A widely used herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) was imprinted on poly (4-vinylpyridine) (4-VP) using (40%) ethyleneglycol dimethacrylate (EGDMA) as crosslinking agent. The classical imprinting technology makes use of a high degree of crosslinking which does not allow the template molecules to move freely. So the binding sites, located in the central area of the three dimensional polymer matrix are hard to be accessed and the template molecules cannot be extracted totally. But here we propose a low crosslinked system with high specificity and selectivity. The imprinted and non-imprinted polymers were characterized by various spectroscopic techniques. The extent of binding was followed by batch equilibration method and compared with the respective non-imprinted polymer. Conditions for maximum specific rebinding were set by altering certain factors like template/monomer ratio, concentration of template solution, rebinding medium, mass of polymer and time of incubation. The selectivity of the imprinted polymer was investigated by comparing the binding with structural analogues of 2,4-D like, phenoxyacetic acid (POA), 4-chlorophenoxyacetic acid (4-CPOA) and 2,4,5-trichlorophenoxyacetic acid (2,4,5-T). The imprinted polymer exhibited high affinity towards the template molecule and was selectively rebound to the specific sites. The binding towards the structural analogues depends on the number of chlorine in the benzene ring.
K. Ensing and de B. Theo, “Tailor-Made Materials for Tailor-Made Applications: Application of Molecular Imprints in Chemical Analysis,” TrAC Trends in Analytical Chemistry, Vol. 18, No. 3, 1999, pp. 138-145.
D. Kriz, O. Ramstrom and K. Mosbach, “Molecular Imprinting-New Possibilities for Sensor Technology,” Analytical Chemistry News and Features, Vol. 69, 1997, pp. 345-349.
F. G. Tamayo, J. L. Casillas and A. Martin-Esteban, “Cleanup of Phenylurea Herbicides in Plant Sample Extracts Using Molecularly Imprinted Polymers,” Analytical and Bioanalytical Chemistry, Vol. 381, No. 6, 2005, pp. 1234-1240. doi:10.1007/s00216-005-3071-1
S. A. Piletsky, S. Alcock and A. P. F. Turner, “Molecular Imprinting: At the Edge of Third Millennium,” Trends in Biotechnology, Vol. 19, No. l, 2001, pp. 9-12. doi:10.1016/S0167-7799(00)01523-7
L. I. Anderson, “Molecular Imprinting: Developments and Applications in the Analytical Chemistry Field,” Journal of Chromatography B: Biomedical Sciences and Applications, Vol. 745, No. l, 2000, pp. 3-13. doi:10.1016/S0378-4347(00)00135-3
B. Sellergren, “Molecularly Imprinted Polymers: Man-Made Mimics of Antibodies and their Application in Analytical Chemistry,” Elsevier, 2001.
K. Haupt, “Imprinted Polymers—Tailor-Made Mimics of Antibodies and Receptors,” ChemInform, Vol. 34. No. 15, 2003, pp. 171-178. doi:10.1002/chin.200315284
T. D. Panasyuk, M. Vladimir, U. Mathias and S. Otto, “Impedometric Herbicide Chemosensors Based on Molecularly Imprinted Polymers,” Analytica Chimica Acta, Vol. 435, No. 1, 2001, pp. 157-162. doi:10.1016/S0003-2670(00)01280-0
M. T. Muldoon and L. H. Stanker, “Molecularly Imprinted Solid Phase Extraction of Atrazine from Beef Liver Extracts,” Analytical Chemistry, Vol. 69, No. 5, 1997, pp. 803-808. doi:10.1021/ac9604649
K. P. L. Mitch, F. C. Cheuk and H. W. L. Michael, “A Sol-Gel Derived Molecular Imprinted Luminiscent PET Sensing Materials for 2,4-Dichlorophenoxyacetic Acid,” Journal of Materials Chemistry Articles, Vol. 11, 2001, pp. 2985-2991.
