The Development of Molecular Imprinting Technology for Caffeine Extraction

Molecularly Imprinted Polymers (MIPs) is a type of macromolecule formed by application of molecularly imprinting technology, which creates cavities in synthetic polymeric matrices which are highly selective to an imprinted template. MIPs were synthesized experimentally using methacrylic acid (MAA), divinylbenzene-80 (DVB-80), azobisisobutyronitrile (AIBN) and methanol as a monomer, cross-linker, initiator and porogen, respectively. The Non-Imprinted Polymer (NIP) was produced simultaneously to serve as a control polymer. The rational design approach was theoretically conducted by Ab Initio Molecular Orbital Studies using Gaussian 09 computational software package at the theoretical level of DFT B3LYP/6-31 (d,p). The basis set is used to optimize the number of monomers and their binding site with the template. In both studies, MIPs were prepared with different ratios of template to monomer form a complex of 1:3, 1:4 and 1:5. Experimentally, the MIPs synthesized via precipitation polymerization technique produced homogenous spherical beads distribution where the complex 1:3 gave the best. Theoretical studies support this experimental finding where the complex 1:3 gave the highest interaction energy between caffeine and MAA, -45.29 kJ/mol followed by 1:4, -43.52 kJ/mol and 1:5, -43.11 kJ/mol.

Caffeine, Computational study, Extraction, Molecularly Imprinted Polymers (MIPs), Monomer-template interaction

Chin, I.P., Wen, P.C., Joseph, K.A., Yu, C.W., Chao, K.C., Lee, Y.D., 2003. Molecularly Imprinted Polymeric Beads for Decaffeination. Journal of Medical and Biological Engineering, Volume 23(2), pp. 53?56

Davies, M.P., Biasi, V.D., Perrett, D., 2004. Approaches to the Rational Design of Molecularly Imprinted Polymers. Analytica Chimica Acta, Volume 504, pp. 7?14

Dong, H., Wang, Y., Ou, Y., She, J., Shen, X., Li, J., Zhang, C., Liu, L., 2014. Preparation of Molecularly Imprinted Polymer for Chiral Recognition of Racemic 1,1'-Binaphthalene-2,2'-Diamine by HPLC. Acta Chromatographica, Volume 26(4), pp. 683?693

Dong, W., Yan, M., Liu, Z., Wu, G., Li, Y., 2007. Effect of Solvents on the Adsorption Selectivity of Molecularly Imprinted Polymers: Molecular Simulation and Experimental Validation. Separation and Purification Technology, Volume 53, pp. 183?188

Farrington, K., Magner, E., Regan, F., 2006. Predicting the Performance of Molecularly Imprinted Polymers: Selective Extraction of Caffeine by Molecularly Imprinted Solid Phase Extraction. Analytica Chimica Acta, Volume 566, pp. 60?68

Hage, D.S., Anguizola, J.A., Bi, C., Li, R., Matsuda, R., Papastavros, E., Pfaunmiller, E., Vargas, J., Zheng, X.W., 2012. Pharmaceutical and Biomedical Applications of Affinity Chromatography: Recent Trends and Developments. Journal of Pharmaceutical and Biomedical Analysis, Volume 69, pp. 93?105

Kim, W.J., Kim, J.D., Kim, J., Oh, S.G., Lee, Y.W., 2008. Selective Caffeine Removal from Green Tea using Supercritical Carbon Dioxide Extraction. Journal of Food Engineering, Volume 89, pp. 303?309

Liu, Y., Wang, F., Tan, T., Lei, M., 2007. Study of the Properties of Molecularly Imprinted Polymers by Computational Analysis. Analytica Chimica Acta, Volume 581, pp. 137?146

Lou, Z., Er, C., Li, J., Wang, H., Zhu, S., Sun, J., 2012. Removal of Caffeine from Green Tea by Microwave-enhanced Vacuum Ice Water Extraction. Analytica Chimica Acta, Volume 716, pp. 49?53

Metilda, P., Prasad, K., Kala, R., Gladis, J.M., Rao, T.P., Naidu, G.R.K., 2006. Ion Imprinted Polymer Based Sensor for Monitoring Toxic Uranium in Environmental Samples. Analytica Chimica Acta, Volume 582, pp. 147?153

Muhammad, T., Nur, Z., Piletska, E.V., Yimit, O., Piletsky, S.A., 2012. Rational Design of Molecularly Imprinted Polymer: the Choice of Cross-linker. Analyst, Volume 137(11), pp. 2623?2628

Ng, S.M., Narayanaswamy, R., 2006. Fluorescence Sensor using a Molecularly Imprinted Polymer as a Recognition Receptor for the Detection of Aluminium Ions in Aqueous Media. Anal Bioanal Chem, Volume 386, pp. 1235?1244

Nwuha, V., 2000. Novel Studies on Membrane Extraction of Bioactive Components of Green Tea in Organic Solvent: Part 1. Journal of Food Engineering, Volume 44, pp. 233?238

Pardeshi, S., Patrikar, R., Dhodapkar, R., Kumar, A., 2012, Validation of Computational Approach to Study Monomer Selectivity Toward the Template Gallic Acid for Rational Molecularly Imprinted Polymer Design. J Mol Model, Volume 18(11), pp. 4797?4810

Riahi, S., Eynollahi, S., Ganjali, M.R., Norouzi, P., 2010. Computational Approach to Investigation of Template/Monomer Complex in Imprinted Polymers: Dinitrobenze Sensor. International Journal Electrochemical Science, Volume 5, pp. 509?516

Tadi, K.K., Motghare, R.V., 2013. Computational and Experimental Studies on Oxalic Acid Imprinted Polymer. Journal of Chemical Sciences, Volume 125(2), pp. 413?418