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91.
Duc-Truc Pham Philip Clements Christopher J. Easton John Papageorgiou Bruce L. May 《Supramolecular chemistry》2013,25(6):510-519
This study shows that stereochemical factors largely determine the extent to which 6-(4′-t-butylphenylamino)-naphthalene-2-sulphonate, BNS? and its dimer, (BNS? )2, are complexed by β-cyclodextrin, βCD, and a range of linked βCD dimers. Fluorescence and 1H NMR studies, respectively, show that BNS? and (BNS? )2 form host–guest complexes with βCD of the stoichiometry βCD.BNS? (10? 4 K 1 = 4.67 dm3 mol? 1) and βCD.BNS2 2 ? (10? 2 K 2′ = 2.31 dm3 mol? 1), where the complexation constant K 1 = [βCD.BNS? ]/([βCD][BNS? ]) and K 2′ = [βCD. (BNS? )2]/([βCD.BNS? ][BNS? ]) in aqueous phosphate buffer at pH 7.0, I = 0.10 mol dm3 at 298.2 K. (The dimerisation of BNS? is characterised by 10? 2 K d = 2.65 dm3 mol? 1.) For N,N-bis((2AS,3AS)-3A-deoxy-3A-β-cyclodextrin)succinamide, 33βCD2su, N-((2AS,3AS)-3A-deoxy-3A-β-cyclodextrin)-N′-(6A-deoxy-6A-β-cyclodextrin)urea, 36βCD2su, N,N-bis(6A-deoxy-6A-β-cyclodextrin)succinamide, 66βCD2su, N-((2AS,3AS)-3A-deoxy-3A-β-cyclodextrin)-N′-(6A-deoxy-6A-β-cyclodextrin)urea, 36βCD2ur, and N,N-bis(6A-deoxy-6A-β-cyclodextrin)urea, 66βCD2ur, the analogous 10? 4 K 1 = 11.0, 101, 330, 29.6 and 435 dm3 mol? 1 and 10? 2 K 2′ = 2.56, 2.31, 2.59, 1.82 and 1.72 dm3 mol? 1, respectively. A similar variation occurs in K 1 derived by UV–vis methods. The factors causing the variations in K 1 and K 2 are discussed in conjunction with 1H ROESY NMR and molecular modelling studies. 相似文献
92.
2-Arylazo-5,5,10,10,15,15,20,20-octamethylcalix[4]pyrroles (azo-OMCPs) have been synthesised by the reaction of calix[4]pyrrole with aryldiazonium chloride in 15–45% yields. The solution-state binding studies of the synthesised hosts were investigated by absorption spectroscopy and 1H NMR in DMSO and CDCl3, respectively. These receptors, appended with electron-donating and electron-withdrawing groups, displayed enhanced affinity and selectivity for fluoride anion. Well-defined colour change in the visible region of the spectrum was observed upon addition of fluoride ion in DMSO solution of azo-OMCPs. Detailed NMR studies in CDCl3 revealed that azo-OMCPs with nitro and chloro groups have higher binding affinity for fluoride ion. 相似文献
93.
Interaction between tetramethylcucurbit[6]uril (TMeQ[6], host) and the hydrochloride salt of α-furaldehyde-isonicotinyl-hydrazone hydrochloride (FIHH+, guest) was investigated using X-ray crystallography and spectroscopic methods. X-ray crystallography showed that the π–π stacking effect and hydrogen bonding resulted in the formation of a dumbbell-shaped supramolecule which contained two FIHH+@TMeQ[6] host–guest inclusion complexes. The host–guest interaction provided identifiable changes in the vibrational frequencies in the IR spectra. 1H NMR spectral analysis established a similar interaction model and revealed that TMeQ[6] preferred to include the furan moiety over the pyridine moiety of the FIHH+ guest molecule. Absorption spectrophotometric analysis suggested that the host and guest interact in a ratio of 1:1 with a stability constant K s = (3.52 ± 0.74) × 106 l mol? 1.pH titration confirmed that the host–guest interaction led to a clear change in the protonation constant of the title guest. Quantum chemical calculations were used to determine the possible mechanism of formation of the dumbbell-shaped complex. 相似文献
94.
