Effect of cyclodextrins on saccharide sensing function of a fluorescent phenylboronic acid in water.

An inclusion complex consisting of a fluorescent phenylboronic acid (C1-APB) and beta-cyclodextrin (beta-CD) acts as a supramolecular saccharide sensor whose response mechanism is based on photoinduced electron transfer (PET). This study evaluated four kinds of cyclodextrins (alpha-CD, beta-CD, gamma-CD, and NH(2)-beta-CD) by comparing their pH profiles, and confirmed that beta-CD was the best host for C1-APB because the C1-APB/beta-CD complex exhibited high affinity for saccharides as well as high fluorescent recovery upon saccharide binding. An investigation of the beta-CD concentration effect revealed the formation of a 1:1 inclusion complex of C1-APB with beta-CD. The observed saccharide selectivity of the C1-APB/beta-CD complex is in the following order: D-fructose (4039 +/- 69 M(-1)) > D-ribose (1083 +/- 26 M(-1)) > L-arabinose (474 +/- 11 M(-1)) > D-galactose (318 +/- 3 M(-1)) > maltotoriose (135 +/- 5 M(-1)) > D-glucose (114 +/- 2 M(-1)) > maltose (81 +/- 2 M(-1)). In addition to monomer emission, dimer emission from pyrene dimers was observed in the spectra for the C1-APB/gamma-CD complex, which allowed a ratiometric analysis. This study shows that the combination of a simple fluorescent probe, C1-APB, with various CDs diversifies the response systems for saccharide recognition.     

A spectroscopic study of the inclusion of azulene by beta- and gamma-cyclodextrins

The inclusion of azulene (AZ) inside the cavities of beta-cyclodextrin (beta-CD) and gamma-cyclodextrin (gamma-CD) was studied using absorption, fluorescence and induced-circular dichroism spectroscopy. The inclusion of AZ into the cavity of beta-CD has a stoichiometry of 1:1, whereas that of AZ/gamma-CD complex is 1:2. The equilibrium constants for the formation of the two complexes were calculated to be 780+/-150 M(-1) for AZ:beta-CD and (4.5+/-0.86)x10(5) M(-2) for AZ:(gamma-CD)(2). The latter is due to a stepwise equilibrium mechanism in which a 1:1 complex is formed with a binding constant of 775 M(-1), followed by the formation of a 1:2 complex with a binding constant of 580 M(-1). The difference between the two binding constant values is slight, indicating an almost equal contribution from each of the gamma-CD molecules to the overall binding in AZ:(gamma-CD)(2). From the induced-circular dichroism spectra, the inclusion of AZ was found to be axial in AZ:beta-CD and nearly axial in AZ:(gamma-CD)(2).     

Thermodynamic study on the effects of beta-cyclodextrin inclusion with berberine.

The fluorescence enhancement of berberine (Berb) as a result of complex with beta-cyclodextrin (beta-CD) is investigated. The association constants of alpha-CD and beta-CD with Berb are 60 and 137 M(-1) at 20 degrees C in pH 7.20 aqueous solution. Effects of temperature on the forming inclusion complexes of beta-CD with Berb have been examined through using fluorescence titration. Enthalpy and entropy values calculated from fluorescence data are -33.7 kJ mol(-1) and 74.3 J x mol(-1) K(-1) respectively. It was found that the dielectric constant of beta-CD cavity is about 24 in a rough analogy with absolute alcohol. These results suggest that the extrusion of 'high energy water' molecules from the cavity of beta-CD and hydrophobic interaction upon the inclusion complex formation are the main forces of the inclusion reaction. Effect of pH on the association of beta-CD with Berb was also studied. Mechanism of the inclusion of beta-CD with Berb is further studied by absorption and NMR measurements. Results show that beta-CD forms a 1:1 inclusion complex with Berb.     

