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At least 1,099 records · Page 61Linked to original sources
PubMed2005

Inorganic nanocrystal self-assembly via the inclusion interaction of beta-cyclodextrins: toward 3D spherical magnetite.

Synthesis and three-dimensional (3D) assembly of magnetite nanocrystals were realized by a one-pot procedure, in which Fe(acac)3 (acac = acetylacetonate) was partly reduced by hydrazine accompanied with ethylene glycol and spontaneously assembled into spherical nanostructures in the presence of surfactants including beta-cyclodextrin, oleic acid, and oleylamine. The size of the assembled spheres can coarsely be controlled in a limited range (100 nm to 2 microm) by changing the reaction temperature and the concentration of beta-cyclodextrin. X-ray diffraction and far Fourier transform infrared spectroscopy were employed to clarify the structures of magnetite in the assembled spheres. Electron diffraction pattern in a selected-area exhibits a high-crystallinity characteristic of cubic structure magnetite. We found that the formation of spherical magnetite aggregates highly depends on the presence of beta-cyclodextrin, while oleic acid and oleylamine improve the morphology of individual magnetite nanoparticles in the assembled spheres. In addition, the thermal gravimetric analysis and differential thermal analysis were applied to determine the content of magnetite in the products. Magnetic properties were also studied by using a superconducting quantum interference device magnetometer.

Ferrosoferric Oxide↗
PubMed2005

Fluorescence anisotropy decay and solvation dynamics in a nanocavity: coumarin 153 in methyl beta-cyclodextrins.

Fluorescence anisotropy decay and solvation dynamics of coumarin 153 (C153) are studied in dimethyl beta-cyclodextrin (DIMEB) and trimethyl beta-cyclodextrin (TRIMEB) nanocavity in water. C153 binds to DIMEB and TRIMEB to form both 1:1 and 1:2 (C153:cyclodextrin) complexes. The anisotropy decays of C153 in DIMEB and TRIMEB are found to be biexponential. The fast component of anisotropy decay (approximately 1000 ps) is attributed to the 1:1 complex and the slower one (approximately 2500 ps) to the 1:2 complex. From the components of the anisotropy decay, the length of the 1:1 and 1:2 complexes are estimated. Solvation dynamics of C153 in DIMEB exhibits a very fast (2.4 ps) component (41%) and two slower components of 50 ps (29%) and 1450 ps (30%). Solvation dynamics in TRIMEB is described by three slow components of 10.3 ps (24%), 240 ps (45%), and 2450 ps (31%). Possible origins of the ultraslow components are discussed.

Coumarins↗
PubMed2006

In search of fully uncomplexed cyclodextrin in the presence of micellar aggregates.

The chemical behavior of beta-cyclodextrin/nonionic surfactant mixed systems has been investigated using the basic hydrolysis of N-methyl-N-nitroso-p-toluenesulfonamide as a chemical probe. The experimental results prove that at the cmc, there are significant quantities of uncomplexed beta-CD in equilibrium with the micellar aggregates. In contrast to the expected situation, the percentage of uncomplexed beta-CD in equilibrium with the micellar system increases on increasing the hydrophobicity of the surfactant molecule. This behavior is due to the existence of two simultaneous processes: complexation of surfactant monomers by cyclodextrin and the process of self-assembly to form micellar aggregates. The autoaggregation of surfactant monomers is expected to be more important than the complexation process in this mixed system. Varying the hydrophobicity of the surfactant monomer enabled us to determine that the percentages of uncomplexed cyclodextrin in equilibrium with the micellar system were in the range of 5-95%.

Hydrolysis↗
PubMed2006

Dielectric studies of water clusters in cyclodextrins: Relevance to the transition between slow and fast forms of thrombin.

Cyclodextrins are useful models in the study of hydrogen bonded water clusters. In alpha-cyclodextrin hexahydrate (alpha-CD.6H2O), water molecules are ordered and occupy well-defined positions whereas in the larger beta-cyclodextrin dodecahydrate (beta-CD.12H2O), there is considerable disorder with water molecules freely arranged over several possible sites. Here it is shown that beta-CD exhibits substantial structural flexibility and proton mobility compared with alpha-CD which is relatively very rigid and exhibits negligible short-range protonic conduction. These properties are directly controlled by the effective dielectric constant of the molecule, which is determined by the rotational freedom of water molecules in the hydrogen bond network. This model may be relevant to proteins where water clusters of this kind are found on the protein surface and occasionally in the protein interior. The case of thrombin, an allosteric enzyme incorporating a network of 20 internal hydrogen bonded water molecules, is discussed.

