Structure of a cyclodextrin functionalized anionic clay: XRD analysis, spectroscopy, and computer simulations

Carboxy-methyl beta-cyclodextrin (CMCD) cavities have been intercalated within the galleries of anionic clay, Mg-Al layered double hydroxide (LDH). The cyclodextrin functionalized LDH has been reported to adsorb neutral and nonpolar guest molecules. X-ray diffraction, IR, and Raman vibrational spectroscopy and (13)C CPMAS NMR have been used to characterize the confined CMCD molecules, whereas molecular dynamics simulations have been used to probe the interlayer arrangement and orientation of the intercalated species. Spectroscopic measurements as well as MD simulations show that there is no significant change in the geometry of the CMCD cavity on intercalation. Within the galleries of the anionic clay, the CMCD anions are arranged as bilayers with the carboxy methyl substituents, located at the narrower opening of the bucket-like cyclodextrin toroid, anchored to the LDH sheet. This arrangement leaves the wider opening of the CMCD anion facing away from the layers allowing the interior of the cyclodextrin cavity to be accessible to guest molecules. Finally, the hydrophobicity of the anchored cyclodextrin cavity has been characterized using fluorescence from pyrene included within it.     

Inclusion of poly-aromatic hydrocarbon (PAH) molecules in a functionalized layered double hydroxide

The internal surface of an Mg-Al layered double hydroxide has been functionalized by anchoring carboxy-methyl derivatized β-cyclodextrin cavities to the gallery walls. Neutral polyaromatic hydrocarbon (PAH) molecules have been included within the functionalized solid by driving the hydrophobic aromatic molecules from a polar solvent into the less polar interior of the anchored cyclodextrin cavities by a partitioning process. The optical (absorption and emission) properties of the PAH molecules included within the functionalized Mg-Al layered double hydroxide solid are similar to that of dilute solutions of the PAH in non-polar solvents. The unique feature of these hybrid materials is that they are thermally stable over a wide temperature range with their emission properties practically unaltered. Dedicated to Prof J Gopalakrishnan on his 62nd birthday.     

Aromatic molecules in restricted geometries: photophysics of naphthalene included in a cyclodextrin functionalized layered solid

The galleries of an Mg-Al layered double hydroxide have been functionalized by intercalation of carboxymethyl beta-cyclodextrin cavities. The anchored cavities form a random array of identical-sized hydrophobic nanopockets arranged in a bilayer fashion in the interlamellar space of the layered solid. Naphthalene molecules have been included within these cavities by partitioning from a polar solvent. The fluorescence from the included naphthalene shows an unusual behavior--the excimer to monomer emission intensity decreases with increasing concentration of included naphthalene. This is shown to be a consequence of the absence of translational mobility of the naphthalene--cyclodextrin adduct in the functionalized solid. Two types of included naphthalene have been identified: a preformed excimer-like species characterized by the absence of rise time in decay measurements and a monomeric species that is incapable of excimer formation due to the absence of suitably located included naphthalenes in its proximity. The concentration of each species and the enthalpy for excimer formation have been determined from the temperature variation of fluorescence intensities.     

Insertion of iodine in a functionalized inorganic layered solid

The galleries of a Mg-Al layered double hydroxide have been functionalized by intercalation of (carboxymethyl)-beta-cyclodextrin cavities. The functionalized inorganic solid can adsorb iodine molecules from vapor as well as nonaqueous and aqueous solutions. The adsorbed iodine complexes with the grafted cyclodextrin cavities, disassociating heterolytically to form polyiodide species. Electronic and Raman spectra provide conclusive evidence for the existence of linear symmetric triodide, I(3)(-), and pentaiodide, I(5)(-), species within the cyclodextrin cavities confined in the layered double hydroxide.     

Covalently linked, water-dispersible, cyclodextrin: reduced-graphene oxide sheets

Reduced-graphene oxide (rGO) sheets have been functionalized by covalently linking β-cyclodextrin (β-CD) cavities to the sheets via an amide linkage. The functionalized β-CD:rGO sheets, in contrast to rGO, are dispersible over a wide range of pH values (2-13). Zeta potential measurements indicate that there is more than one factor responsible for the dispersibility. We show here that planar aromatic molecules adsorbed on the rGO sheet as well as nonplanar molecules included in the tethered β-CD cavities have their fluorescence effectively quenched by the β-CD:rGO sheets. The β-CD:rGO sheets combine the hydrophobicity associated with rGO along with the hydrophobicity of the cyclodextrin cavities in a single water-dispersible material.     

