CONFORMATIONAL ENANTIOMERISM OF BILIRUBIN AND PAMOIC ACID INDUCED BY PROTONATED AMINOCYCLODEXTRINS

The conformational enantiomerism of (4Z, 15Z)-bilirubin IXα(1) induced by protonated heptakis(6-amino-6-deoxy)-β-cyclodextrin (amino-β-CDX) has been studied in aqueous media by means of CD spectroscopy. A bisignate CD Cotton effect suggests that the dianion of 1 associated with protonated amino-β-CDX selectively takes a conformation with (P)-helicity. The results clearly indicate that the electrostatic binding between the CO2– groups of 1 and the NH3+ groups of amino-β-CDX and the simultaneous inclusion of a dipyrrinone moiety of 1 into the chiral CDX cavity are essential for the conformational enantiomerism of 1. This has also been applied to the amino-γ-CDX-induced conformational enantiomerism of pamoic acid.

[1]  J. Nowick,et al.  Molecular Recognition between Uncharged Molecules in Aqueous Micelles. , 1994, Journal of the American Chemical Society.

[2]  J. Nowick,et al.  Molecular recognition in micelles: the roles of hydrogen bonding and hydrophobicity in adenine-thymine base-pairing in SDS micelles , 1993 .

[3]  M. Komiyama.  .alpha.-Cyclodextrin-catalyzed regioselective phosphorus-oxygen(2') cleavages of 2',3'-cyclic monophosphates of ribonucleosides , 1989 .

[4]  J. Gawroński,et al.  Complementarity and chiral recognition enantioselective complexation of bilirubin , 1987 .

[5]  Yuan Cheng,et al.  Hydrogen Bonding in Micelle Formation , 1994 .

[6]  J. Snir,et al.  Optical properties of bilirubin-serum albumin complexes in aqueous solution. I. Dependence on pH. , 1972, Biochimica et biophysica acta.

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

[8]  W. Saenger,et al.  Inclusion Compounds. XIX.1a The Formation of Inclusion Compounds of α-Cyclodextrin in Aqueous Solutions. Thermodynamics and Kinetics , 1967 .

[9]  T. Schiestel,et al.  Host-guest supramolecular chemistry. 34. The incremental approach to noncovalent interactions: coulomb and van der Waals effects in organic ion pairs , 1992 .

[10]  F. Cramer,et al.  Molecular recognition by energy dissipation, a new enzymatic principle: the example isoleucine-valine , 1987 .

[11]  D. Armstrong,et al.  Liquid chromatographic separation of enantiomers using a chiral .beta.-cyclodextrin-bonded stationary phase and conventional aqueous-organic mobile phases , 1985 .

[12]  F. Cramer,et al.  Über Einschlußverbindungen, XV. Spaltung von Racematen mit Cyclodextrinen , 1959 .

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

[14]  R. Petter,et al.  Cooperative binding by aggregated mono-6-(alkylamino)-.beta.-cyclodextrins , 1990 .

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

[16]  A. Coleman,et al.  Self-assembling systems of the amphiphilic cationic per-6-amino-.beta.-cyclodextrin 2,3-di-O-alkyl ethers , 1992 .

[17]  M. Hyun,et al.  A rational approach to the design of highly effective chiral stationary phases for the liquid chromatographic separation of enantiomers. , 1984, Journal of pharmaceutical and biomedical analysis.

[18]  M. Sisido,et al.  A chiral pyrene excimer in .gamma.-cyclodextrin cavity , 1985 .

[19]  A. Eliseev,et al.  Aminocyclodextrins as Selective Hosts with Several Binding Sites for Nucleotides , 1993 .

[20]  T. Tomita,et al.  Design and Synthesis of a Trifunctional Chiral Porphyrin with C2 Symmetry as a Chiral Recognition Host for Amino Acid Esters , 1994 .

[21]  E. Anslyn,et al.  Complexation of Phosphoric Acid Diesters with Polyaza-Clefts in Chloroform: Effects of Phosphodiester Dimerization, Changing Cavity Size, and Preorganizing Amine Recognition Units , 1994 .

[22]  K. Tsujihara,et al.  The Highly Selective Sulfonylation of Cycloheptaamylose and Syntheses of Its Pure Amino Derivatives , 1977 .

[23]  M. H. Zhang,et al.  Understanding bilirubin conformation and binding. Circular dichroism of human serum albumin complexes with bilirubin and its esters. , 1988, The Journal of biological chemistry.

[24]  F. Reniero,et al.  Asymmetric reductions by sodium borohydride of ketone-.beta.-cyclodextrin complexes , 1985 .

[25]  H. Schneider,et al.  Complexation of nucleosides, nucleotides, and analogs in an azoniacyclophane. Van der Waals and electrostatic binding increments and NMR shielding effects , 1992 .

[26]  Kazunori Yamamoto,et al.  Hydrophobic hydration and hydrophobic interaction of carboxylic acids in aqueous solution: mass spectrometric analysis of liquid fragments isolated as clusters , 1990 .

[27]  Hiroshi M Yamamoto,et al.  Polyaminocyclodextrins as remarkably active catalysts for the decarboxylation of oxalacetate , 1990 .

[28]  G. Whitesides,et al.  Structural Preferences of Hydrogen-Bonded Networks in Organic Solution - the Cyclic CA3.cntdot.M3 "Rosette" , 1994 .

[29]  E. Fischer.  Einfluss der Configuration auf die Wirkung der Enzyme , 1894 .

[30]  A. Chamberlin,et al.  Enantioselective and Diastereoselective Molecular Recognition of Cyclic Dipeptides by a C2 Macrolactam Host , 1994 .

[31]  J. Nowick,et al.  Molecular recognition in aqueous micellar solution: adenine-thymine base-pairing in SDS micelles , 1992 .

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

[33]  J. Rebek,et al.  Convergent Functional Groups. 15. Synthetic and Structural Studies of Large and Rigid Molecular Clefts , 1994 .

[34]  Y. Yoshimura,et al.  Binding sites of pyrene and related compounds and chiral excimer formation in the cavities of cyclodextrins and branched cyclodextrins , 1988 .

[35]  D. Armstrong,et al.  Theoretical considerations concerning the separation of enantiomeric solutes by liquid chromatography. , 1988, Analytical chemistry.

[36]  J. Ostrow,et al.  Ionization and self-association of unconjugated bilirubin, determined by rapid solvent partition from chloroform, with further studies of bilirubin solubility. , 1992, Journal of lipid research.

[37]  J. Lehn,et al.  Cyclodextrin chemistry. Selective modification of all primary hydroxyl groups of α- and β-cyclodextrins , 1978 .

[38]  W. C. Purdy,et al.  Circular dichroism, ultraviolet, and proton nuclear magnetic resonance spectroscopic studies of the chiral recognition mechanism of .beta.-cyclodextrin , 1992 .

[39]  Susan E. Brown,et al.  Substituent effects and chiral discrimination in the complexation of benzoic, 4-methylbenzoic and (RS)-2-phenylpropanoic acids and their conjugate bases by β-cyclodextrin and 6A-amino-6A-deoxy-β-cyclodextrin in aqueous solution: potentiometric titration and 1H nuclear magnetic resonance spectroscopi , 1993 .

[40]  J. An,et al.  Circular dichroism of bilirubin-amine heteroassociation complexes , 1987 .

[41]  J. Lehn,et al.  Chiral recognition of aromatic carboxylate anions by an optically active abiotic receptor containing a rigid guanidinium binding subunit , 1989 .