Novel behavior of O-methylated beta-cyclodextrins in inclusion of meso-tetraarylporphyrins

[structure: see text] The mechanism for formation of extremely stable 1:2 inclusion complexes of water-soluble meso-tetraarylporphyrins with heptakis(2,3,6-tri-O-methyl)-beta-cyclodextrin (TMe-beta-CD) in aqueous solutions has been studied by means of NMR spectroscopy and isothermal titration calorimetry. To simplify the system, 5,10,15-tris(3,5-dicarboxylatophenyl)-20-phenylporphyrin (1) was used as a guest porphyrin, because 1 forms only a 1:1 inclusion complex with cyclodextrin (CD). As host compounds, native beta-CD and the O-methylated-beta-CDs such as heptakis(2,3-di-O-methyl)- (2,3-DMe-beta-CD), heptakis(2,6-di-O-methyl)- (2,6-DMe-beta-CD), and TMe-beta-CDs were used. The thermodynamic parameters for complexation such as binding constants (K) and enthalpy (DeltaH degrees ) and entoropy changes (DeltaS degrees ) were determined by means of isothermal titration calorimetry. The K value for complexation of 1 with CD increases in the order beta-CD (K = (1.2 +/- 0.1) x 10(3) M(-)(1)) < 2,6-DMe-beta-CD ((1.2 +/- 0.1) x 10(4) M(-)(1)) < TMe-beta-CD ((6.9 +/- 0.4) x 10(6) M(-)(1)) < 2,3-DMe-beta-CD ((8.5 +/- 0.5) x 10(6) M(-)(1)), indicating participation of the secondary OCH(3) groups in extremely strong complexation of 1 with CD. Complex formation of 1 with beta-CD and 2,6-DMe-beta-CD is an enthalpically and entropically favorable process, while that with TMe-beta-CD and 2,3-DMe-beta-CD is an enthalpically much more favorable but an entropically less favorable process. The thermodynamic parameters suggest that inclusion of 1 into the cavities of TMe-beta-CD and 2,3-DMe-beta-CD is promoted by van der Waals interactions, which are stronger than those in the cases of beta-CD and 2,6-DMe-beta-CD. (13)C NMR spectra show that the conformations of both TMe-beta-CD and 2,3-DMe-beta-CD are altered upon inclusion of 1, while those of beta-CD and 2,6-DMe-beta-CD are mostly retained. On the basis of these results, it can be concluded that induced-fit type complexation of 1 with TMe-beta-CD and 2,3-DMe-beta-CD causes extremely strong binding of the host to the guest.     

Spectroscopic study of orange G-beta-cyclodextrin complex and its analytical application

The mechanism of the inclusion of orange G and beta-cyclodextrin (beta-CD) has been studied by using both spectrophotometry and infrared spectroscopy. Effects of the pH, concentrations of beta-CD, and ionic strength on the inclusion complex of beta-CD and orange G were examined. The result showed that orange G reacts with beta-CD to form a 1:1 host-guest complex with an apparent formation constant of 3.03 x 10(3)mol(-1)l. The thermodynamic parameters of inclusion complex, DeltaG(0), DeltaH(0), and DeltaS(0) were obtained. Based on the enhancement of the absorbance of orange G produced through complex formation, a ratiometric method spectrophotometrically for the determination of orange G in bulk aqueous solution in the presence of beta-CD was developed, which overcome the effect of condition change on the determination of orange G. The linear relationship between the absorbance and orange G concentration was obtained in the range of 1.0 x 10(-5) to 4.0 x 10(-5)mol l(-1), with a correlation coefficient of 0.9998. The detection limit was 3.6 x 10(-6)mol l(-1). The principal advantage of the proposed method is high accuracy because ratiometry was used in measurement.     

