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91.
Leonard S Van Schepdael A Iványi T Lázár I Rosier J Vanstockem M Vermeersch H Hoogmartens J 《Electrophoresis》2005,26(3):627-632
A capillary electrophoretic (CE) method was developed for the separation of diastereoisomers of a new human immunodeficiency virus (HIV) protease inhibitor TMC114. In total 16 isomers of this drug have been synthesized (eight pairs of enantiomers). We succeeded in the separation of the eight diastereoisomers, but no enantiomers could be separated. Because of the high similarity and water-insolubility of these isomers, the separation is a real challenge. Different CE modes were tried out: capillary zone electrophoresis (CZE), nonaqueous capillary electrophoresis (NACE), micellar electrokinetic capillary chromatography (MEKC), and microemulsion electrokinetic capillary chromatography (MEEKC). Only MEEKC offered resolution of these compounds. 相似文献
92.
Barriga S Fuertes P Marcos CF Rakitin OA Torroba T 《The Journal of organic chemistry》2002,67(18):6439-6448
We report the synthesis of some new polysulfur-nitrogen heterocycles by cycloaddition reactions to readily available tricyclic condensed 1,2-dithiole-3-thiones. Thus, treatment of bis[1,2]dithiolopyrrole ketothione 1 with diacyl acetylenes gave the bis-aducts 2a-d. On the other hand, cycloaddition of bis[1,2]dithiolo[1,4]thiazine ketothione 3 with 1 equiv of acyl or diacyl acetylenes gave [1,3]dithiolylidenyl[1,2]dithiolo[1,4]thiazines 4a-f in fair to high yields. Catalysis by scandium triflate was used in the reactions that implied the less reactive dipolarophiles. Treatment of 3 with 2 equiv of DBA gave the bis-aduct 5a, and reaction of 4c with DMAD gave the mixed bis-adduct 5b. Cyclic voltammetry of selected examples showed irreversible processes that were influenced by the electrochemical activity of peripheral groups bonded to the heterocyclic system. 相似文献
93.
Katleen Boussu Jérémie De Baerdemaeker Charles Dauwe Marc Weber Kelvin G Lynn Diederik Depla Steliana Aldea Ivo F J Vankelecom Carlo Vandecasteele Bart Van der Bruggen 《Chemphyschem》2007,8(3):370-379
This study presents a methodology for an in-depth characterization of six representative commercial nanofiltration membranes. Laboratory-made polyethersulfone membranes are included for reference. Besides the physical characterization [molecular weight cut-off (MWCO), surface charge, roughness and hydrophobicity], the membranes are also studied for their chemical composition [attenuated total reflectance Fourier spectroscopy (ATR-FTIR) and X-ray photoelectron spectroscopy (XPS)] and porosity [positron annihilation spectroscopy (PAS)]. The chemical characterization indicates that all membranes are composed of at least two different layers. The presence of an additional third layer is proved and studied for membranes with a polyamide top layer. PAS experiments, in combination with FIB (focused ion beam) images, show that these membranes also have a thinner and a less porous skin layer (upper part of the top layer). In the skin layer, two different pore sizes are observed for all commercial membranes: a pore size of 1.25-1.55 angstroms as well as a pore size of 3.20-3.95 angstroms (both depending on the membrane type). Thus, the pore size distribution in nanofiltration membranes is bimodal, in contrast to the generally accepted log-normal distribution. Although the pore sizes are rather similar for all commercial membranes, their pore volume fraction and hence their porosity differ significantly. 相似文献
94.
Heterobinuclear oxometalate anions based upon [CrMoO7]2-, [CrWO7]2-, and [MoWO7]2- were generated and transferred to the gas phase by the electrospray process from acetonitrile solutions containing two of the salts (Bu4N)2[MO4] (M = Cr, Mo, W). Their reactivities were examined and compared with those of the related homobinuclear anions based upon [M2O7]2- (M = Cr, Mo, W). Particular emphasis was placed upon reactions relevant to gas-phase catalytic cycles described previously for oxidation of alcohols by [Mo2O6(OH)]- (Waters, T.; O'Hair, R. A. J.; Wedd, A. G. J. Am. Chem. Soc. 2003, 125, 3384-3396). The protonated anions [MM'O6(OH)]- each reacted with methanol with loss of water to form [MM'O6(OCH3)]- at a rate that was intermediate between those of [M2O6(OH)]- and [M'2O6(OH)]-. The butylated anions [MM'O6(OBu)]- were generated by collisional activation of the ion-pairs {Bu4N+ [MM'O7]2-}-. Collisional activation of [MM'O6(OBu)]- resulted in either the loss of butanal (redox reaction) or the loss of butene (elimination reaction), with the detailed nature of the observations depending on the nature of both M and M'. Selective 18O labeling indicated that the butoxo ligands of [CrMoO6(OBu)]- and [CrWO6(OBu)]- were located on molybdenum and tungsten, respectively. This structural insight allowed a more detailed comparison of reactivity with the homobinuclear species, and highlighted the importance of the neighboring metal center in these reactions. 相似文献
95.
