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141.
Holt JJ Calitree BD Vincek J Gannon MK Detty MR 《The Journal of organic chemistry》2007,72(7):2690-2693
9-formyljulolidine was oxidized via a microwave-assisted Willgerodt-Kindler reaction to the N-piperidine or N-morpholine julolidine-9-thioamide. 9-formyl-1,1,7,7-tetramethyljulolidine gave the corresponding N-piperidine tetramethyljulolidine-9-thioamide. The thioamides were converted to the corresponding carboxamides with trifluoroacetic anhydride. The amide group directed ortho-metalation in the julolidine system, but not in the tetramethyljulolidine system. The resulting anion was captured by dichalcogenide electrophiles. The resulting products were converted to chalcogenoxanthones with phosphorus oxychloride and triethylamine (POCl3/Et3N). 相似文献
142.
The non-stoichiometry and chemical diffusion coefficient of SrFe1−xCoxO3-δ have been measured by steady state and transient thermogravimetry in the temperature range 750–1200 °C at different oxygen
partial pressures. At high oxygen partial pressures, the chemical diffusion coefficient was in the range 1·10−4 – 7·10−4 cm2/s. This, combined with high concentration of disordered vacancies make these materials perhaps the fastest solid oxygen ion
diffusers known at high temperatures and high oxygen partial pressures. However, due to the high concentration of defects
in SrFe1−xCoxO3-δ the compound transforms from a cubic (disordered) perovskite to a brownmillerite type of structure under reduced oxygen partial
pressures below approx. 900 °C. Due to this phase transition, the mobility of oxygen vacancies in SrFe1−xCoxO3-δ decreases up to about an order of magnitude at 850 °C. We also observe an ordering effect at 1000 °C, although smaller in
size, and this is suggested to be due to short range ordering of four-coordinated polyhedra of Fe. For possible use as oxygen
separation membranes, phase stability against sulphur and carbon containing atmospheres is also discussed with respect to
the formation of carbonates and sulphates.
Paper presented at the 6th Euroconference on Solid State Ionics, Cetraro, Calabria, Italy, Sept. 12–19, 1999. 相似文献
143.
David J. Holt William D. Barker Paul R. Jenkins David L. Davies Shaun Garratt John Fawcett David R. Russell Subtrata Ghosh 《Angewandte Chemie (International ed. in English)》1998,37(23):3298-3300
Even eight-membered rings (such as in 2 ) can be formed by ring-closing metathesis of glucose derivatives such as 1 . Enantiomerically pure tricyclic spiro compounds can also be prepared. 相似文献
144.
145.
The structure and surface composition of a Ni3Sn alloy at conditions relevant for the steam reforming reaction was investigated using density functional theory calculations. Both the flat Ni3Sn(0 0 0 1) surface and a surface with steps in the closed packed direction [1 0 0]were considered. The adsorption geometries and energies of the species CO, C, OH and H were calculated. Chemical potentials were used to map out which adsorbates are on the surface under varying conditions. It was found that adsorbates preferably bind to Ni as nearest neighbor with Sn as second-nearest neighbor. The binding energy is slightly stronger than on pure Ni. Adsorbate binding to Sn was found to be very unfavorable. Binding free energies indicate that at high temperature the alloy surface will be predominantly covered by CO and C, and at low temperatures one may find H and almost no OH. Even though the nominal composition of the investigated alloy is Ni3Sn, the surface composition may differ significantly depending on temperature and pressure of the gas phase. This effect was investigated by calculating segregation energies both in the absence and in the presence of adsorbates. For the flat surface, it was found that only the bulk termination is present under relevant conditions. In contrast, it was found that for steps preferential adsorption of CO and C on Ni sites may lead to adsorption-induced segregation at temperatures below 400 °C. When taking segregation into account, the most stable Ni3Sn surfaces will not bind CO or C at the same condition that Ni does. This is in excellent agreement with the previously proven ability of Ni-Sn alloys to inhibit graphite formation. 相似文献
146.
