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991.
7-Benz[c] acridinemethanols as tetracyclic analogs of the 2-phenyl-4-quinolinemethanol antimalarials
Andre Rosowsky Michael Chaykovsky Sandra A. Yeager Richard A. St. Amand May Lin Edward J. Modest 《Journal of heterocyclic chemistry》1971,8(5):809-820
A series of new 7-benz[c]acridinemethanols and 5,6-dihydro-7-benz[c]acridinemethanols was prepared as rigid, tetracyclic analogs of the antimalarial 2-phenyl-4-quinolinemethanols. Condensation of 5,7-dichloroisatin with 6-chloro-, 7-chloro-, and 6,7-dichloro-1-tetralone furnished halogenated 5,6-dihydro-7-benz[c]acridinecarboxylic acids, which were transformed into the corresponding acid chlorides, acyl malonates, α-bromomethyl ketones, and epoxides. Fully aromatic members of the series obtained via dehydrogenation of the 5,6-dihydro acids were likewise converted into epoxides via the acylmalonate route. Although all the epoxides studied proved to be exceptionally resistant to ring-opening by di-n-butylamine, probably on account of steric effects, they could be cleaved readily with piperidine or morpholine. Nmr spectra of the resulting amino alcohols suggest that these compounds exist in a single preferred conformation stabilized by internal O-H····N hydrogen bonding, and that free rotation about the side chain C-C bond does not occur at room temperature. 相似文献
992.
Pyrolytic process has a promising potential for the environmentally friendly upgrading of lignocellulosic and plastic waste.
Thermogravimetry and pyrolysis-gas chromatography-mass spectrometry (Py-GC/MS) were used to get information about the reactive
decomposition of PCL in binary mixtures with microcrystalline cellulose (MC) or sisal fibres (SF). Preliminary thermogravimetric
investigation showed that biomass is thermally degraded at lower temperatures than PCL and this process has a predominant
influence on the thermal behaviour of the mixtures. Discrepancies between the experimental and predicted TG/DTG profiles were
considered as a measurement of the extent of interactions occurring on co-pyrolysis. It was found that reactivity of PCL was
slightly increased in PCL-SF binary mixtures. Evolution of acidic products from cellulose and hemicelluloses decomposition
may promote PCL degradation in binary mixtures with SF. It seems that the co-pyrolysis process could have potential for the
environmentally friendly transformation of biocomposites. 相似文献
993.
Ibrahim El-Sayed El-Kholy Morcos Michael Mishrikey Hassan Mostafa Feid-Allah 《Journal of heterocyclic chemistry》1981,18(1):105-110
The reaction of piperidine, morpholine, piperazine or dimethylamine with several coumarins, 3-bromocoumarin, 4,6-diaryl-2H-pyran-2-ones and 3-bromo-4,6-diaryl-2H-thiopyran-2-ones gave o-hydroxycinnamic acid amides, benzofurans, open-chain δ-oxoamides and thiophene derivatives, respectively. 相似文献
994.
This article describes a new complementary peptide separation and purification concept that makes use of a novel mixed-mode reversed-phase/weak anion-exchange (RP/WAX) type stationary phase. The RP/WAX is based on N-(10-undecenoyl)-3-aminoquinuclidine selector, which is covalently immobilized on thiol-modified silica particles (5 microm, 100 A pore diameter) by radical addition reaction. Remaining thiol groups are capped by radical addition with 1-hexene. This newly developed separation material contains two distinct binding domains in a single chromatographic interactive ligand: a lipophilic alkyl chain for hydrophobic interactions with lipophilic moieties of the solute, such as in the reversed-phase chromatography, and a cationic site for anion-exchange chromatography with oppositely charged solutes, which also enables repulsive ionic interactions with positively charged functional groups, leading to ion-exclusion phenomena. The beneficial effect that may result from the combination of the two chromatographic modes is exemplified by the application of this new separation material for the chromatographic separation of the N- and C-terminally protected tetrapeptide N-acetyl-Ile-Glu-Gly-Arg-p-nitroanilide from its side products. Mobile phase variables have been thoroughly investigated to optimize the separation and to get a deeper insight into the retention and separation mechanism, which turned out to be more complex than any of the individual chromatography modes alone. A significant anion-exchange retention contribution at optimal pH of 4.5 was found only for acetate but not for formate as counter-ion. In loadability studies using acetate, peptide masses up to 200 mg could be injected onto an analytical 250 mm x 4 mm i.d. RP/WAX column (5 microm) still without touching bands of major impurity and target peptide peaks. The corresponding loadability tests with formate allowed the injection of only 25% of this amount. The analysis of the purified peptide by capillary high-performance liquid chromatography (HPLC)-UV and HPLC-ESI-MS employing RP-18 columns revealed that the known major impurities have all been removed by a single chromatographic step employing the RP/WAX stationary phase. The better selectivity and enhanced sample loading capacity in comparison to RP-HPLC resulted in an improved productivity of the new purification protocol. For example, the yield of pure peptide per chromatographic run on RP/WAX phase was by a factor of about 15 higher compared to the standard gradient elution RP-purification protocol. 相似文献
995.