Allosteric Site↗
PubMed2006

Molecular recognition in cyclodextrin complexes of amino acid derivatives: the effects of kinetic energy on the molecular recognition of a pseudopeptide in a nonconstraining host environment as revealed by a temperature-dependent crystallographic study.

The crystal structure of a triclinic 2:2 inclusion complex of beta-cyclodextrin with N-acetyl-L-phenylalanine methyl ester has been determined at several temperatures between 298 and 20 K to further study molecular recognition using solid-state supramolecular beta-cyclodextrin complexes. The study reveals kinetic energy dependent changes in guest molecule conformations, orientations, and positions in the binding pocket presented by the crystal lattice. Accompanying these changes are observable differences in guest-guest interactions and hydrogen-bonding interactions in the binding pocket that involve guest molecules, water of hydration molecules, and beta-cyclodextrin molecules. On the basis of the differences observed in the crystal structures, we present a solid-state example of a system that displays the properties of both classical and quantum chemical models. At higher temperatures, the structure conforms to a classical mechanical model with dynamic disorder. At lower temperatures, the observations conform to examples in which there is static disorder representative of models in which quantum states differing in conformation, position, and orientation of components in the crystal structure are occupied. Ab initio theoretical calculations on the different guest molecule conformations have been carried out. Superpositions of theoretical electrostatic surface potential diagrams on the observed molecular positions in the complexes provide confidence that the deconvolution of the guest molecule disorder is acceptable. Temperature-dependent solid-state magic angle spinning deuteron NMR measurements provide evidence for large-amplitude, diffusive motion on a microsecond time scale in the complex.

Amino Acids↗
PubMed2004

Structural properties of nonionic cyclodextrin colloids in water.

The amphiphilic character in water of a novel class of chemically modified cyclodextrins has been investigated by means of small-angle X-ray scattering and light scattering. The introduction ofhydrophilic oligo(ethylene glycol) onto the secondary side of heptakis[6-alkylthio-6-deoxy-2-oligo(ethylene glycol)]-beta-cyclodextrins produces an enhanced water solubility of these molecules. Shape and dimensions of the generated micellar aggregates, analyzed in terms of a suitable core-shell model, remain stable in the wide concentration range explored. The highly associative behavior of these macromolecules is evidenced by the very low value of the critical micelle concentration (cmc), which is about 2 orders of magnitude smaller than the cmc usually obtained for traditional surfactant. Despite the complex geometry of this novel macromolecule, shape and dimensions of generated micellar aggregates can be properly described according to the thermodynamic approaches generally used for amphiphilic molecules and block copolymers. Results show how the modulation of hydrophobic and hydrophilic components sensitively influence the structural features of the generated aggregates thus offering the possibility to control molecular organization in a manner similar to that for traditional colloids. For all the classes of the investigated systems, the small micelles have been found in equilibrium with polydisperse large aggregates of entangled micelles. These novel nonionic colloidal systems combine inclusion and transport properties of host macrocycles, such as cyclodextrin, together with the increased stability of colloidal aggregates, and may be of interest for their potential application as innovative drug delivery systems.

Circular Dichroism↗
PubMed2005

Orientational effect of surface-confined cyclodextrin on the inclusion of bisphenols.

The molecular recognition of various kinds of bisphenols (BPs) and a bisphenol A-polymer conjugate (BPA-polymer) by a self-assembled monolayer (SAM) of thiolated beta-cyclodextrin (CD) on a gold electrode was examined using cyclic voltammetry (CV). Based on the inhibitory effect of BPs on the inclusion of hydroquinone (HQ) as a probe by the surface-confined CD, the association constants (K(assoc)) of BPs with the immobilized beta-CD were estimated. The K(assoc) values for BPs with the SAM of 3-dithiobis(undecanoylamido)-3-deoxy-beta-cyclodextrin (DTUA-beta-CD) were smaller than those in the free beta-CD system reported previously. A similar tendency was obtained when 6-(lipoylamido)-6-deoxy-beta-cyclodextrin (LP-beta-CD) was used in place of DTUA-beta-CD. The K(assoc) values for all the BPs except for bisphenol B with the SAM of LP-beta-CD were always larger than those with the SAM of DTUA-beta-CD, due to a difference in the orientation of the beta-CD moiety in the SAMs. Furthermore, adsorption and desorption processes of the BPA-polymer from the surface-confined beta-CD was followed using local surface plasmon resonance spectroscopy.

Amides↗
PubMed2006

Self-assembly of beta-cyclodextrin in water. Part 1: Cryo-TEM and dynamic and static light scattering.

