Electrospinning of cyclodextrin functionalized polyethylene oxide (PEO) nanofibers

By means of the electrospinning technique we have successfully synthesized cyclodextrin (CD) functionalized polyethylene oxide (PEO) nanofibers (PEO/CD) with the ultimate goal to develop functional nanowebs. Three different types of CDs; α-CD, β-CD and γ-CD are incorporated individually in electrospun PEO nanofibers. The aqueous solutions containing different amount of PEO (3%, 3.5% and 4% (w/v), with respect to solvent) and CDs (25% and 50% (w/w), with respect to PEO) are electrospun and bead-free nanofibers are obtained. The presence of the CDs in the PEO solutions is found to facilitate the electrospinning of bead-free nanofibers from the lower polymer concentrations and this behavior is attributed to the high conductivity and viscosity of the PEO/CD solutions. The presence of CDs in the electrospun PEO nanofibers is confirmed by Fourier transform infrared (FTIR) spectroscopy studies. The 2-D X-ray diffraction (XRD) spectra of PEO/CD nanowebs did not show any significant diffraction peaks for CDs indicating that the CD molecules are distributed within the polymer matrix without any phase separated crystalline aggregates.     

Physicochemical characterization of cholesterol-beta cyclodextrin inclusion complexes

Study and characterization of molecular complexes between cholesterol and beta cyclodextrin has been done using X-ray diffraction, thermogravimetric analysis (TG), differential scanning calorimetry (DSC) and nuclear magnetic resonance spectroscopy (¹³C NMR). Whatever the value of the molar ratio cholesterol/βCD used during the preparation, the same compound is always obtained. Corresponding to a molar ratio 1/3 (cholesterol/βCD), this compound is a stable hydrate which, contrary toβCD, contains at room temperature a large amount of molecules of water. It can be dehydrated under low pressure but the thermal degradation occurs at 200°C (250°C forβCD). This implies that cholesterol is strongly bounded toβCD.     

Crystal packing patterns of cyclodextrin inclusion complexes

Cyclodextrin inclusion complexes crystallize in two basically different patterns, the cage and the channel type. The cage type occurs when cyclodextrins are packed crosswise (fishbone) or, if they are packed side-by-side, in layers and adjacent layers are displaced by about one half molecule. In each case, the internal cavity of one cyclodextrin is closed on both sides by neighbouring cyclodextrins. On the other hand, channel complexes are formed if cyclodextrins are stacked like coins in a roll so that cavities line up to produce long channels. In these crystal structures, cyclodextrins can be arranged in head-to-head or head-to-tail mode. In the smaller -cyclodextrin, cage type structures are formed with small, molecular guests whereas long molecular guests and ionic guest molecules induce channel type structures. The latter are generally preferred with the - and -cyclodextrin series which is probably due to the higher tendency for self aggregation in these two members of the cyclodextrin family.Part XXII of the series Topography of Cyclodextrin Inclusion Complexes. For part XXI, see ref. 6.     

人参皂苷与环糊精包合物的研究进展

人参皂苷是从人参、西洋参和三七中提取的主要活性成分,其药效价值相当高,但因其在水中几乎不溶,生物利用度极低,因此极大的限制了其在临床上的应用.环糊精具有独特的性质,其"腔内疏水、腔外亲水",可以选择性的包合人参皂苷等客体分子.环糊精与人参皂苷形成包合物后可以改变客体分子的某些物理化学性能,如水溶性、稳定性以及光学性质等,以此来提高其生物利用度.     

Electrospinning of cyclodextrin functionalized chitosan/PVA nanofibers as a drug delivery system

A new type of nanofibrous structure from chitosan bearing carboxymethyl-β-cyclodextrin (CS-g-β-CD) as a novel drug delivery system was synthesized by grafting carboxymethyl-β-cyclodextrin (CM β-CD) onto chitosan (CS) in the presence of water soluble 1-ethyl-3-(3-dimethylaminopropyl) carbodiimide (EDC) as the condensing agent and N-hydroxysuccinimide (NHS). Defect free mats containing CS-g-β-CD have been fabricated using electrospinning of an aqueous solution of poly(vinyl alcohol) (PVA)/CS-g-β-CD blends. The morphology and diameter of the electrospun nanofibers were examined by scanning electron microscopy (SEM). The average fiber diameter was in the range of 130–210 nm. SEM images showed that the morphology and diameter of the nanofibers were mainly affected by weight ratio of the blend at constant applied voltage. The results revealed that increasing CS-g-β-CD content in the blends decreases the average fiber diameter. It was observed that the PVA/CS-g-β-CD nanofibrous mat provided a slower release of the entrapped drug in compare to PVA/CS nanofibrous mat.     