E. Yimaz, K. Haupt and K. Mosbach, “The Use of Immobilized Templates—A New Approach in Molecular Imprinting,” Angewandte Chemie International Edition, Vol. 39, No. 12, 2000, pp. 2115-2118. doi:10.1002/1521-3773(20000616)39:12 3.0.CO;2-V
J. F. Wang, A. G. Cormack, D. C. Sherrington and E. Khoshdel, “Monodisperse, Molecularly Imprinted Polymer Microspheres Prepared by Precipitation Polymerization for Affinity Separation Applications,” Angewandte Chemie International Edition, Vol. 42, No. 43, 2003, pp. 5336-5338. doi:10.1002/anie.200352298
S. C. Zimmerman, M. S. Wendland, N. A. Rakow, I. Zharov and K. S. Suslick, “Synthetic Hosts by Monomolecular Imprinting inside Dendrimers,” Nature, Vol. 418, 2002, pp. 399-403. doi:10.1038/nature00877
C. H. Lu, W. H. Zhou, B. Han, H. H. Yang, X. Chen and X. R. Wang, “Surface Imprinted Core-Shell Nanoparticles for Sorbent Assays,” Analytical Chemistry, 79, No. 14, 2007, pp. 5457-5461. doi:10.1021/ac070282m
C. D. Ki and J. Y. Chang, “Preparation of a Molecularly Imprinted Polymeric Nanocapsule with Potential Use in Delivery Applications,” Macromolecules, Vol. 39, No. 9, 2006, pp. 3415-3419. doi:10.1021/ma052480q
S. Lu, G. Cheng and X. Pang, “Study on Preparation of Protein-Imprinted Soft-Wet Gel Composite Microspheres with Magnetic Susceptibility and Their Characteristics 1. Preparation and Particle Morphology,” Journal of Applied Polymer Science, Vol. 100, No. 1, 2006, pp. 684-694. doi:10.1002/app.23411
G. Wulff, “Molecular Imprinting in Cross-Linked Materials with the Aid of Molecular Templates—A Way towards Artificial Antibodies,” Angewandte Chemie International Edition, Vol. 34, No. 17, 1995, pp. 1812-1832. doi:10.1002/anie.199518121
D. Kriz and K. Mosbach, “Competitive Amperometric Morphine Sensor Based on an Agarose Immobilized Molecularly Imprinted Polymer,” Analytica Chimica Acta, Vol. 300, No. 1-3, 1995, pp. 71-75. doi:10.1016/0003-2670(94)00368-V
M. Kempe and K. Mosback, “Binding Studies on Substrate and Enantioselective Molecularly Imprinted Polymers,” Analytical Letters, Vol. 24, No. 7, 1991, pp. 1137-1145.
C. Yu and K. Mosbach, “Influence of Mobile Phase Composition and Cross-Linking Density on the Enan- tiomeric Recognition Properties of Molecularly Imprinted Polymers,” Journal of Chromatography A, Vol. 888, No. 1-2, 2000, pp. 63-72. doi:10.1016/S0021-9673(00)00556-2
D. J. O’Shannessy, G. Ekberg, L. I. Anderson and K. Mosbach, “Recent Advances in the Preparation and Use of Molecularly Imprinted Polymers for Enantiomeric Resolution of Aminoacid Derivatives,” Journal of Chromatography A, Vol. 470, No. 2, 1989, pp. 391-399. doi:10.1016/S0021-9673(01)83567-6
Z. Quing-Zhi, K. Haupt, K. Dietmar and N. Reinhard, “Molecularly Imprinted Polymers for Met Sulfuron-Methyl and Its Binding Characteristics for Sulfonylurea Herbicides,” Analytica Chimica Acta, Vol. 468, 2002, pp. 217-227. doi:10.1016/S0003-2670(01)01437-4
R. J. Umpleby, G. T. Rushton, R. N. Shah, A. M. Rampey, J. C. Bradshaw, J. K. Berch and K. D. Shimizu, “Recognition Directed Site-Selective Chemical Modification of Molecularly Imprinted Polymers,” Macromolecules, Vol. 34, No. 24, 2001, pp. 8446-8452. doi:10.1021/ma010903s
S. Lachlan, I. H. Clovia, A. McCluskey and M. C. Bowyer, “Synthesis and Evaluation of a Molecularly Imprinted Polymer Selective to 2,4,6-Trichlorophenol,” Australian Journal of Chemistry, Vol. 57, 2004, pp. 759-764. doi:10.1071/CH04004
C. Baggiani, C. Giovannoli, L. Anfossi and C. Tozzi, “Molecularly Imprinted Solid-Phase Extraction Sorbent for the Clean-up of Chlorinated Phenoxyacids from Aqueous Samples,” Journal of Chromatography A, Vol. 938, No. 1-2, 2001, pp. 35-44. doi:10.1016/S0021-9673(01)01126-8
F. Lanza and B. Sellergren, “Method for Synthesis and Screening of Large Groups of Molecularly Imprinted Polymers,” Analytical Chemistry, Vol. 71, 1999, pp. 2092-2096. doi:10.1021/ac981446p
H. S. Andersson, J. G. Karlsson, S. A. Piletsky, A. Koch-Schmidt, K. Mosbach and I. A. Nicholls, “Study of the Nature of Recognition in Molecularly Imprinted Polymers, II [1]: Influence of Monomer-Template Ratio and Sample Load on Retention and Selectivity,” Journal of Chromatography A, Vol. 848, 1999, pp. 39-49. doi:10.1016/S0021-9673(99)00483-5