Molecular Recognition Study of a Supramolecular System

Abstract The competitive inclusion method was used to determine the stability constants (log K a ) for complexation of natural α-cyclodextrin ( 1 ) with aliphatic amino acids in acidic solution. The stability constants (log K a ) for the complexation of modified α-cyclodextrin, mono- [6-(1-pyridinio)-6-deoxy]-α-cyclodextrin ( 2 ), with these biological molecules were measured using the differential spectra method. Both natural α-cyclodextrin ( 1 ) and chemically modified α-cyclodextrin ( 2 ) can recognize not only the size of guest amino acid molecules and the length of their hydrophobic side chains, but also the chirality of enantiotopic L / D -amino acids. The longer the hydrophobic side chain borne on an amino acid, the more stable the complex formed by α-cyclodextrin hosts ( 1 ) and ( 2 ). Host compounds ( 1 ) and ( 2 ) preferably include L -amino acids, which would benefit from discrimination of L / D -amino acids. Introduction of a positively charged 1-pyridinio moiety to C-6 of α-cyclodextrin apparently enlarges the inclusion ability and enantioselectivity by electrostatic interaction. Comparing the data obtained in acidic medium with those formerly measured in pH 7.20 phosphate buffer solution, a result can be given: when the pH of the medium increases, the complexation ability and selectivity of modified α-cyclodextrin ( 2 ) for most amino acids examined here are slightly enhanced, showing the highest enantioselectivity up to 10.3 for L / D -serine.

[1]  H. Ikeda,et al.  Fluorescent cyclodextrins for molecule sensing: Fluorescent properties, NMR characterization, and inclusion phenomena of N-dansylleucine-modified cyclodextrins , 1996 .

[2]  T. I. Richardson,et al.  Complexes of Lysine, Histidine, and Arginine with Sulfonated Azo Dyes: Model Systems for Understanding the Biomolecular Recognition of Glycosaminoglycans by Proteins , 1996 .

[3]  Baizhan Li,et al.  MOLECULAR RECOGNITION STUDY ON SUPRAMOLECULAR SYSTEM. (III): CHIRAL RECOGNITION OF AROMATIC AMINO ACIDS BY BINUCLEAR CU(II) COMPLEXES WITH CYCLODEXTRI NS , 1996 .

[4]  J. Hasegawa,et al.  Chiral Amino Acid Recognition by a Porphyrin-Based Artificial Receptor , 1995 .

[5]  Robert N. Goldberg,et al.  Thermodynamic and Nuclear Magnetic Resonance Study of the Interactions of .alpha.- and .beta.-Cyclodextrin with Model Substances: Phenethylamine, Ephedrines, and Related Substances , 1995 .

[6]  J. F. Stoddart,et al.  SUPPORTED MONOLAYERS CONTAINING PREFORMED BINDING SITES. SYNTHESIS AND INTERFACIAL BINDING PROPERTIES OF A THIOLATED BETA -CYCLODEXTRIN DERIVATIVE , 1995 .

[7]  R. Goldberg,et al.  A Thermodynamic Study of the Reactions of Cyclodextrins with Primary and Secondary Aliphatic Alcohols, with D- and L-Phenylalanine, and with L-Phenylalanine Amide , 1994 .

[8]  A. Eliseev,et al.  Molecular Recognition of Nucleotides, Nucleosides, and Sugars by Aminocyclodextrins , 1994 .

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

[10]  R. Goldberg,et al.  Thermodynamic and NMR Study of the Interactions of Cyclodextrins with Cyclohexane Derivatives , 1994 .

[11]  Yoshihisa Inoue,et al.  Calorimetric titration of inclusion complexation with modified .beta.-cyclodextrins. Enthalpy-entropy compensation in host-guest complexation: from ionophore to cyclodextrin and cyclophane , 1993 .

[12]  Yoshihisa Inoue,et al.  Thermodynamics of molecular recognition by cyclodextrins. 1. Calorimetric titration of inclusion complexation of naphthalenesulfonates with .alpha.-, .beta.-, and .gamma.-cyclodextrins: enthalpy-entropy compensation , 1993 .

[13]  M. Tanaka,et al.  Chiral recognition and enantiomeric separation of alanine β-naphthylamide by cyclodextrins , 1992 .

[14]  William C. Purdy,et al.  Cyclodextrins and Their Applications in Analytical Chemistry , 1992 .

[15]  F. Toda,et al.  Inclusion of Azulene and Alcohol by β-Cyclodextrin in Aqueous Solution , 1992 .

[16]  K. Lipkowitz,et al.  Enantioselective binding of tryptophan by .alpha.-cyclodextrin , 1992 .

[17]  H. Schneider,et al.  Host guest chemistry. 26. NMR and fluorescence studies of cyclodextrin complexes with guest molecules containing both phenyl and naphthyl units , 1991 .

[18]  D. F. Lewis,et al.  Host properties of cyclodextrins towards anion constituents of antigenic determinants. A thermodynamic study in water and in N,N-dimethylformamide , 1990 .

[19]  D. Kristol,et al.  Cyclodextrin inclusion complexes: studies of the variation in the size of alicyclic guests , 1989 .

[20]  F. Bright,et al.  Thermodynamic study on the effects of beta-cyclodextrin inclusion with anilinonaphthalenesulfonates. , 1989, Analytical chemistry.

[21]  Y. Matsui,et al.  1H NMR study of the regioisomers of primary O-di- and trisubstituted α-cyclodextrins , 1988 .

[22]  Tadashi Mizutani,et al.  Artificial receptors for amino acids in water. Local environmental effect on polar recognition by 6A-amino-6B-carboxy- and 6B-amino-6A-carboxy-.beta.-cyclodextrins , 1986 .

[23]  K. A. Connors,et al.  Complex formation between alpha-cyclodextrin and 4-substituted phenols studied by potentiometric and competitive spectrophotometric methods. , 1983, Journal of pharmaceutical sciences.

[24]  M. Eftink,et al.  Calorimetric studies of p-nitrophenol binding to α- and β-cyclodextrin , 1981 .

[25]  Wolfram Saenger,et al.  Cyclodextrin Inclusion Compounds in Research and Industry , 1980 .

[26]  Y. Matsui,et al.  Binding forces contributing to the association of cyclodextrin with alcohol in an aqueous solution. , 1979 .

[27]  Y. Matsui,et al.  The Binding and Catalytic Properties of a Positively Charged Cyclodextrin , 1978 .

[28]  J. Behr,et al.  Transport of amino acids through organic liquid membranes. , 1973, Journal of the American Chemical Society.

[29]  Joel H. Hildebrand,et al.  A Spectrophotometric Investigation of the Interaction of Iodine with Aromatic Hydrocarbons , 1949 .