Structure and spectroscopic properties of cyclodextrin inclusion complexes

We compare spectroscopic properties of higher order complexes of organic guests (e.g. naphthalene, phenols, indole, C₆₀ fullerene) with cyclodextrins (CDx) to results of molecular modeling investigations. Naphthalene 1:2 complexes with -CDx show high spectral resolution and peculiar triplet properties. Molecular simulations and calculation of the experimentally measured induced circular dichroism (ICD) provide detailed structural information.     

Potentiometric characterisation of cyclodextrin inclusion complexes of local anaesthetics

The complexation of several local anaesthetics by β and γ-cyclodextrins was studied by potentiometry with glass electrode. Tetracaine and dibucaine complexation constants were determined at 25°C in the presence of 0.1 M of NaCl. It was found that prilocaine and lidocaine complexes cannot be detected.     

Study of inclusion complexes of cyclodextrin by cyclic voltammetry

The inclusion complexes of a series of organometallic compound-cyclodextrin and aromatic compound-cyclodextrin have been studied by cyclic voltammetry using glassy carbon electrode. The variations of peak potential and peak current are showed on cyclic voltammogram when the electroactive guest molecules are complexed by cyclodextrins. Dissociation constants of cyclodextrin inclusion complexes have been calculated on the basis of this variation by both potential and current methods. According to the magnitude of dissociation constants the relationship between the stability of cyclodextrin inclusion complex and the degree of matching host molecule with guest molecule has been discussed.     

Inhibition of cyclodextrin acid hydrolysis by some inclusion complexes

Acidic hydrolysis of ??-cyclodextrin in the solution of hydrochloric acid containing some aliphatic alcohols was investigated. The reaction was carried out at 90 °C. It was observed that the rate of the reaction has decreased with the increase in concentration of a guest.     

Ability of the acetotoluides to form cyclodextrin inclusion complexes

Conclusion These series of experiments have shown that the -CD cavity was too small to allow stable inclusion complex formation. p-ACT is the isomer within this series that is best able to form inclusion complexes with -CD, then m-ACT and finally o-ACT. This would seem to indicate that the benzene ring of the molecule is the part of the structure most likely to penetrate the cavity since (a) -CD could not form stable complexes with any of the guest molecules and (b) less effective entry into the -CD cavity is the results of the acetamido group moving from p^–m^–o^– positions. Benzene ring penetration of the CD cavity is therefore required for stable inclusion complex formations in this group of compounds.     

Influence oftert-butyl alcohol on cyclodextrin inclusion complexes of pyrene

The effect oftert-butyl alcohol on complexes of pyrene and various cyclodextrins is investigated. The equilibrium constant for the complexation is derived from the fluorescence decay parameters. A greater than twofold enhancement of pyrene lifetime is observed in the presence oftert-butyl alcohol and -cyclodextrin or -cyclodextrin. As the number of hydroxyl groups decreases, substituted -cyclodextrins show smaller enhancements to both the fluorescence lifetime and the formation constant. These observations are explained by proposing that alcohol molecules are associated with the inclusion complex. This association increases the apparent hydrophobicity of the cyclodextrin cavity, protects the molecule from collisional quenching and deactivation, and provides additional rigidity to the system.     

环糊精包络物的循环伏安法研究

本文采用玻碳电极以循环伏安法研究了水溶液体系中二茂铁衍生物及芳香族衍生物与环糊精(α-CD, α-CD)的包络行为. 当电活性客体分子被包络时, 在循环伏安图上表现为峰电流和峰电位的变化, 用电流和电位法测定了包络物的解离常数, 并根据解离常数的大小次序探讨了主体分子与客体分子之间的匹配情况同包络物稳定性之间的关系.     

环糊精与丹参酮IIA包合作用的研究

通过荧光光谱方法分别研究了丹参酮IIA在溶液的pH为7．5时与β—CD和γ—CD的包合常数,对客体的包结能力β-CD〉γ-CD;并利用热力学方法研究了温度对包合反应的影响,计算了包合过程的熵变、焓变及自由能变化;分子模拟方法进一步证实了该包合物的形成;采用超声波法制备了环糊精与丹参酮IIA的固体包合物,并用红外光谱对固体包合物进行了表征．     

Photoproduction of remarkably stable benzylic radicals in cyclodextrin inclusion complexes

Photolysis of cyclodextrin inclusion complexes of diastereomers of ,′-dimethyldibenzyl ketone in the solid state resulted in stable benzylic radicals at room temperature. These radicals were characterized by their electron spin resonance (ESR) signals, emission and excitation spectra.     