Dopamine Oxidation at Per(6‐deoxy‐6‐thio)‐α‐Cyclodextrin Monolayer Modified Gold Electrodes

The gold electrode is functionalized by sequential self‐assembly of a monolayer of the title thiolated cyclodextrin with and without dopamine included in the cavities. The structure of α‐cyclodextrin modified gold electrode is carefully characterized using STM and AFM. Surface complexation of dopamine is examined and its association constant is evaluated. Chemical reactions accompanying the electrode process of dopamine, which interfere in the electrochemical dopamine determination, are described and the conditions to avoid them are proposed. Dopamine incorporated in the α‐cyclodextrin sites anchored to the electrode surface was found to provide electrochemical contact of the electrode with the solution‐resident dopamine. Dopamine present in the α‐cyclodextrin cavities has different properties compared to dopamine in the bulk buffer solution and can act as a mediator for the dopamine molecules diffusing to the electrode. This unique mediation effect leads to improvement of the sensitivity of dopamine determination using the α‐cyclodextrin modified electrode and a procedure for the determination of dopamine in large excess of ascorbate is proposed.     

Inclusion of ferrocene in a cyclodextrin-functionalized layered metal hydroxide: a new organometallic--organic-LDH nanohybrid

Cyclodextrin cavities have been grafted into a layered metal hydroxide to create hydrophobic nanopockets within the galleries of the inorganic solid. Neutral ferrocene molecules can be included within the grafted cavities by partitioning from a polar solvent to generate a new organometallic-organic-inorganic hybrid. The included ferrocene has been characterized by electronic and Raman spectroscopy. The capability of the cyclodextrin-functionalized solid to separate hydrophobic and hydrophilic derivatives of ferrocene is demonstrated.     

Fluorescent Cyclodextrin/Peptide Hybrids with a Novel Guest‐Responsive Chemosensor in the Peptide Side Chain

Peptides bearing β‐cyclodextrin and 4‐(N,N‐dimethylamino)benzoyl (DMAB) units in the peptide side chains were prepared as chemosensors for molecule detection. The DMAB unit was expected to be included into the cyclodextrin cavity intramolecularly. However, these peptides exhibited no twisted intramolecular charge transfer fluorescence and the normal fluorescence intensity decreased upon the addition of 1‐adamantanol as an exogenous guest, indicating that the DMAB units are shallowly included in the cyclodextrin cavities.     

Investigation of the interactions between the hydrophobic cavities of cyclodextrins and pullulanase

The effects of cyclodextrins and derivatives on the activity and structure of pullulanase were investigated in this study. Our results showed that cyclodextrins and derivatives decreased the activity of pullulanase. This decrease was attributed to the interaction between the hydrophobic cavities of cyclodextrins and pullulanase. The hydrophobic cavity was confirmed to encapsulate the groups of pullulanase molecules by the addition of competitive guests. The results obtained from fluorescence spectroscopy analysis showed that β-CD showed more efficient interactions with pullulanase molecules and the side chain groups of cyclodextrin significantly prevented the interaction between the hydrophobic cavities of β-CD and pullulanase molecules. These findings suggest that the geometric dimension of hydrophobic cavities was crucial for matching between cyclodextrins and pullulanase and steric hindrance caused by side chains led to the decrease of the interaction.     

Crystal Structures of β‐Cyclodextrin Inclusion Complexes with 7‐Hydroxycoumarin and 4‐Hydroxycoumarin and Substituent Effects on Inclusion Geometry

Two inclusion complexes of β‐cyclodextrin‐7‐hydroxycoumarin ( 1 ) and β‐cyclodextrin‐4‐hydroxycoumarin ( 2 ) were prepared and their crystal structures were investigated by single crystal X‐ray crystallography under cryogenic condition. Both structures consist of stacks of face‐to‐face cyclodextrin dimers arranged in brickwork‐like pattern along the crystallographic a‐axis. For complex 1 , each of the two dimeric β‐cyclodextrins includes one 7‐hydroxycoumarin molecule that penetrates deeply into the cyclodextrin dimer and locates its lactonering at the center of the dimer cavity. For complex 2 , each cyclodextrin dimer accommodates three 4‐hydroxycoumarin molecules. One of them is sandwiched between two units of the cyclodextrin dimer, the other two are shallowly included in the cavities of the dimeric cyclodextrins respectively and protrude their lactone rings from the primary end of the cyclodextrin. The substituent effects of guest molecules on inclusion geometry of various coumarin molecules in β‐cyclodextrin were examined.     