Comparative study on the inclusion behavior between meso-tetrakis(4-N-ethylpyridiniurmyl)porphyrin and beta-cyclodextrin derivatives

5,10,15,20-Tetrakis(4-N-ethylpyridiniurmyl)porphyrin (TEPyP) formed 1:1 stoichiometry inclusion complexes with beta-cyclodextrin (beta-CD) and its derivatives including hydroxypropyl-beta-cyclodextrin (HP-beta-CD), sulfobutylether-beta-cyclodextrin (SBE-beta-CD) in basic aqueous solution. The supramolecular system was investigated by the methods of fluorescence, UV-vis absorption spectroscopy, nuclear magnetic resonance (NMR) technique. The inclusion ability of cyclodextrins exhibited remarkable difference for beta-CD, HP-beta-CD and SBE-beta-CD. Association constants as high as K=1.1 x 10(4) M(-1) in the case of HP-beta-CD/TEPyP and 2.0 x 10(5) M(-1) in the case of SBE-beta-CD/TEPyP complexes were determined, whereas a lower value (K=550 M(-1)) was given in the case of beta-CD/TEPyP. The results showed that hydrogen bonding and charge attraction play important roles in the processes of host-guest interaction. The interaction mechanism of inclusion processes could be explained by the analysis of NMR spectroscopy. The supramolecular assembly was formed. beta-CD and HP-beta-CD approached from the primary face of cavities of CDs.     

Molecular recognition thermodynamics and structural elucidation of interactions between steroids and bridged bis(beta-cyclodextrin)s

A series of bridged bis(beta-cyclodextrin(CD))s (2-7) were synthesized, i.e., bridged bis(beta-CD)s 2 and 3 bearing binaphthyl or biquinoline tethers and bridged bis(beta-CD)s 4-7 possessing dithiobis(benzoyl) tether, and their complex stability constants (KS), enthalpy (DeltaH degrees), and entropy changes (DeltaS degrees) for the 1:2 inclusion complexation with representative steroids, deoxycholate, cholate, glycocholate, and taurocholate, have been determined in an aqueous phosphate buffer solution of pH 7.20 at 298.15 K by means of titration microcalorimetry. The original conformations of bridged bis(beta-cyclodextrin)s were investigated by circular dichroism and 1H ROESY spectroscopy. Structures of the inclusion complexes between steroids and bridged bis(beta-CD)s in solution were elucidated by 2D NMR experiments, indicating that anionic groups of two steroid molecules penetrate, respectively, into the two hydrophobic CD cavities in one 6,6'-bridged bis(beta-CD) molecule from the secondary rim to give a 1:2 binding mode upon inclusion complexation. The results obtained from titration microcalorimetry and 2D NMR experiments jointly demonstrate that bridged bis(beta-CD)s 2, 3 and 5-7 tethered by protonated amino group possessing different substituted groups can enhance not only the molecular binding ability toward steroids by electrostatic interaction but also molecular selectivity. Thermodynamically, the resulting 1:2 bis(beta-CD)-steroid complexes are formed by an enthalpy-driven process, accompanied by smaller entropy loss. The increased complex stability mainly results from enthalpy gain, accompanied by large conformational change and extensive desolvation effects for the 1:2 inclusion complexation between bis(beta-CD)s and steroids.     

An effective metallohydrolase model with a supramolecular environment: structures, properties, and activities

A supramolecular inclusion complex, [Zn(L1)(H2O)2(beta-CD)](ClO4)2.9.5 H2O (1) was synthesized and characterized structurally and its first-order active species for hydrolysis of esters, [Zn(L1)(H2O)(OH)(beta-CD)](ClO4) (2), was isolated (L1=4-(4'-tert-butylbenzyl)diethylenetriamine; beta-CD=beta-cyclodextrin). The apparent inclusion stability constant of the host and the guest measured in aqueous solution was (5.91+/-0.03)x10(3) for 1. The measured values of the first- and second-order pK(a) values of coordinated water molecules were 8.20+/-0.08 and 10.44+/-0.08, respectively, and were assigned to water molecules occupying the plane and remaining axial positions in a distorted trigonal bipyramid of the [Zn(L1)(H2O)2(beta-CD)]2+ sphere according to the structural analysis of [Zn(L2)(H2O)}2(mu-OH)](ClO4)3 (3) (L2=4-benzyldiethylenetriamine). p-Nitrophenyl acetate (pNA) hydrolysis catalyzed by 1 at pH 7.5-9.1 and 25.0+/-0.1 degrees C exhibited a first-order reaction with various concentrations of pNA and 1, but the pH profile did not indicate saturated kinetic behavior. Second-order rate constants of 0.59 and 24.0 M(-1) s(-1) were calculated for [Zn(L1)(H2O)(OH)(beta-CD)]+ and [Zn(L1)(OH)2(beta-CD)], respectively; the latter exhibited a potent catalytic activity relative to the reported mononuclear and polynuclear Zn(II) species.     