996.
Liang X Parkinson JA Weishäupl M Gould RO Paisey SJ Park HS Hunter TM Blindauer CA Parsons S Sadler PJ 《Journal of the American Chemical Society》2002,124(31):9105-9112
As platforms for the design of metal-based therapeutic and diagnostic agents, macrocycles are rigid enough to provide strong metal binding sites and orient functional groups stereoselectively, yet flexible enough to accommodate structural changes required for induced-fit recognition of biological targets. We consider the recognition of the Zn(II) complex of the bis-tetraazamacrocycle xylyl-bicyclam, a potent anti-HIV agent, by the coreceptor CXCR4, a G-protein-coupled receptor used by HIV for membrane fusion and cell entry. NMR studies show that the macrocycles of Zn(II)(2)-xylyl-bicyclam perchlorate exist in aqueous solution as two major configurations, trans-I (nitrogen chirality R,S,R,S), and trans-III (S,S,R,R). Acetate addition induced a major structural change. X-ray crystallography shows that the acetate complex contains the unusual cis-V cyclam configuration (R,R,R,R and folded) with bidentate coordination of acetate to Zn(II) plus second-coordination-sphere double H-bond formation between diagonal NH protons on the opposite cyclam face and acetate carboxylate oxygens. Detailed 1D and 2D NMR studies show that the major configuration of Zn(II)(2)-xylyl-bicyclam acetate in aqueous solution is cis-V/trans-I. Molecular modeling shows that an analogous cis-V site can be formed when Zn(II)(2)-xylyl-bicyclam binds to CXCR4, involving the carboxylate groups of Asp262 (Zn(II) coordination) and Glu288 (double H-bonding). The second cyclam can adopt the trans-I (or trans-III) configuration with Zn(II) binding to Asp171. These interactions are consistent with the known structure-activity relationships for bicyclam anti-HIV activity and receptor mutation. Consideration of the anti-HIV activity of xylyl-bicyclam complexes of other metal ions suggests that affinity for carboxylates, configurational flexibility, and kinetic factors may all play roles in receptor recognition. For example, Pd(II) cyclam complexes interact only weakly with axial ligands and are inflexible and inactive, whereas Co(III) cyclams bind carboxylates strongly, are configurationally flexible, and yet have low activity. Our findings should aid the design of new generations of active macrocycles including highly specific chemokine receptor antagonists. 相似文献
997.
Effect of Enzyme Modification of Corn Grits on their Properties as an Adsorbent in a Skarstrom Pressure Swing Cycle Dryer 总被引:1,自引:0,他引:1
Corn grits have been tested as a desiccant in a pressure swing adsorption (PSA) system to produce dry air. Two sizes of unmodified corn grits were tested in the PSA system: 2.16 and 0.978 mm in diameter, which dried moist air to dew points of –42°C and –69°C, respectively. A modification technology has been developed for the corn grits that gives an increase in the operational adsorptive capacity in a pressure swing adsorption system, so that they remove as much moisture from air as molecular sieves at the same conditions. After modification, 2.16 mm corn grits dry moist air to a –56°C dew point and the 0.978 mm corn grits dry air to a –80°C dew point. The modification process creates surface modifications on the corn grits apparently making more adsorption sites easily available. The modification procedure increases the specific surface area of the grits and possibly decreases the crystallinity, which would make more hydroxyl groups available for adsorption of water. Possible applications of using corn grits in the pressure swing adsorption system include industrial gas dryers, sorptive cooling air conditioners, and recycling equipment for industrial solvents. 相似文献
998.