Preparation and properties of cyclodextrin inclusion compounds of organometallic complexes. Ferrocene inclusion compounds

Inclusion compounds of ferrocene(FcH) and its derivatives with cyclodextrins(CDs; -CD, -CD, and -CD) were prepared. CD-ferrocene inclusion compounds were obtained in a crystalline state in high yield. -CD and -CD formed 11 stoichiometric inclusion compounds with ferrocene and its derivatives. -CD formed 21 (CD:guest) complexes with ferrocene and the monosubstituted derivatives, but did not form complexes with 1,1-disubstituted derivatives, -CD-FcH and -CD-FcH complexes are thermally stable and do not liberate ferrocene on heating at 100°C in vacuo. The cyclodextrin inclusion compounds were characterized by¹H-NMR, IR, UV, and CD spectra. A large positive induced Cotton effect was observed in the case of -CD-FcH complex, while the -CD-FcH complex showed a negative spectrum. The binding mode is discussed. -Cyclodextrin was found to form inclusion complexes in ethylene glycol, diethylene glycol, triethylene glycol, methyl cellosolve, ethyl cellosolve, methyl alcohol, and glycerine solutions. -CD also formed complexes in ethylene glycol solution. The binding of ferrocene by -CD is stronger in ethylene glycol than in dimethyl sulfoxide and dimethyl formamide.     

Thermoanalytical method for studying the guest content in cyclodextrin inclusion complexes

The interaction of cypermethrin with β-cyclodextrin was investigated using different (coprecipitation, suspension, kneading and ‘melting in solution’) complexation methods and qualifying the resulted complexes by UV-spectrophotometry, thermal methods (TG, DTG and DSC) and X-ray powder diffraction. The total guest content of complexes can be measured by UV-spectrophotometry in aqueous ethanol solution, while the uncomplexed guest fraction of samples can be determined by DSC based on a previous calibration curve, which was found between the melting enthalpy change of cypermethrin and the guest content of physical mixture samples. The combination of both analytical methods enables the determination of really complexed guest content.     

Constrained polymer chain behavior observed in their non-stoichiometric cyclodextrin inclusion complexes

Much has been learned from inclusion compounds (IC’s) formed between guest polymers and host cyclodextrins (CDs) [polymer-CD-ICs] by examining the properties of the fully covered guest polymers, as well as those coalesced neat bulk samples of guest polymers obtained upon removal of the host CDs. However, what can be gained from studying the properties of the restrained unthreaded portions of polymer chains that “dangle” from non-stoichiometric (n-s)-polymer-CD-IC’s? We attempt to assist in answering this question by observing (n-s)-polymer-CD-IC’s formed between amorphous atactic-poly(methyl methacrylate) (PMMA) and γ-CD, as well as the IC formed between a synthesized poly(ε-caprolactone)-poly(propylene glycol)-poly(ε-caprolactone) (PCL-PPG-PCL) triblock copolymer and β-CD, which was presumed to have threaded and unthreaded PPG and PCL blocks. Though our (n-s)-PMMA-γ-CD-IC samples were found to exhibit extremely heterogeneous behaviors, glass transition temperature increases of up to 27?°C above that of neat PMMA were observed. X-ray diffraction data indicates modest γ-CD crystallinity at partial coverages of PMMA, with a crystal structure similar to that of the IC with full coverage. On the other hand, XRD, DSC and FTIR data revealed an almost total disruption of PCL block crystallinity upon complexation of PCL-PPG-PCL with β-CD, suggesting either partial threading and coverage of the PCL blocks by β-CD or their partial mixing with the PPG blocks covered with β-CD.     

Stretching a polymer brush by making in situ cyclodextrin inclusion complexes

The interaction between poly(ethylene oxide) (PEO) chains grafted onto polystyrene latex particles and alpha-, beta-, and gamma-cyclodextrins (CD) was studied by small-angle neutron scattering. The particles were contrast-matched to the solvent in order that only the scattering from the polymer layers was detected. The signal from the layers was fitted to a double-exponential volume fraction profile. The effects of adding cyclodextrin on the polymer profile are shown as a function of cyclodextrin concentration. The polymer layers are seen to extend on addition of CD, which is consistent with a complexation between the grafted PEO and the CD molecules. The effect is the strongest with alpha-CD.     

环糊精及其包络物的分子力学研究

本文用分子力学方法研究了环糊精及其包络物的性质, 探讨了包络过程及其驱动力, 与电化学实验结果对比获得一致性结伦。