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101.
Stereoselective syntheses of novel 5,6-difunctionalized-2-azabicyclo[2.1.1]hexanes containing 5-anti-fluoro or hydroxyl in one methano bridge and a variety of syn- or anti-chloro, fluoro, hydroxy, methyl, or phenyl substituents in the other methano bridge have been effected. Rearrangements of iodides to alcohols were initiated using Selectfluor. Rearrangement of alcohols to fluorides was initiated using Deoxo-Fluor. Ring opening of 2-azabicyclo[2.2.0]hex-5-ene exo-epoxide with organocopper reagents is regioselective at C(5). 相似文献
102.
103.
Dickson JL Binks BP Johnston KP 《Langmuir : the ACS journal of surfaces and colloids》2004,20(19):7976-7983
Stable carbon dioxide-in-water emulsions were formed with silica nanoparticles adsorbed at the interface. The emulsion stability and droplet size were characterized with optical microscopy, turbidimetry, and measurements of creaming rates. The increase in the emulsion stability as the silica particle hydrophilicity was decreased from 100% SiOH to 76% SiOH is described in terms of the contact angles and the resulting energies of attachment for the silica particles at the water-CO(2) interface. The emulsion stability also increased with an increase in the particle concentration, CO(2) density, and shear rate. The dominant destabilization mechanism was creaming, whereas flocculation, coalescence, and Ostwald ripening played only a minor role over the CO(2) densities investigated. The ability to stabilize these emulsions with solid particles at CO(2) densities as low as 0.739 g/mL is particularly relevant in practical applications, given the difficulty in stabilizing these emulsions with surfactants, because of the unusually weak solvation of the surfactant tails by CO(2). 相似文献
104.
A previous method for the determination of penicillins by direct titration with potassium iodate under strongly acidic conditions has been extended to the assay of some selected cephalosporins. Results are presented, including error and precision analyses, for the determination of cephaloridine, cephalothin and cephalexin. The appropriate stoichiometries are 1 mol cephalosporin to 3 mol iodate for cephalothin and cephaloridine; 1 mol to 2 mol iodate for cephalexin. An irreversible aqueous end-point technique has been compared with the chloroform layer method; the latter gives more precise results for the determination of cephaloridine and cephalothin (0.8% and 1.3% r.s.d. respectively). Comparable precision was obtained by either technique for the determination of cephalexin (1.39% r.s.d.). 相似文献
105.
Rudd DJ Sazinsky MH Merkx M Lippard SJ Hedman B Hodgson KO 《Inorganic chemistry》2004,43(15):4579-4589
The diiron active site in the hydroxylase of Methylococcus capsulatus (Bath) methane monooxygenase (MMOH) has been studied in the oxidized form by X-ray absorption spectroscopy (XAS). Previous investigations by XAS and X-ray crystallography have identified two different distances (3.0 and 3.4 angstroms) between the two Fe atoms in the dinuclear site. The present study has employed a systematic extended X-ray absorption fine structure (EXAFS) fitting methodology, utilizing known and simulated active site and relevant model structures, to determine unambiguously the Fe-Fe separation in the oxidized form of MMOH. Consistent and unique fits were only possible for an Fe-Fe distance of 3.0 angstroms. This methodology was then applied to study potential changes in the active site local structure in the presence of MMOD, a protein of unknown function in multicomponent MMO. Fe K-edge and EXAFS analyses revealed negligible changes in the diiron site electronic and geometric structure upon addition of MMOD to oxidized MMOH. 相似文献
106.
Singh SB Herath K Guan Z Zink DL Dombrowski AW Polishook JD Silverman KC Lingham RB Felock PJ Hazuda DJ 《Organic letters》2002,4(9):1431-1434
[structure: see text]. Integramides A and B are two novel 16-mer linear peptides rich in C(alpha)-methyl amino acids that were isolated from fungal extracts of Dendrodochium sp. by employing a bioassay-guided isolation procedure using recombinant HIV-1 integrase. The structure and stereochemistry were elucidated by a combination of 2D NMR and ESI- and FAB-MS including MS/MS studies and by Marfey's method. Integramides A and B inhibited the coupled reaction of HIV-1 integrase with IC50 values of 17 and 10 microM, respectively. 相似文献
107.
A series of donor-stabilized N-silylphosphoranimine salts [DMAP.PCl2=NSiMe3]+X- (DMAP = 4-(dimethylamino)pyridine) were prepared by the reaction of Cl3P=NSiMe3 with DMAP in the presence of silver salts AgX (X = OSO2CF3, BF4, and SbF6). Repeating the reaction in the absence of AgX gave the chloride salt [DMAP.PCl2=NSiMe3]Cl which has been shown to be in equilibrium with free DMAP and Cl3P=NSiMe3. Attempts to stabilize a N-silylphosphoranimine cation with phosphine donors led to unexpected imine transfer chemistry. For example, Cl3P=NSiMe3 reacts with phosphines, R3P (R = nBu and Ph), to produce the metathesis products PCl3 and R3P=NSiMe3 which subsequently react together to afford the N-phosphinophosphoranimines R3P=N-PCl2 and ClSiMe3 as a byproduct. 相似文献
108.
An array of eight interdigitated microband gold electrodes (IDEs) has been developed together with electrophoretic separation for analysis of chlorinated hydroquinones (ClHQs) and benzoquinones (ClBQs). The IDE chip positioned very close to the separation capillary outlet served as an amplification/detection system without the requirement for frequent "capillary-electrode" alignment. ClHQs, electrophoretically migrating to the IDE surface, were oxidized at +1.1 V by seven electrodes of the array and then detected by the remaining electrode, poised at -0.1 V. Conversely, ClBQs were detected at +1.1 V by the detecting electrode after having been reduced at the 7 adjacent electrodes poised at -0.1 V. There was an amplification effect on both the detecting electrode as well as the adjacent electrodes because of the recycle between ClHQs and ClBQs. The detecting "amplification" current response was dependent on the potentials applied, the position of the detecting electrode on the array, the number of adjacent electrodes being used for recycling and the distance between the oxidative and reductive electrodes. Micellar electrokinetic chromatography (MEKC) separation of the analytes was achieved using 30 mM sodium dodecyl sulfate (SDS) with a detection limit in the range of 2-20 micro M. In addition to a facile "capillary-electrode" alignment, the important aspect described here was the capability of detecting through recycling a reduced compound (in the case of ClHQs) at a negative potential to circumvent fouling and electroactive interferences. An appealing feature was also the concurrent oxidation/reduction detection for each compound to ascertain peak assignment, as interfering compounds are less likely to exhibit the same oxidative/reductive characteristics and electrophoretic mobilities as the target analytes. 相似文献
109.
[reaction: see text] A formal enantioselective synthesis of allocolchicine and a synthesis of a C-ring analogue have been achieved by employing an intramolecular direct arylation of an aryl chloride to form the biaryl carbon-carbon bond and the seven-membered ring. 相似文献
110.
Keith C. C. Bancroft Laila H. Morcos Guindi Arthur F. Temple 《Journal of heterocyclic chemistry》1978,15(8):1521-1523
Several 2,1,3-benzothiadiazin-4(3H) one 2,2-dioxides were synthesized as possible sweetening agents by reacting sulfamoyl chloride with various anthranilic acid derivatives. The isolation of 1-methyl-4-methoxy-2,1,3-benzothiadiazine 2,2-dioxide and preparation of 3,4-dihydro-2,1,3-benzothiadiazine 2,2-dioxide is also reported. 相似文献