Improved syntheses of bis(beta-cyclodextrin) derivatives, new carriers for gadolinium complexes

In the last decade a number of reports have been published on the synthesis and characterization of bridged cyclodextrin dimers (bis-CDs) connected with linkers of different lengths and structures. These dimers, having two hydrophobic cavities in close proximity, display much higher binding affinities and molecular selectivities than parent CDs, forming stable supramolecular adducts. We describe new synthetic protocols for the preparation of bis(beta-CDs) bearing 2-2', 3-3' and 6-6' bridges. Some of the critical steps were carried out either under high-intensity ultrasound (US) or microwave (MW) irradiation. Bis(beta-CDs) containing 6-6' ureido- and thioureido-bridges were prepared in high yields by a MW-promoted aza-Wittig reaction using polymer-bound triphenylphosphine, while those containing 2,2' and 3,3' bridges were prepared from mono-alkenyl beta-CDs by the cross-metathesis reaction (homodimerization) in the presence of 2(nd)-generation Grubbs catalyst under sonochemical conditions. By these improved protocols CD dimers could be obtained in gram amounts to prepare stable adducts of bis-CDs with contrast agents (CAs) containing gadolinium(iii) chelates. In the case of Gd(iii) chleate "G-1" the inclusion complexes were found to be 2 to 3 orders of magnitude more stable than that formed by beta-CD (K(ass) = 4.3 x 10(4) M(-1)vs 8.0 x 10(2) M(-1)). Relaxivity increased as well by factors of 3 and 4, viz. from 9.1 mM(-1) s(-1) (beta-CD) to 27.7 and 35 mM(-1) s(-1).     

Heterodimerization of dye-modified cyclodextrins with native cyclodextrins

The heterodimerization behavior of dye-modified beta-cyclodextrins (1-6) with native cyclodextrins (CDs) was investigated by means of absorption and induced circular dichroism spectroscopy in an aqueous solution. Three types of azo dye-modified beta-CDs (1-3) show different association behaviors, depending on the positional difference and the electronic character of substituent connected to the CD unit in the dye moiety. p-Methyl red-modified beta-CD (1), which has a 4-(dimethylamino)azobenzene moiety connected to the CD unit at the 4' position by an amido linkage, forms an intramolecular self-complex, inserting the dye moiety in its beta-CD cavity. It also associates with the native alpha-CD by inserting the moiety of 1 into the alpha-CD cavity. The association constants for such heterodimerization are 198 M(-1) at pH 1.00 and 305 M(-1) at pH 6.59, which are larger than the association constant of 1 for beta-CD (43 M(-1) at pH 1.00). Methyl red-modified 2, which has the same dye moiety as that for 1 although its substituent position is different from that of 1, does not associate even with alpha-CD due to the stable self-intramolecular complex, in which the dye moiety is deeply included in its own cavity of beta-CD. Alizarin yellow-modified CD (3), which has an azo dye moiety different from that of 1 and 2, caused a slight spectral variation upon addition of alpha-CD, suggesting that the interaction between 3 and alpha-CD is weak. On the other hand, phenolphthalein-modified beta-CD (4), which forms an intermolecular association complex in its higher concentrations, binds with beta-CD with an association constant of 787 M(-1) at pH 10.80, where 4 exists as the dianion monomer in the absence of beta-CD. p-Nitorophenol-modified beta-CDs (5 and 6), each having p-nitorophenol moieties with a different connecting part with an amido and amidophenyl group, respectively, associated with alpha-CD with association constants of 66 and 16 M(-1) for 5 and 6, respectively. The phenyl unit in the connecting part of 6 may prevent the smooth binding with alpha-CD. All these results suggest that the dye-modified CDs, in which the dye part is not tightly included in its CD cavity, associate with the native CD to form heterodimer composed of two different CD units by inserting the dye moiety into the native CD unit. The resulting heterodimers have a cavity that can bind another appending moiety of host molecules. On this basis, more ordered molecular arrays or the supramolecular hereropolymers can be constructed.     

