Predicting the performance of molecularly imprinted polymers: Selective extraction of caffeine by molecularly imprinted solid phase extraction

A rational design approach was taken to the planning and synthesis of a molecularly imprinted polymer capable of extracting caffeine (the template molecule) from a standard solution of caffeine and further from a food sample containing caffeine. Data from NMR titration experiments in conjunction with a molecular modelling approach was used in predicting the relative ratios of template to functional monomer and furthermore determined both the choice of solvent (porogen) and the amount used for the study. In addition the molecular modelling program yielded information regarding the thermodynamic stability of the pre-polymerisation complex. Post-polymerisation analysis of the polymer itself by analysis of the pore size distribution by BET yielded significant information regarding the nature of the size and distribution of the pores within the polymer matrix. Here is proposed a stepwise procedure for the development and testing of a molecularly imprinted polymer using a well-studied compound—caffeine as a model system. It is shown that both the physical characteristics of a molecularly imprinted polymer (MIP) and the analysis of the pre-polymerisation complex can yield vital information, which can predict how well a given MIP will perform.

[1]  M. Hennion,et al.  Experimental comparison of three monoclonal antibodies for the class-selective immunoextraction of triazines. Correlation with molecular modeling and principal component analysis studies. , 2003, Journal of chromatography. A.

[2]  Ian A. Nicholls,et al.  Receptor and transport properties of imprinted polymer membranes – a review , 1999 .

[3]  O. Brüggemann.  Chemical reaction engineering using molecularly imprinted polymeric catalysts , 2001 .

[4]  P. Cormack,et al.  Molecularly imprinted polymers: synthesis and characterisation. , 2004, Journal of chromatography. B, Analytical technologies in the biomedical and life sciences.

[5]  G. Theodoridis,et al.  Selective solid-phase extraction sorbent for caffeine made by molecular imprinting. , 2002, Journal of chromatography. A.

[6]  M. Syu,et al.  An allosteric model for the binding of bilirubin to the bilirubin imprinted poly(methacrylic acid-co-ethylene glycol dimethylacrylate) , 2005 .

[7]  Naresh Magan,et al.  Effect of the solvent on recognition properties of molecularly imprinted polymer specific for ochratoxin A. , 2004, Biosensors & bioelectronics.

[8]  J. Haginaka,et al.  Separation and sensing based on molecular recognition using molecularly imprinted polymers. , 1999, Journal of chromatography. B, Biomedical sciences and applications.

[9]  Sergey A. Piletsky,et al.  MIP-based solid phase extraction cartridges combined with MIP-based sensors for the detection of microcystin-LR. , 2003, Biosensors & bioelectronics.

[10]  E. Turiel,et al.  Characterisation and quality assessment of binding sites on a propazine-imprinted polymer prepared by precipitation polymerisation. , 2004, Journal of chromatography. B, Analytical technologies in the biomedical and life sciences.

[11]  I. Nicholls,et al.  Spectroscopic Evaluation of Molecular Imprinting Polymerization Systems , 1997 .

[12]  F. Iemma,et al.  Molecularly imprinted solid phase extraction for detection of sudan I in food matrices , 2005 .

[13]  Zheng Liu,et al.  A computational and experimental investigation of the interaction between the template molecule and the functional monomer used in the molecularly imprinted polymer , 2005 .

[14]  Meiping Zhao,et al.  Theoretical and experimental study of nicotinamide molecularly imprinted polymers with different porogens , 2005 .

[15]  G. Masci,et al.  Use of molecularly imprinted polymers in the solid-phase extraction of clenbuterol from animal feeds and biological matrices. , 2001, Journal of chromatography. B, Biomedical sciences and applications.

[16]  Börje Sellergren,et al.  Molecularly imprinted polymers : man-made mimics of antibodies and their applications in analytical chemistry , 2001 .

[17]  A. Molinelli,et al.  Towards the rational development of molecularly imprinted polymers: 1H NMR studies on hydrophobicity and ion-pair interactions as driving forces for selectivity. , 2005, Biosensors & bioelectronics.

[18]  D. Sherrington,et al.  A new molecularly imprinted polymer for the selective extraction of naproxen from urine samples by solid-phase extraction. , 2004, Journal of chromatography. B, Analytical technologies in the biomedical and life sciences.

[19]  Kenneth M. Merz,et al.  Study of hydrogen bonding interactions relevant to biomolecular structure and function , 1992 .

[20]  Yuanjian Deng,et al.  Capillary electrophoretic separation and theoretical study of inclusion complexes of sulfobutyl ether β‐cyclodextrin with estrogens , 2004 .

[21]  M. Hennion,et al.  Retention mechanism of analytes in the solid-phase extraction process using molecularly imprinted polymers. Application to the extraction of triazines from complex matrices. , 2004, Journal of chromatography. B, Analytical technologies in the biomedical and life sciences.

[22]  K. Haupt,et al.  Porogen formulations for obtaining molecularly imprinted polymers with optimized binding properties , 2005 .

[23]  C. Baggiani,et al.  Molecularly imprinted solid-phase extraction sorbent for the clean-up of chlorinated phenoxyacids from aqueous samples. , 2001, Journal of chromatography. A.

[24]  I. Nicholls,et al.  Probing the molecular basis for ligand-selective recognition in molecularly imprinted polymers selective for the local anaesthetic bupivacaine , 2001 .

[25]  M. Whitcombe,et al.  Predicting the selectivity of imprinted polymers , 1998 .

[26]  Klaus Mosbach,et al.  Highly enantioselective and substrate-selective polymers obtained by molecular imprinting utilizing noncovalent interactions. NMR and chromatographic studies on the nature of recognition , 1988 .

[27]  F. Deschamps,et al.  Simple NMR experiments as a means to predict the performance of an anti-17α-ethynylestradiol molecularly imprinted polymer , 2001 .

[28]  J. Stewart.  Optimization of parameters for semiempirical methods II. Applications , 1989 .

[29]  Sergey A. Piletsky,et al.  Recognition of ephedrine enantiomers by molecularly imprinted polymers designed using a computational approach , 2001 .

[30]  Sergey A. Piletsky,et al.  Polymer cookery: Influence of polymerization conditions on the performance of molecularly imprinted polymers , 2002 .