Johan Garssen Theresa L. Buckley Henk Van Loveren 《Photochemistry and photobiology》1998,68(2):205-210
The aim of this study was to investigate the possible role of sensory nerves in UV light-induced systemic immunomodulation. Contact hypersensitivity to the low molecular weight compound picrylchloride was used as a model for cellular immunity that can be suppressed by low (i.e. suberythemal) doses of UV light even after exposure at a distant locus (i.e. systemic immunosuppression). In sensory nerve-depleted mice, achieved by two subcutaneous injections with the neurotoxin capsaicin before the age of 4 weeks, UV light exposure failed to inhibit contact hypersensitivity responses to picrylchloride. This indicates that sensory nerves are at least partially involved in the induction of systemic immunosuppression by UV light. In order to analyze whether sensory neuropeptides, such as calcitonin gene-related peptide (CGRP) and tachykinins, are involved in UV light-induced systemic immunosuppression, mice were pretreated with selective antagonists prior to each UV light exposure. These experiments indicated that CGRP but not the tachykinins plays a crucial role in the UV light-induced systemic immunosuppression. 相似文献
96.
Haes AJ Zhao J Zou S Own CS Marks LD Schatz GC Van Duyne RP 《The journal of physical chemistry. B》2005,109(22):11158-11162
A novel method to produce solution-phase triangular silver nanoparticles is presented. Ag nanoparticles are prepared by nanosphere lithography and are subsequently released into solution. The resulting nanoparticles are asymmetrically functionalized to produce either single isolated nanoparticles or dimer pairs. The structural and optical properties of Ag nanoparticles have been characterized. Mie theory and the Discrete Dipole Approximation method (DDA) have been used to model and interpret the optical properties of the released Ag nanoparticles. 相似文献
97.
Gary H. Van Domeselaar Glen S. Kwon Lena C. Andrew David S. Wishart 《Colloids and surfaces. B, Biointerfaces》2003,30(4):323-334
This work describes a simple, versatile solid-phase peptide-synthesis (SPPS) method for preparing micelle-forming poly(ethylene oxide)-block-peptide block copolymers for drug delivery. To demonstrate its utility, this SPPS method was used to construct two series of micelle-forming block copolymers (one of constant core-composition and variable length; the other of constant core length and variable composition). The block copolymers were then used to study in detail the effect of size and composition on micellization. The various block copolymers were prepared by a combination of SPPS for the peptide block, followed by solution–phase conjugation of the peptide block with a proprionic acid derivative of poly(ethylene oxide) (PEO) to form the PEO-b-peptide block copolymer. The composition of each block component was characterized by mass spectrometry (MALDI and ES-MS). Block copolymer compositions were characterized by 1H NMR. All the block copolymers were found to form micelles as judged by transmission electron microscopy (TEM) and light scattering analysis. To demonstrate their potential as drug delivery systems, micelles prepared from one member of the PEO-b-peptide block copolymer series were physically loaded with the anticancer drug doxorubicin (DOX). Micelle static and dynamic stability were found to correlate strongly with micelle core length. In contrast, these same micellization properties appear to be a complex function of core composition, and no clear trends could be identified from among the set of compositionally varying, fixed length block copolymer micelles. We conclude that SPPS can be used to construct biocompatible block copolymers with well-defined core lengths and compositions, which in turn can be used to study and to tailor the behavior of block copolymer micelles. 相似文献
98.
Summary The general objective is to provide an alternative methodology based on capillary electrophoresis (CE) to characterize flavonoids from honey and hence determine its botanical origin. The specific objective is to compare the separation of flavonoids by CE with those achieved by HPLC to assess CE as an alternative technique for the determination of honey flavonoids. Fourteen different flavonoids isolated from honey were analysed by MECC and compared to the HPLC separations. It was difficult to find specific experimental conditions to separate all the flavonoids from honey in a single MEKC run. Three chromatographic conditions are optimized and, depending on the flavonoid markers sought in honey, the appropriate detection method should be chosen. Compared to the HPLC results, it is clear that CE could be an alternative technique in honey flavonoids analysis and particularly in the study of its geographical and floral origin. 相似文献
99.
Vanommeslaeghe K Van Alsenoy C De Proft F Martins JC Tourwé D Geerlings P 《Organic & biomolecular chemistry》2003,1(16):2951-2957
Histone deacetylase (HDAC) inhibitors have recently attracted considerable interest because of their therapeutic potential for the treatment of cell proliferative diseases. An X-ray structure of a very potent inhibitor, Trichostatin A (TSA), bound to HDLP (an HDAC analogue isolated from Aquifex aeolicus), is available. From this structure, an active site model (322 atoms), relevant for the binding of TSA and structural analogues, has been derived, and TSA has been minimized in this active site at HF 3-21G* level. The resulting conformation is in excellent accordance with the X-ray structure, and indicates a deprotonation of the hydroxamic acid in TSA by His 131. Also, a water molecule was minimized in the active site. In addition to a similar deprotonation, in accordance with a possible catalytic mechanism of HDAC as proposed by Finnin et al. (M. S. Finnin, J. R. Donigian, A. Cohen, V. M. Richon, R. A. Rifkind and P. A. Marks, Nature, 1999, 401, 188-193), a displacement of the resulting OH- ion in the active site was observed. Based on these results, the difference in energy of binding between TSA and water was calculated. The resulting value is realistic in respect to experimental binding affinities. Furthermore, the mechanism of action of the His 131-Asp 166 charge relay system was investigated. Although the Asp residue in this motif is known to substantially increase the basicity of the His residue, no proton transfer from His 131 to Asp 166 was observed on binding of TSA or water. However, in the empty protonated active site, this proton transfer does occur. 相似文献
100.