Spectrofluorimetric study of the beta-cyclodextrin:vitamin K3 complex and determination of vitamin K3

Vitamin K(3) (menadione) is an oil-soluble vitamin and not naturally fluorescent but yields fluorescence when it is reduced. However, it is possible to yield a fluorescent derivative in the region of 407 nm in aqueous medium when complexed to beta-cyclodextrin (CD). A 1:1 stoichiometric ratio and a formation constant of 373+/-34 l mol(-1) were obtained for the binary inclusion complex between menadione and beta-CD. The measurements were performed at pH 6.2 adjusted by adding 0.1 mol l(-1) citrate buffer solution and 6.4 x 10(-3) mol l(-1) of beta-CD concentration. The calibration graph was linear over the range 0.1-2.0 mg l(-1) with a repeatability of 2.2%; the detection limit was 0.022 mg l(-1) and the limit of quantification limit was 0.073 mg l(-1). The procedure was applied to pharmaceutical formulations.     

Study on the inclusion behavior between meso-tetrakis[4-(3-pyridiniumpropoxy)phenyl]prophyrin tetrakisbromide and beta-cyclodextrin derivatives in aqueous solution

The interaction of a cationic water-soluble porphyrin, 5,10,15,20-tetrakis[4-(3-pyridiniumpropoxy)phenyl]prophyrin tetrakisbromide (TPPOC3Py), with beta-CD and HP-beta-CD in aqueous solution has been studied by UV-vis, 1H NMR, 2D-NOESY and MALDI-TOF MS, and it reveals that a stable 1:1 inclusion complex between TPPOC3Py and HP-beta-CD or beta-CD has formed, in which one of the meso substituents of porphyrin ring has deeply penetrated through the cavity of HP-beta-CD from secondary face. The inclusion constants of the complexes of TPPOC3Py-beta-CD and TPPOC3Py-HP-beta-CD are (1.6+/-0.2)x10(3) M-1 and (8.9+/-0.4)x10(4) M-1, respectively.     

Study on the supramolecular multirecognition mechanism of beta-naphthol/beta-cyclodextrin/anionic surfactant in a tolnaftate hydrolysis system

Based on the fact that tolnaftate degrade to beta-naphthol sodium (RONa) at 5.00 mol/L NaOH solution and RO(-) was protonated to ROH after being acidified and adjusted to the pH 4.50 by acetic acid-sodium acetate buffer solution, we studied and discussed the mechanism of the supramolecular multirecognition interaction among the anionic surfactants sodium lauryl sulfate (SLS), beta-cyclodextrin (beta-CD), and beta-naphthol (ROH) by means of fluorescence spectrum, surface tension of the solution, infrared spectrograms, and (1)HNMR spectroscopy. The apparent formation constant of the ternary inclusion complex was determined to be (5.48 +/- 0.13) x 10(3) L(2)/mol(2). The thermodynamic parameters (DeltaG degrees, DeltaH degrees, DeltaS degrees ) for the formation of the inclusion complexes were obtained from the van't Hoff equation. It was indicated that the multiple and synergistic protection effect of SLS and beta-CD on the excited singlet state ROH played very important roles in the enhancement of the fluorescence of ROH. Results showed that, at room temperature, the naphthalene ring of ROH and the hydrophobic hydrocarbon chain of SLS were included into the cavity of beta-CD to form a ROH/SLS/beta-CD ternary inclusion complex with stoichiometry of 1:1:1, which provided effective protection for the excited state of ROH and increased the fluorescent intensity of ROH obviously.     

