7 ~ 1 10 "4 56. 3 ± 0. 7 31. 3 - - 62. 7 1 5 5 10 "7 ~ 1 10 "4 51. 7 ± 0. 5 a 3 ± Average from three measurements ± standard deviation NPOE Nierophenyl octyl ether DOP Dioctyl phthalate NaTFPB Sodiom tetrakis 3 5-bis trifluoro-methyl phenyl borate. 3. 3 ph ph 1 ~11 2 ph 7. 0 ~ 8. 5 ph > 8. 5 ph ph < 7. 0 13 3. 4 3 MIP 2 ph 0. 1 mmol /L 1. 0 10 "7 ~ 1. 0 10 "4 mol /L 55. 7 mv /decade 7. 0 10 "8 mol /L Fig. 2 Effect of sample ph on the electrode response MIP NIP of 0. 1 mmol /L clenbuterol
3 357 MIP MIP NIP 3. 5 14 Nicolskii-Eisenman 3 K pot J 15 I 2 Fig. 3 Calibration curves for clenbuterol-mip NIP and blank membranes Na + K + Ca 2 + Mg 2 + NH + 4 logk pot I J "7. 57 "5. 94 "7. 43 "7. 78 "6. 17 "2. 50 Na + K + 2 n = 3 Table 2 Potentiometric selectivity coefficients for the MIPbased clenbuterol ISE n = 3 3. 6 95% Interfering ion logk Interfering ion logk 4 Na + "7. 57 "6. 28 a Cu 2 + "7. 35 1 10 "5 ~ 1 10 "4 mol /L K + "5. 94 "4. 96 a Zn 2 + "7. 84 5 s 1 H + "6. 86 Ractopamine ion "2. 50 10 "5 ~1 10 "4 mol /L 1 10 "4 ~ Ca 2 + "7. 43 Ethylenediamine ion "6. 06 Mg 2 + "7. 78 NH 4 + "6. 17 1 10 "5 mol /L a NIP Values in parentheses are t he selectivity coefficients for NIP membrane electrode 4 1 6. 4% 3. 7 0. 22!m 3 98% ~ 107% 3 min 3 Table 3 Application of the proposed electrode to determination of clenbuterol in pig urine samples spiked with different amounts of clenbuterol Sample Added Found n = 3 a 1 27. 7 29. 6 #1. 6 107 2 83. 1 84. 7 #3. 3 102 3 138. 5 135. 4 #4. 5 98 4 166. 2 171. 2 #4. 4 103 Recovery % 4 a # Average from three measurements ± standard deviation Fig. 4 Potential response of the MIP based ISE
358 40 References 1 van Vyncht G Preece S Gaspar P Maghuin-Rogister G Depauw E. J. Chromatogr. A 1996 750 1-2 43 ~ 49 2 WU Yin-Liang YANG Ting SHAN Ji-Hao HUANGFU Wei-Guo. Chinese J. Anal. Chem. 2010 38 6 833 ~ 837. 2010 38 6 833 ~ 837 3 WU Yin-Liang LI Xiao-Wei LIU Su-Ying SHEN Jian-Zhong YANG Ting. Chinese J. Anal. Chem. 2006 34 8 1083 ~ 1086. 2006 34 8 1083 ~ 1086 4 HU Hua-Jun FU Tao ZHANG Ming-Zhou HONG Zhi CHEN Zong-Lun LIU Jun. Chinese J. Anal. Chem. 2010 38 12 1727 ~ 1731. 2010 38 12 1727 ~ 1731 5 Roda A Manetta A C Piazza F Simoni F Lelli R. Talanta 2000 52 2 311 ~ 318 6 Sokalski T Ceresa A Zwickl T Pretsch E. J. Am. Chem. Soc. 1997 119 46 11347 ~ 11348 7 Bakker E Pretsch E. Angew. Chem. Int. Ed. 2007 46 30 5660 ~ 5668 8 Ding J W Qin W. J. Am. Chem. Soc. 2009 131 41 14640 ~ 14641 9 Haupt K Mosbach K. Chem. Rev. 2000 100 7 2495 ~ 2504 10 HU Yu-Fang ZHANG Zhao-Hui ZHANG Hua-Bin YU Xiao-Xiao YAO Shou-Zhuo. Chem. J. Chinese Universities 2009 30 9 1703 ~ 1708. 2009 30 9 1703 ~ 1708 11 Yoshimatsu K Reimhult K Krozer A Mosbach K Sode K Ye L. Anal. Chim. Acta 2007 584 1 112 ~ 121 12 Liang R N Song D A Zhang R M Qin W. Angew. Chem. Int. Ed. 2010 49 2556 ~ 2559 13 Shan J Pan C Zhang J Niu W. Acta Chromatogr. 2008 20 1 43 ~ 57 14 Bakker E. J. Electrochem. Soc. 1996 143 4 L83 ~ L85 15 Smith M J Manahan S E. Anal. Chem. 1973 45 6 836 ~ 839 Potentiometric Sensor Based on Molecularly Imprinted Polymer for Rapid Determination of Clenbuterol in Pig Urine LIANG Rong-Ning 1 GAO Qi 1 2 QIN Wei * 1 1 Chinese Academy of Sciences and Shandong Provincial Key Laboratory of Coastal Zone Environmental Processes Yantai Institute of Coastal Zone Research Chinese Academy of Sciences Yantai 264003 China 2 Graduate University of Chinese Academy of Sciences Beijing 100049 China Abstract A polymeric membrane ion-selective electrode for the determination of clenbuterol is described. It is based on a molecularly imprinted polymer MIP as an ionophore for molecular recognition which can be synthesized by precipitation polymerization using clenbuterol hydrochloride as a template molecule. Under the optimized conditions the proposed membrane electrode exhibits Nernstian response to the protonated clenbuterol over the concentration range of 1. 0 10 "7-1. 0 10 "4 mol /L with a slope of 55. 7 mv /decade and the detection limit is 7. 0 10 "8 mol /L. The MIP-based sensor shows excellent selectivity rapid response time and satisfactory long-term stability. The potentiometric sensor has been successfully applied to determine the clenbuterol in pig urine samples with recoveries between 98% and 107% and an analytical time of less than 3 min. Keywords Molecularly imprinted polymer Potentiometric sensor Clenbuterol Received 10 August 2011 accepted 22 September 2011