A. R. Cunningham S. L. Cunningham D. M. Consoer S. T. Moss M. H. Karol 《SAR and QSAR in environmental research》2013,24(3):273-285
Structure–activity relationship (SAR) models are recognized as powerful tools to predict the toxicologic potential of new or untested chemicals and also provide insight into possible mechanisms of toxicity. Models have been based on physicochemical attributes and structural features of chemicals. We describe herein the development of a new SAR modeling algorithm called cat-SAR that is capable of analyzing and predicting chemical activity from divergent biological response data. The cat-SAR program develops chemical fragment-based SAR models from categorical biological response data (e.g. toxicologically active and inactive compounds). The database selected for model development was a published set of chemicals documented to cause respiratory hypersensitivity in humans. Two models were generated that differed only in that one model included explicate hydrogen containing fragments. The predictive abilities of the models were tested using leave-one-out cross-validation tests. One model had a sensitivity of 0.94 and specificity of 0.87 yielding an overall correct prediction of 91%. The second model had a sensitivity of 0.89, specificity of 0.95 and overall correct prediction of 92%. The demonstrated predictive capabilities of the cat-SAR approach, together with its modeling flexibility and design transparency, suggest the potential for its widespread applicability to toxicity prediction and for deriving mechanistic insight into toxicologic effects. 相似文献
95.
O. Takahashi Y. Masuda A. Muroya T. Furuya 《SAR and QSAR in environmental research》2013,24(5-6):547-558
In general, the docking scoring tends to have a size dependence related to the ranking of compounds. In this paper, we describe a novel method of parameter optimization for docking scores which reduce the size dependence and can efficiently discriminate active compounds from chemical databases. This method is based on a simplified theoretical model of docking scores which enables us to utilize large amounts of data of known active and inactive compounds for a particular target without requiring large computational resources or a complicated procedure. This method is useful for making scoring functions for the identification of novel scaffolds using the knowledge of active compounds for a particular target or a customized scoring function for an interesting family of drug targets. 相似文献
96.
97.
98.
ZnO nanocrystals, rod-, carnation-, and flower-like structures, have been synthesized in a high yield through low-temperature synthetic methods. Well-aligned ZnO nanorods having hexagonal wurtzite structure were grown on the ZnO thin films assembled by a spin-coating method. The morphologies of ZnO seed films are affected by pHs of sol–gel solutions, resulting smaller sizes and homogeneous roughness at higher pHs and higher number of spin-coating times. The carnation-like structures, average size of about 2–3 μm, were assembled by tens of uniform ZnO nanosheet petals of ∼50 nm in thickness when a different volume ratio of the precursory solution was used. ZnO nanocrystals on the facets of the compact ZnO nanorods have grown to linear nanorods having an average diameter of ∼500 nm and length of ∼2 μm. Furthermore, a noticeable difference in the growth of ZnO nanocrystals in the presence of various surfactants, polyvinylpyrrolidone, polyvinylsulphonic acid, and polyethyleneimine, has been observed and discussed. 相似文献
99.
Phosphate glasses with compositions of 44P2O5 + 17K2O + 9Al2O3 + (30 − x)CaF2 + xDy2O3 (x = 0.05, 0.1, 0.5, 1.0, 2.0, 3.0 and 4.0 mol %) were prepared and characterized by X-ray diffraction (XRD), differential thermal analysis (DTA), Fourier transform infrared (FTIR), optical absorption, emission and decay measurements. The observed absorption bands were analyzed by using the free-ion Hamiltonian (HFI) model. The Judd–Ofelt (JO) analysis has been performed and the intensity parameters (Ωλ, λ = 2, 4, 6) were evaluated in order to predict the radiative properties of the excited states. From the emission spectra, the effective band widths (Δλeff), stimulated emission cross-sections (σ(λp)), yellow to blue (Y/B) intensity ratios and chromaticity color coordinates (x, y) have been determined. The fluorescence decays from the 4F9/2 level of Dy3+ ions were measured by monitoring the intense 4F9/2 → 6H15/2 transition (486 nm). The experimental lifetimes (τexp) are found to decrease with the increase of Dy3+ ions concentration due to the quenching process. The decay curves are perfectly single exponential at lower concentrations and gradually changes to non-exponential for higher concentrations. The non-exponential decay curves are well fitted to the Inokuti–Hirayama (IH) model for S = 6, which indicates that the energy transfer between the donor and acceptor is of dipole–dipole type. The systematic analysis of revealed that the energy transfer mechanism strongly depends on Dy3+ ions concentration and the host glass composition. 相似文献
100.
Afshan Banu D.E. Vasundhara Ravi S. Lamani I.A.M. Khazi Noor Shahina Begum 《Journal of Saudi Chemical Society》2013,17(2):211-217
The preparation of 2-(4-fluorobenzyl)-6-(4-methoxyphenyl)-5-morpholin-1-ylmethyl imidazo[2,1-b][1,3,4]thiadiazole via the intermediate 2-(4-fluorobenzyl)-6-(4-methoxyphenyl)Imidazo[2,1-b][1,3,4] thiadiazole is described. Elemental analysis, IR spectrum, 1H NMR and X-ray crystal structure analyses were carried out to determine the compositions and molecular structures of the two compounds. The crystal packing exhibits intermolecular C–H?O, C–H?N, C–H?F and π–π stacking interactions leading to the formation of the supramolecular network. 相似文献