In this article, we report evidence of beta-cyclodextrin (beta-CD) self-aggregation in water. A critical aggregation concentration (cac) between 2 and 3 mM was determined by using dynamic (DLS) and static (SLS) light scattering to investigate the presence of beta-cyclodextrin aggregates. Transmission electron microscopy at cryogenic temperature (Cryo-TEM) was used to detect the structural features of cyclodextrin self-aggregates. The results show the occurrence of polymorphism depending on the beta-CD concentration: polydisperse nearly spherical objects with diameters of about 100 nm are present at lower concentrations, whereas micrometer planar aggregates are predominant at higher concentrations.

Microscopy, Electron, Transmission↗
PubMed2006

Bundle-shaped cyclodextrin-Tb nano-supramolecular assembly mediated by C60: intramolecular energy transfer.

A bundle-shaped nano-supramolecular assembly possessing numerous luminescent cyclodextrin-Tb polyads and photosensitizing C(60) units has been constructed through the end-to-end inclusion complexation of cyclodextrin cavities with C(60)s, and its properties have been comprehensively characterized. Further investigations on the luminescence properties of the cyclodextrin-Tb polyad and the bundle-shaped assembly demonstrate that a pyridine --> Tb --> C(60) intramolecular energy transfer process is operative when a solution of the assembly is exposed to UV light.

Crystallization↗
PubMed1991

Cyclodextrin sulfates: characterization as polydisperse and amorphous mixtures.

Alpha- and beta-cyclodextrins and their hydroxypropyl derivatives were converted by the reaction with chlorosulfonic acid in pyridine to the corresponding sulfates. Cyclodextrin sulfates were shown by fast-atom bombardment mass spectrometry (negative ion mode, triethanolamine matrix) to be mixtures with nearly symmetrical distributions of degree of substitution by sulfate groups and by powder X-ray diffraction to be amorphous. Thus, in these aspects, cyclodextrin sulfates are similar to the potent drug solubilizers hydroxypropylcyclodextrins.

Cyclodextrins↗
PubMed1991

Absorption enhancing effect of cyclodextrins on intranasally administered insulin in rats.

The absorption enhancing effect of alpha-, beta-, and gamma-cyclodextrin (CD), dimethyl-beta-cyclodextrin (DM beta CD), and hydroxypropyl-beta-cyclodextrin (HP beta CD) on intranasally administered insulin was investigated in rats. Coadministration of 5% (w/v) DM beta CD to the insulin solution resulted in a high bioavailability, 108.9 +/- 36.4% (mean +/- SD, n = 6), compared to i.v. administration, and a strong decrease in blood glucose levels, to 25% of their initial values. Coadministration of 5% alpha-CD gave rise to an insulin bioavailability of 27.7 +/- 11.5% (mean +/- SD, n = 6) and a decrease in blood glucose to 50% of its initial value. The rate of insulin absorption and the concomitant hypoglycemic response were delayed for the alpha-CD-containing solution as compared to the DM beta CD preparation. The other CDs, HP beta CD (5%), beta-CD (1.8%), and gamma-CD (5%), did not have significant effects on nasal insulin absorption. DM beta CD at a concentration of 5% (w/v) induces ciliostasis as measured on chicken embryo tracheal tissue in vitro, but this effect is reversible. In conclusion, DM beta CD is a potent enhancer of nasal insulin absorption in rats.

Absorption↗
PubMed2004

Combined approach using capillary electrophoresis and NMR spectroscopy for an understanding of enantioselective recognition mechanisms by cyclodextrins.

This tutorial review describes the contribution of chiral capillary electrophoresis in combination with other instrumental techniques, especially nuclear magnetic resonance spectroscopy, to a better understanding of the chiral recognition mechanisms by cyclodextrins. Aspects such as affinity pattern of enantiomers towards various cyclodextrins as well as the stoichiometry of the resulting complexes, the equilibrium constants and the structure of complexes are addressed. In addition to the aforementioned techniques, the usefulness of complementary instrumental and molecular modeling techniques for an understanding of the chiral recognition mechanisms of cyclodextrins is also illustrated.

Cyclodextrins↗
PubMed2003

A facile synthesis of novel cyclodextrin derivatives incorporating one beta-(1,4)-glucosidic bond and their unique inclusion ability.

Novel cyclodextrin derivatives incorporating one (1,4)-glucosidic bond are easily synthesized in three steps from permethylated alpha- and beta-cyclodextrins, and such host molecules show inclusion selectivity for sodium m-nitrobenzoate over the corresponding p-isomer, in contrast to the cases of the parent permethylated alpha- and beta-cyclodextrins.

Cyclodextrins↗
PubMed2004

Cyclodextrin effect on solvolysis of substituted benzoyl chlorides.

