Enantiomeric recognition by molecularly imprinted polymers using hydrophobic interactions

Molecularly imprinted polymers prepared using acrylamide as the hydrogen bonding functional monomer exhibited good enantiomeric recognition properties in aqueous solutions. Our results indicate that the recognition improved with increased mobile phase water percentage and ionic strength, and was also very much pH dependent upon the ionisation properties of the sample molecules. The results can be interpreted in terms of specific hydrophobic interactions between the enantiomeric species and the recognition sites of imprinted polymers. A study of substrate selectivity showed differences between a pure organic system and a water/organic system as the mobile phases. The hydrophobicity of the test compounds was found to be an important parameter in determining the selectivity.

[1]  T. Shepodd,et al.  "Hydrophobic" binding of water-soluble guests by high-symmetry, chiral hosts. An electron-rich receptor site with a general affinity for quaternary ammonium compounds and electron-deficient .pi. systems , 1988 .

[2]  Hans-Jörg Schneider,et al.  Mechanisms of Molecular Recognition : Investigations of Organic Host–Guest Complexes , 1991 .

[3]  Michael J. Whitcombe,et al.  A NEW METHOD FOR THE INTRODUCTION OF RECOGNITION SITE FUNCTIONALITY INTO POLYMERS PREPARED BY MOLECULAR IMPRINTING : SYNTHESIS AND CHARACTERIZATION OF POLYMERIC RECEPTORS FOR CHOLESTEROL , 1995 .

[4]  Charles Tanford,et al.  The hydrophobic effect , 1980 .

[5]  K Mosbach,et al.  Sugar binding polymers showing high anomeric and epimeric discrimination obtained by noncovalent molecular imprinting. , 1994, Analytical biochemistry.

[6]  Klaus Mosbach,et al.  Drug assay using antibody mimics made by molecular imprinting , 1993, Nature.

[7]  K Mosbach,et al.  Molecularly imprinted polymer beads:  suspension polymerization using a liquid perfluorocarbon as the dispersing phase. , 1996, Analytical chemistry.

[8]  G. Wenz.  Cyclodextrins as Building Blocks for Supramolecular Structures and Functional Units , 1994 .

[9]  F. Arnold,et al.  Molecular imprinting: selective materials for separations, sensors and catalysis , 1995 .

[10]  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 .

[11]  K. Shea,et al.  Designed catalysts. A synthetic network polymer that catalyzes the dehydrofluorination of 4-fluoro-4-(p-nitrophenyl)butan-2-one , 1994 .

[12]  E. Frieden.  Non-covalent interactions. Keyto biological flexibility and specificity. , 1975, Journal of chemical education.

[13]  B. Sellergren,et al.  Chiral ion-exchange chromatography. Correlation between solute retention and a theoretical ion-exchange model using imprinted polymers. , 1993, Journal of chromatography. A.

[14]  J. Forman,et al.  CIRCULAR DICHROISM STUDIES OF MOLECULAR RECOGNITION WITH CYCLOPHANE HOSTS IN AQUEOUS MEDIA , 1995 .

[15]  Jean-Marie Lehn,et al.  Supramolecular Chemistry—Scope and Perspectives Molecules, Supermolecules, and Molecular Devices (Nobel Lecture) , 1988 .

[16]  K Mosbach,et al.  Mimics of the binding sites of opioid receptors obtained by molecular imprinting of enkephalin and morphine. , 1995, Proceedings of the National Academy of Sciences of the United States of America.

[17]  Donald J. Cram.  The Design of Molecular Hosts, Guests, and Their Complexes (Nobel Lecture)† , 1988 .

[18]  G. Wulff,et al.  Enzyme‐analogue built polymers, 29. The preparation of defined chiral cavities for the racemic resolution of free sugars , 1991 .

[19]  F. Diederich,et al.  Dissolution of Cholesterol in Water by a Synthetic Receptor , 1994 .

[20]  Frances H. Arnold,et al.  Synthetic Bis-Metal Ion Receptors for Bis-Imidazole "Protein Analogs" , 1994 .

[21]  K. Mosbach,et al.  Preparation of Ca2+ selective sorbents by molecular imprinting using polymerisable ionophores , 1991 .

[22]  J. Rebek.  Molecular recognition and biophysical organic chemistry , 1990 .

[23]  F. Diederich,et al.  Steroid complexation by cyclophane receptors in aqueous solution: Substrate selectivity, enthalpic driving force for cavity inclusion, and enthalpy-entropy compensation , 1995 .

[24]  Colin F. Poole,et al.  Contemporary Practice of Chromatography , 1984 .

[25]  Cameron Alexander,et al.  Bacteria-Mediated Lithography of Polymer Surfaces , 1996 .

[26]  J. Forman,et al.  Molecular recognition in aqueous media. New binding studies provide further insights into the cation-π interaction and related phenomena , 1993 .

[27]  S. Bystroem,et al.  Selective reduction of steroid 3- and 17-ketones using lithium aluminum hydride activated template polymers , 1993 .

[28]  Katsuhiko Ariga,et al.  Molecular Recognition of Nucleotides by the Guanidinium Unit at the Surface of Aqueous Micelles and Bilayers. A Comparison of Microscopic and Macroscopic Interfaces , 1996 .

[29]  R. Breslow,et al.  CHOLESTEROL RECOGNITION AND BINDING BY CYCLODEXTRIN DIMERS , 1996 .

[30]  G. Wulff.  Molecular Imprinting in Cross‐Linked Materials with the Aid of Molecular Templates— A Way towards Artificial Antibodies , 1995 .

[31]  K. Mosbach,et al.  Molecular imprinting of a transition state analogue leads to a polymer exhibiting esterolytic activity , 1989 .

[32]  L. Andersson,et al.  Application of molecular imprinting to the development of aqueous buffer and organic solvent based radioligand binding assays for (s)-propranolol. , 1996, Analytical chemistry.

[33]  K. Shea,et al.  Imprinted Polymer Membranes for the Selective Transport of Targeted Neutral Molecules , 1996 .

[34]  L. Fischer,et al.  Direct enantioseparation of .beta.-adrenergic blockers using a chiral stationary phase prepared by molecular imprinting , 1991 .

[35]  Olof Ramström,et al.  The Emerging Technique of Molecular Imprinting and Its Future Impact on Biotechnology , 1996, Bio/Technology.

[36]  M. Kempe.  Antibody-mimicking polymers as chiral stationary phases in HPLC. , 1996, Analytical chemistry.

[37]  Charles J. Pedersen,et al.  The Discovery of Crown Ethers (Noble Lecture) , 1988 .