Spectral properties and inclusion of 3-(4'-dimethylaminophenyl)-1-(2-furanyl)prop-2-en-1-one in organized media of micellar solutions, beta-cyclodextrin and viscous medium

On the line of a previous work on the spectral properties of some of heteroaryl chalcone, the absorption and fluorescence emission spectral properties of 3-(4'-dimethylaminophenyl)-1-(2-furanyl)prop-2-en-1-one (DMAFP), have been investigated in organized media of aqueous micellar and beta-cyclodextrin (beta-CD) solutions. While the absorption spectra are less sensitive to the nature of the added surfactant or beta-CD, the characteristics of the intramolecular charge transfer (ICT) fluorescence are highly sensitive to the properties of the medium. The ICT maximum is strongly blue-shifted with a great enhancement in the fluorescence quantum yield on adding micellar or beta-CD. This indicates the solubilization of DMAFP in the micellar core and formation of an inclusion complex with beta-CD. The critical micelle concentrations (CMC) as well as the polarity of the micellar core of SDS, CTAB and TX-100 have been determined. The CMC values are in good agreement with the reported values while the polarity is lower indicating that DMAFP molecules are incorporated in the micellar core not at the micellar interface. The inclusion constants of binding of DMAFP in micellar or beta-CD have been also determined. The thermodynamic parameters of formation of DMAFP:CD inclusion complex have been calculated from the temperature dependence of the fluorescence spectra of the formed complex. The highly negative value of formation entropy (DeltaS=-98.0Jmol(-1)K(-1)) reflects the high restrictions imposed on the movement of both the host and included guest molecules which is consistent with the increase of the fluorescence yield and blue shift of the fluorescence maximum.     

Inclusion complexes of Fe(III) tetrakis(4-sulfonatophenyl)porphyrin with cyclodextrins in aqueous solutions

In aqueous solutions, inclusion complexation of Fe(III) tetrakis(4-sulfonatophenyl)porphyrin (FeTSPP) with alpha-cyclodextrin (alpha-CD), beta-CD, gamma-CD, and heptakis(2,3,6-tri-O-methyl)-beta-CD (TM-beta-CD) has been examined by means of absorption and induced circular dichroism spectroscopy. FeTSPP has been found to form inclusion complexes with beta-CD, gamma-CD, and TM-beta-CD in pH 3.2 buffers. At pH 10.1, where FeTSPP self-associates to form an oxo-bridged dimer, FeTSPP also forms inclusion complexes with alpha-CD, beta-CD, gamma-CD, and TM-beta-CD. The stoichiometries of the CD-FeTSPP inclusion complexes are 1:1, except for TM-beta-CD in pH 10.1 buffers where its 1:1 inclusion complex associates with TM-beta-CD to form a 2:1 inclusion complex at high TM-beta-CD concentrations. Equilibrium constants of FeTSPP for the formation of the 1:1 inclusion complexes have been evaluated for beta-CD, gamma-CD, and TM-beta-CD. Induced circular dichroism spectra of FeTSPP in alpha-CD and beta-CD solutions exhibit a signal pattern (a negative sign) that is different from those in acidic and basic solutions containing gamma-CD and that in basic solution containing TM-beta-CD, suggesting different inclusion modes towards FeTSPP.     

Spectrofluorimetric study of the beta-cyclodextrin-ibuprofen complex and determination of ibuprofen in pharmaceutical preparations and serum

The inclusion complexation of ibuprofen in beta-cyclodextrin (beta-CD) has been examined by means of spectrofluorimetry at both acid and alkaline pH. The results suggest that stable 1:1 complexes are formed in both media. The analysis of the pK(a) values for ibuprofen in both the absence and presence of beta-CD (4.12 and 4.66, respectively) suggests that in the inclusion complex the carboxylic group is located outside the cyclodextrin (CD) but interacting with it. Further structural characterization of the complex was carried out by means of am1 semiempiral calculations. Based on the obtained results, a spectrofluorimetric method for the determination of ibuprofen in the presence of beta-CD at 10 degrees C was developed in the range of 4.7-58 mug ml(-1). Better limits of detection (1.6 mug ml(-1)) and quantification (4.7 mug ml(-1)) were obtained in this latter case with respect to those obtained in the absence of beta-CD. The method was satisfactorily applied to the quantification of ibuprofen in pharmaceutical preparations. A novel spectrofluorimetric determination of ibuprofen in the presence of beta-CD was also developed for serum samples at concentration levels between 5 and 70 mug ml(-1). It uses second-order fluorescence excitation-emission matrices coupled to an algorithm based on self-weighted alternating trilinear decomposition (SWATLD), and avoids resorting to separative instrumental analyses.     