A kinetic study was carried out on the solvolysis of substituted benzoyl chlorides in the presence of alpha-, beta- and gamma-CD. Combination of the substituent dependent mechanism for solvolysis of benzoyl chlorides and the complexation ability of the cyclodextrin yields the following experimental behavior: (i) catalysis by beta- and gamma-CD for solvolysis of electron-attracting substituted benzoyl chlorides due to the reaction with its hydroxyl group C(6); (ii) absence of alpha-CD influence on solvolysis of benzoyl chlorides with electron withdrawing substituents; (iii) inhibition of solvolysis of benzoyl chlorides with electron-donating groups. This behavior is observed for solvolysis of meta/para substituted substrates in the presence of beta-CD, solvolysis of meta-substituted benzoyl chlorides in the presence of alpha-CD and solvolysis of para-substituted benzoyl chlorides in the presence of gamma-CD. This decrease in the rate constant is a consequence of the complexation of the substrate in the cyclodextrin cavity and its low solvation ability, causing the rate of solvolysis in its interior to be negligible. (iv) The solvolysis of meta-substituted benzoyl chlorides in the presence of gamma-CD yields a new behavior where the reaction of the complexed substrate is not negligible in the interior of the cyclodextrin cavity, which has been interpreted as a consequence of incomplete expulsion of hydration water from its cavity when the complexation takes place. (v) The experimental results obtained in the presence of alpha-CD show that meta-substituted benzoyl chlorides give rise to host : guest complexes with 1 : 1 stoichiometries, whereas those which are para-substituted cause a 2 : 1 stoichiometry to be formed. This difference in behavior has been interpreted taking into account the size of the different benzoyl chlorides and their accommodation in the alpha-CD cavity.

Benzoates↗
PubMed2005

Evidence of a self-inclusion phenomenon for a new class of mono-substituted alkylammonium-beta-cyclodextrins.

A new class of mono-substituted N-alkyl-N,N-dimethylammonium-beta-cyclodextrins has been synthesized in a three step procedure from the native beta-cyclodextrin. The structural analysis of these compounds undertaken by combined use of 1D and 2D NMR spectra indicate that the two methyl groups bound on the nitrogen are magnetically inequivalent due to a self-inclusion phenomenon of the alkyl chain inside the CD cavity. A variable-temperature 1H NMR study showed that these mono-substituted CD derivatives formed temperature-independent intramolecular complexes with their own alkylammonium substituent. The strength of the interaction between the alkyl moiety and the cyclodextrin cavity has been evaluated by a competitive method using an adamantane derivative. Finally, surface tension measurements demonstrated the surface active character of these compounds and confirmed their self-inclusion ability.

Magnetic Resonance Spectroscopy↗
PubMed2005

A unique tetramer of 4:5 beta-cyclodextrin-ferrocene in the solid state.

A single crystal of a unique 4:5 inclusion complex between beta-cyclodextrin and ferrocene was prepared and the structure was determined by X-ray crystallographic analysis, showing that four of the five ferrocenes were included in the cavities of four beta-cyclodextrins along the axial orientation of the tetramer, while another was co-included between two beta-cyclodextrins from the equatorial orientation.

Combinatorial Chemistry Techniques↗
PubMed2006

Evidence for complexes of different stoichiometries between organic solvents and cyclodextrins.

The influence of the organic solvent on the acid and basic hydrolysis of N-methyl-N-nitroso-p-toluenesulfonamide (MNTS) in the presence of alpha- and beta-cyclodextrins has been studied. The observed rate constant was found to decrease through the formation of an unreactive complex between MNTS and the cyclodextrins. In the presence of dioxane, acetonitrile or DMSO, the inhibitory effect of beta-CD decreased on increasing the proportion of organic cosolvent as a result of a competitive reaction involving the formation of an inclusion complex between beta-CD and the cosolvent. The disparate size of the organic solvent molecules resulted in stoichiometric differences between the complexes; the beta-CD-dioxane and beta-CD-DMSO complexes were 1 : 1 whereas the beta-CD-acetonitrile complex was 1 : 2. The basic and acid hydrolysis of MNTS in the presence of alpha-CD showed a different behavior; thus, the reaction gave both 1 : 1 and 2 : 1 alpha-CD-MNTS complexes, of which only the former was reactive. This result was due to the smaller cavity size of alpha-CD and the consequent decreased penetration of MNTS into the cavity in comparison to beta-CD. The acid hydrolysis of MNTS in the presence of alpha-CD also revealed decreased penetration of MNTS into the cyclodextrin cavity, as evidenced by the bound substrate undergoing acid hydrolysis. In addition, the acid hydrolysis of MNTS in the presence of acetonitrile containing alpha-CD gave 1 : 1 alpha-CD-acetonitrile inclusion complexes, which is consistent with a both a reduced cavity size and previously reported data.

Acetonitriles↗