Molecular Recognition of Bridged Bis （β－cyclodextrin） s Linked by Phenylenediseleno Tether on the Primary or Secondary Side with Fluorescent Dyes

A novel β‐cyclodextrin dimer, 2, 2′‐o‐phenylenediseleno‐bridged bis (β‐cyclodextrin) (2), has been synthesized by reaction of mono‐[2‐O‐(p‐tolylsulfonyl)]‐β‐cyclodextrin and poly(o‐phenylenediselenide). The complexation stability constants (K₂) and Gibbs free energy changes (‐ΔG°) of dimer 2 with four fluorescence dyes, that is, ammonium 8‐anilino‐1‐naphthalenesulfonate (ANS), sodium 6‐(p‐toluidino)‐2‐naphthalenesulfonate (TNS), Acridine Red (AR) and Rhodamine B (RhB) have been determined in aqueous phosphate buffer solution (pH = 7.2, 0.1 mol‐L^?1) at 25 °C by means of fluorescence spectroscopy. Using the present results and the previously reported corresponding data of β‐cyclodextrin (1) and 6, 6′‐o‐phenylenediseleno‐bridged bis (β‐cyclodextrin) (3), binding ability and molecular selectivity are compared, indicating that the bis (β‐cyclodextrin)s 2 and 3 possess much higher binding ability toward these dye molecules than parent β‐cyclodextrin 1, but the complex stability constant for 2 linked from the primary side is larger than that of 3 linked from the secondary side, which is attributed to the more effective cooperative binding of two hydrophobic cavities of host 3 and the size/shape‐fit relationship between host and guest. The binding constant (K₂,) upon inclusion complexation of host 3 and AR is enhanced by factor of 27.3 as compared with that of 1. The 2D ¹H NOESY spectrum of host 2 and RhB is performed to confirm the binding mode and explain the relative weak binding ability of 2.     

Encapsulation of norharmane in cyclodextrin: formation of 1:1 and 1:2 inclusion complexes

Steady state absorption and fluorometric techniques have been used to investigate the photophysics of norharmane (NHM), a bioactive fluorophore, in aqueous as well as aqueous cyclodextrin (CD) environments. The absorption and steady state fluorescence spectral studies reveal the formation of two types of inclusion complexes between the fluorophore and beta-cyclodextrin (beta-CD) depending on the relative population of the two. The stoichiometries and association constants of these complexes have been determined monitoring the fluorescence data. alpha-and gamma-cyclodextrin (alpha-CD, gamma-CD) do not have appreciable effect on the spectral pattern of the fluorophore. The differential fluorimetric behavior of NHM in different CD environments has been rationalized from the variation of the relative dimensions of the probe and the CD cavities.     

Analytical applications of gold electrodes modified with monolayers of thiolated cyclodextrins

The sequential method for the preparation of cyclodextrin monolayers is used to prepare modified electrodes responsive towards selected guest molecules: ferrocene, ibuprofen, methylene blue, dopamine and menadione. The inclusion into cyclodextrin cavities is monitored using cyclic voltammetry and the mediating role of the immobilized molecules towards solution species is shown on the example of dopamine oxidation.     

Computational studies of 1:2 complex between retinol propionate and β cyclodextrin

[M05-2X/6-31G*:PM3MM] and [B3LYP/6-31G*:PM3] ONIOM2 methods have been used to investigate the vitamin A propionate/β cyclodextrin complex with 1:2 stoichiometry. Both methods give almost the same lowest energy minimum. The minimum energy structure of the complex is found in good agreement with experimental data. In this configuration, the major structure of propionate of vitamin A (PVA) is embedded inside the two cavities of βCD while the propionate group is kept outside. However, the three methyl groups of PVA are positioned in the free space between both βCD molecules. The driving forces for complexation are dominated by Van der Waals interactions between PVA and the βCD molecules assisted with multiple hydrogen bond interactions between the two cyclodextrin molecules. These interactions were investigated using the natural bond orbital approach.     

Photoinduced intermolecular electron transfer from dimethyl aniline to 7-amino coumarin dyes in the surface of beta-cyclodextrin

The photoinduced electron-transfer reaction between Coumarin dyes and N,N-dimethylaniline has been investigated using steady-state and Time-resolved fluorescence spectroscopy in the surface of beta-cyclodextrin in dimethyl formamide (DMF) solvent. The electron-transfer rate constant has been correlated with the free-energy change during the process. We have observed a diffusion-controlled ET process in pure DMF by showing a normal Marcus region. However, the picture is different in presence of cyclodextrin. Here the ET is retarded at higher free-energy region. This unusual feature in bimolecular electron-transfer reaction is assumed to be arising from the different binding possibility of the Coumarin molecules to the cyclodextrin moity.     

