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1.
环糊精包络物的循环伏安法研究 总被引:23,自引:0,他引:23
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. 相似文献
2.
R. Vaitkus G. Grinciene E. Norkus 《Journal of inclusion phenomena and macrocyclic chemistry》2011,69(3-4):345-347
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. 相似文献
3.
P. Cloudy J. M. Létoffé P. Germain J. P. Bastide A. Bayol S. Blasquez R. C. Rao B. Gonzalez 《Journal of Thermal Analysis and Calorimetry》1991,37(11-12):2497-2506
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. 相似文献
4.
Wolfram Saenger 《Journal of inclusion phenomena and macrocyclic chemistry》1984,2(3-4):445-454
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. 相似文献
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6.
The steady-state fluorescence emission from the local anaesthetic tetracaine (TCA) in water–solvent mixtures and in the presence of α-, β- and γ-cyclodextrin (CD) was investigated at various pH values. Emission was observed from the locally and the intramolecular charge transfer excited states. The TCA–CD system was found to be characterised by 1:1 associate in every case. The association constants of each complex were determined. 相似文献
7.
The electrospinning of polymer-free nanofibers from highly concentrated (160%, w/v) aqueous solutions of hydroxypropyl-β-cyclodextrin (HPβCD) and its inclusion complexes with triclosan (HPβCD/triclosan-IC) was achieved successfully. The dynamic light scattering (DLS) and rheology measurements indicated that the presence of considerable HPβCD aggregates and the high solution viscosity were the key factors in obtaining electrospun HPβCD and HPβCD/triclosan-IC nanofibers without the use of any polymeric carrier. The HPβCD and HPβCD/triclosan-IC solutions containing 20% (w/w) urea yielded no fibers but only beads and splashes because of the depression of the self-aggregation of the HPβCD. The inclusion complexation of triclosan with HPβCD was studied by isothermal titration calorimetry (ITC) and turbidity measurements. The characteristics of the HPβCD and HPβCD/triclosan-IC nanofibers were investigated by Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA), X-ray diffraction (XRD), and differential scanning calorimetry (DSC). It was found that the electrospinning of HPβCD/triclosan-IC solution having a 1:1 molar ratio was optimal for obtaining nanofibers without any uncomplexed guest molecules. 相似文献
8.
G. Köhler G. Grabner C. TH. Klein G. Marconi B. Mayer S. Monti K. Rechthaler K. Rotkiewicz H. Viernstein P. Wolschann 《Journal of inclusion phenomena and macrocyclic chemistry》1996,25(1-3):103-108
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. 相似文献
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Magaly A. M. Lyra José L. Soares-Sobrinho Regina C. B. Q. Figueiredo Jana M. Sandes ádley A. N. Lima R?mulo P. Tenório Danilo A. F. Fontes Fabiana L. A. Santos Larissa A. Rolim Pedro J. Rolim-Neto 《Journal of inclusion phenomena and macrocyclic chemistry》2012,73(1-4):397-404
The current chemotherapy for Chagas disease is still based on benznidazole, which has low solubility, but complexation with cyclodextrins provides a way of increasing the solubility. The objective of this work was to characterize the inclusion complexes formed between benznidazole (BNZ) and randomly 2-methyled-β-cyclodextrin (RM-β-CD) in aqueous solution and study cytotoxicity and trypanocidal. BNZ:RM-β-CD solution complex systems were prepared and characterized using the phase solubility diagram, nuclear magnetic resonance and a photostability assays, also to investigate the in vitro trypanocidal activity with epimastigote forms of Trypanossoma cruzi and the study of cytotoxicity against mammal cells. The phase-solubility diagram displayed an A L-type feature, providing evidence of the formation of soluble inclusion complexes. The continuous variation method showed the existence of a complex with 1:1 stoichiometry. Toxicity assays demonstrated that inclusion complexes were able to reduce the toxic effects caused by benznidazole alone and that this did not interfere with the trypanocidal activity of the benznidazole. The use of inclusion complexes benznidazole:cyclodextrin is thus a promising alternative for the development of a safe and stable liquid formulation and a new option for the treatment of Chagas disease. 相似文献
11.
Joseph J Dreiss CA Cosgrove T 《Langmuir : the ACS journal of surfaces and colloids》2008,24(18):10005-10010
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. 相似文献
12.
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. 相似文献
13.
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. 相似文献
14.
Gregory Nelson Gabor Patonay Isiah M. Warner 《Journal of inclusion phenomena and macrocyclic chemistry》1988,6(3):277-289
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. 相似文献
15.
V. Pushkara Rao Matthew B. Zimmt Nicholas J. Turro 《Journal of photochemistry and photobiology. A, Chemistry》1991,60(3):355-360
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. 相似文献
16.
John B. Cunniff Paul Vouros 《Journal of the American Society for Mass Spectrometry》1995,6(5):437-447
The results of previous works that have claimed to detect cyclodextrin inclusion complexes via the “soft” ionization technique of electrospray ionization mass spectrometry are revisited. A more extensive study of cyclodextrin mixtures with amino acids and small peptides demonstrates that amino acid and peptide “complexes” are detected by electrospray mass spectrometry regardless of the presence (or not) of an aromatic moiety on the side chain. Amino acids that may be least likely to form hydrophobic inclusion complexes with cyclodextrin in solution generally show the most intense complex ions. The data suggest that these “complexes” are, in all likelihood, electrostatic adducts formed during the electrospray process. Systematic controls are suggested to ensure that “false positives” do not negate many of the claims concerning the detection of solution-derived noncovalent compounds. 相似文献
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A. Harada S. Takahashi 《Journal of inclusion phenomena and macrocyclic chemistry》1984,2(3-4):791-798
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. 相似文献
19.
Judit Orgoványi L. Pöppl Klára H.-Otta G. A. Lovas 《Journal of Thermal Analysis and Calorimetry》2005,81(2):261-266
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. 相似文献
20.
Brandon R. Williamson Alan E. Tonelli 《Journal of inclusion phenomena and macrocyclic chemistry》2012,72(1-2):71-78
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. 相似文献