The refolding of the reduced-denatured insulin from bovine pancreas was investigated with the size exclusion chromatography (SEC). It was shown that the reduced-denatured insulin originally denatured with 7.0 mol L?1 guanidine hydrochloride (GuHCI) or 8.0 mol L?1 urea could not be refolded with a non-oxidized mobile phase. Although the oxidized and reduced glutathione (GSSG and GSH) were employed in the oxidized mobile phase, the reduced-denatured insulin still could not be renatured. However, in the presence of 2.0 mol Lt-1 urea in the oxidized mobile phase employed, the reduced-denatured insulin can be refolded with SEC, and the aggregation of denatured insulin can be diminished by urea. In addition, the disulfide exchange of reduced-denatured insulin also can be accelerated with GSSG/GSH in the oxidized mobile phase. The three disulfide bridges of insulin were formed correctly and the reduced-unfolded insulin can be renatured completely. The results were further tested with reversed-phase liquid chromatography (RPLC) and hydrophobic interaction chromatography (HIC). 相似文献
999.
Brieler FJ Grundmann P Fröba M Chen L Klar PJ Heimbrodt W Krug von Nidda HA Kurz T Loidl A 《Journal of the American Chemical Society》2004,126(3):797-807
Arrays of highly ordered Zn(1-x)MnxS quantum wires with x ranging from 0.01 to 0.3 and with lateral dimensions of 3, 6, and 9 nm were synthesized within mesoporous SiO2 host structures of the MCM-41 and SBA-15 type. The hexagonal symmetry of these arrays (space group p6m) and the high degree of order was confirmed by X-ray diffraction and transmission electron microscopy (TEM) studies. Physisorption measurements show the progressive filling of the pores of the SiO2 host structures, while TEM and Raman studies reveal the wire-like character of the incorporated Zn(1-x)MnxS nanostructures. X-ray absorption near-edge structure, extended X-ray absorption fine structure, photoluminescence excitation (PLE), and electron paramagnetic resonance studies confirm the good crystalline quality of the incorporated Zn(1-x)MnxS guest species and, in particular, that the Mn2+ ions are randomly distributed and are situated on tetrahedrally coordinated cation sites of the Zn(1-x)MnxS wires for all x up to 0.3. The amount of Mn2+ ions loosely bound to the surface of the Zn(1-x)MnxS nanowires is less than 4% of the total Mn content even for the 3 nm nanostructures up to the highest Mn content of x = 0.3. The effects of the reduction of the lateral dimensions on electronic properties of the diluted magnetic semiconductor were studied by PLE spectroscopy. Due to the quantum confinement of the excitons in the wires an increase of the direct band gap with decreasing particle size is observed. 相似文献
1000.
Spies MA Woodward JJ Watnik MR Toney MD 《Journal of the American Chemical Society》2004,126(24):7464-7475
Free energy profiles for alanine racemase from Bacillus stearothermophilus have been determined at pH 6.9 and 8.9 from global analysis of racemization progress curves. This required a careful statistical design due to the problems in finding the global minimum in mean square for a system with eight adjustable parameters (i.e., the eight rate constants that describe the stepwise chemical mechanism). The free energy profiles obtained through these procedures are supported by independent experimental evidence: (1). steady-state kinetic constants, (2). solvent viscosity dependence, (3). spectral analysis of reaction intermediates, (4). equilibrium overshoots for progress curves measured in D(2)O, and (5). the magnitudes of calculated intrinsic kinetic isotope effects. The free energy profiles for the enzyme are compared to those of the uncatalyzed and the PLP catalyzed reactions. At pH 6.9, PLP lowers the free energy of activation for deprotonation by 8.4 kcal/mol, while the inclusion of apoenzyme along with PLP additionally lowers it by 11 kcal/mol. 相似文献