Study of inclusion complex formation between tropaeolin OO and beta-cyclodextrin by spectrophotometry and Infrared spectroscopy

The mechanism of the inclusion of tropaeolin OO (TPOO) and beta-cyclodextrin (beta-CD) has been studied by spectrophotometry. The inclusion depth of the guest molecule in the host molecule was demonstrated by infrared spectrometry. Effect of the pH, concentrations of beta-CD, solvents and ionic strength on the inclusion of TPOO and beta-CD were examined. The result showed that TPOO reacts with beta-CD to form a 1:1 host-guest complex with an apparent formation constant of 1.50 x 10(3) l mol(-1). The thermodynamic parameters of inclusion reaction, DeltaG degrees , DeltaH degrees and DeltaS degrees were obtained.     

Complexation study of midazolam hydrochloride with beta-cyclodextrin: NMR spectroscopic study in solution

(1)H NMR spectroscopic study of midazolam hydrochloride (MDL), beta-cyclodextrin (beta-CD) and their mixtures confirmed the formation of beta-CD-MDL inclusion complex in aqueous solution. The stoichiometry of the complexes was determined by Scott's method to be 1:1, and the association constant (K(a)) was calculated to be 108 M(-1). It was confirmed on the basis of 2D ROESY spectral data that only a fluorine-substituted aromatic ring acted as guest in complexation. Most of the aromatic signals of MDL exhibited induced shift changes as well as splitting, in the presence of beta-CD, indicating chiral differentiation of MDL by beta-CD.     

Separation of basic drug enantiomers by capillary zone electrophoresis using glucuronyl glucosyl beta-cyclodextrin as a chiral selector.

Separations of basic drug enantiomers have been investigated using glucuronyl glucosyl beta-cyclodextrin (GUG beta-CD) as a chiral selector in the background electrolyte by capillary zone electrophoresis. The effects of GUG beta-CD concentration and running buffer pH on the migration times and resolution of 16 basic drug enantiomers were precisely examined using a linear polyacrylamide-coated capillary. High resolution of 16 basic drug enantiomers was generally attained with a running buffer pH 2.5 or 3.5 containing 10 mM GUG beta-CD. Next, we compared the chiral resolution abilities of GUG beta-CD with those of beta-CD and maltosyl beta-CD (G2 beta-CD). GUG beta-CD showed higher resolution for basic drug enantiomers tested than beta-CD and G2 beta-CD. This could be due to that hydrogen bonding or ionic interactions of uncharged and charged glucuronyl glucosyl groups of GUG beta-CD with an analyte could stabilize the inclusion complex.     

Structure and intramolecular flexibility of beta-cyclodextrin complex with (-)-epigallocatechin gallate in aqueous solvent

The probable structure of the inclusion complex of beta-cyclodextrin (beta-CD) and (-)-epigallocatechin gallate (EGCg) in D2O was investigated using several NMR techniques. EGCg formed a 1:1 complex with beta-CD, in which the A ring and a portion of the C ring of EGCg were included at the head of the phenolic hydroxyl group attached to C7 of EGCg in the beta-CD cavity from the wide secondary hydroxyl group side. In the 1:1 complex with beta-CD, EGCg maintained the conformation in which the B and B' rings of EGCg took pseudoequatorial and pseudoaxial positions with respect to the C ring, respectively. The structure of the inclusion complexes of beta-CD and EGCg obtained from NMR experiments supported those determined from AM1 semiempirical SCF MO calculations well.