Synthesis of Anthracene Derivatives with Azaacene-Containing Iptycene Wings and the Utilization as a Dopant for Solution-Processed Organic Light-Emitting Diodes

Substituted acene derivatives are regarded as promising materials for organic electronic devices such as organic light-emitting diodes (OLEDs). In particular, anthracene derivatives are known to exhibit good fluorescence property, with the air stability and solubility in common organic solvents expected to give advantages for solution-processed device fabrication. In this study, a series of bistriisopropylsilyl(TIPS)ethynyl anthracene derivatives with azaacene-containing iptycene wings have been synthesized by using condensation reactions. Effects of size of azaacenes on optical properties and packing structures were investigated. UV/Vis absorption and fluorescence spectra indicate that the π-elongation of iptycene units has small effects on the overall π-system, which is also supported by electrochemical measurements. Secondly, single-crystal X-ray analysis implies that the molecules likely have interactions with the iptycene units of adjacent molecules, while the iptycene wings and TIPSethynyl groups can prevent the central anthracene unit from undesirable non-radiative energy loss. Finally, the most emissive derivative was used as a dopant for solution-processed OLEDs, showing obvious electroluminescence with a luminance of over 920 cd m⁻².     

A polyrotaxane series containing alpha-cyclodextrin and naphthalene-modified alpha-cyclodextrin as a light-harvesting antenna system

Supramolecular light-harvesting antenna systems were constructed by using polyrotaxanes, in which cyclodextrin (CD) rings of alpha-CD and naphthalene (energy donor)-appended alpha-CD are threaded by a poly(ethylene glycol) chain with anthracene (energy acceptor) units at both ends (5-8). The effects of the component ratio of the polyrotaxanes on the efficiencies of energy migration and energy transfer were examined by fluorescence emission and excitation spectra and anisotropy and by fluorescence decay measurements. The observed results were explained by using the Forster mechanism.     

Isosteric heats of sorption of 1-naphthol and phenol from aqueous solutions by beta-cyclodextrin polymers

The sorption of phenol and 1-naphthol from aqueous solutions by beta-cyclodextrin polymers has been analyzed using the isosteric heat approach. This has proven to be a useful tool for comparing the interactions between the sorbents and the sorbates. With the purpose of ascertaining the role of the cyclodextrin cavities and the crosslinking network in the sorption process, analogous sucrose polymers have been prepared using the same crosslinking reagents (epichlorohydrin, succinyl chloride, 1,6-hexamethylene diisocyanate, and toluene-2,4-diisocyanate). The two studied sorbates, phenol and 1-naphthol, also show important differences in their affinities for the cyclodextrin cavities and the crosslinking networks.     

环糊精聚合物的高分子效应

环糊精以其独特的包络性能而引人注目, 现已广泛应用于色谱分离、选择性合成的催化剂、食品、医药及农药等多种领域。环糊精聚合物被证实亦具有包络、缓释及催化的能力, 以及较好的机械强度和化学稳定性。目前环糊精聚合物主要应用在色谱分离、空气净化和食品工业等方面。本文综述了环糊精高分子化后所表现出的高分子效应, 为环糊精聚合物的合成和应用提供参考。     

Fluorescence Studied of Dissociation Constant of Cyclodextrin With Phenol Derivatives

α-and β-cyclodextrins consisting of six and seven glucose residues respectively, have lipophilic cavities with different inner diameters. They form host-guest inclusion complexes with hydrophobic organic and organometallic guest molecules in aqueous solution. These host-guest complexes have proved to be excellent model systems for studying the nature of noncovalent bonding forces in aqueous media. They have provided valuable insights into the hydrophobic effect and London dispersion forces and are good model for understanding the specificity of enzyme substrate interactions [1] Evidence for the formation of inclusion complexes have been provided from calovimetric titration [2] NMR[33], circular dichroism[4], U V[1] and fluorescence spectra[5] and conductometric method[6] etc. H ere we report a new fluorimetric method for a study on the reaction of the host-guest inclusion complexes of cyclodextrin with phenols. Dissociation constants (Kd) of the inclusion complexes of some phenols with α-β-cyclodextrin are estimated based on the variation of the fluorescent intensity and modified Harad' equations.