Different organic borates, phosphates, sulphates, and carboxylic acids are evaluated as extraction carriers in three-phase liquid-phase microextraction (LPME). Hydrophilic basic drugs form ion-pairs with the carriers and are extracted as ion-pair complexes into an organic liquid membrane of n-octanol or peppermint oil immobilized in the pores of a polypropylene hollow fiber. From this point, the basic drugs are released into a 20-microL solution of 50mM HCl placed inside the lumen of the hollow fiber (acceptor solution). Simultaneously, the carrier is neutralized by protons from the acceptor solution (protonated to maintain the charge balance). Both water-soluble and water-insoluble carriers are tested. One promising candidate among the water-soluble carriers is 1-heptanesulfonic acid. This is added to the sample solution to a final concentration of 25mM and served to ion-pair the analytes within the sample solution. Among the less water-soluble candidates, a mixture of di(2-ethylhexyl) phosphate (DEHP) and tris(2-ethylhexyl) phosphate (TEHP) serve as efficient carriers. Ten percent (w/w) of each of DEHP and TEHP are added to the organic liquid membrane, and these carriers principally worked through ion-pairing with the analytes at the interface between the sample solution and the organic liquid membrane. Several carriers are found to be compatible with human plasma samples, and bromthymol blue is particularly efficient in combination with these protein-containing matrices. Following optimization of the conditions for bromthymol blue, including saturation of the plasma samples with sodium sulphate, extraction recoveries between 45% and 75% are obtained for eight model drugs after 60 min of extraction. With bromthymol blue as the carrier, highly acceptable validation data are obtained for phenylpropanolamine and practolol extracted from human plasma. 相似文献
147.
Basic drug substances were transported across a thin artificial organic liquid membrane by the application of 300 V d.c. From a 300 microl aqueous donor compartment (containing 10 mM HCl), the drugs migrated through a 200 microm artificial liquid membrane of 2-nitrophenyl octyl ether immobilized in the pores of a polypropylene hollow fiber, and into a 30 microl aqueous acceptor solution of 10 mM HCl inside the lumen of the hollow fiber. The transport was forced by an electrical potential difference sustained over the liquid membrane, resulting in electrokinetic migration of drug substances from the donor compartment to the acceptor solution. Within 5 min of operation at 300 V, pethidine, nortriptyline, methadone, haloperidol, and loperamide were extracted with recoveries in the range 70-79%, which corresponded to enrichments in the range 7.0-7.9. The chemical composition of the organic liquid membrane strongly affected the permeability, and may serve as an efficient tool for controlling the transport selectivity. Water samples, human plasma, and human urine were successfully processed, and in light of the present report, electrokinetic migration across thin artificial liquid membranes may be an interesting tool for future isolation within chemical analysis. 相似文献
148.
Koh SE McDonald KD Holt DH Dulcey CS Chaney JA Pehrsson PE 《Langmuir : the ACS journal of surfaces and colloids》2006,22(14):6249-6255
The work function of indium tin oxide (ITO) substrates was modified with phosphonic acid molecular films. The ITO surfaces were treated prior to functionalization with a base cleaning procedure. The film growth and coverage were quantified by contact angle goniometry and XPS. Film orientation was determined by reflection/absorption infrared spectroscopy using ITO-on-Cr substrates. The absolute work functions of nitrophenyl- and cyanophenyl-phosphonic acid films in ITO were determined by Kelvin probe measurement to be 5.60 and 5.77 eV, respectively. 相似文献
149.
150.
This study examined the hypothesis that filamentous actin associated with the complex cytoskeleton of the kangaroo sperm head and tail may be contributing to lack of plasma membrane plasticity and a consequent loss of membrane integrity during cryopreservation. In the first study, the distribution of G and F actin within Eastern Grey Kangaroo (EGK, Macropus giganteus) cauda epididymidal spermatozoa was successfully detected using DNAse-FITC and a monoclonal F-actin antibody (ab205, Abcam), respectively. G-actin staining was most intense in the acrosome but was also observed with less intensity over the nucleus and mid-piece. F-actin was located in the sperm nucleus but was not discernable in the acrosome or sperm tail. To investigate whether cytochalasin D (a known F-actin depolymerising agent) was capable of improving the osmotic tolerance of EGK cauda epididymal spermatozoa, sperm were incubated in hypo-osmotic media (61 and 104 mOsm) containing a range of cytochalasin D concentrations (0-200 microM). Cytochalasin D had no beneficial effect on plasma membrane integrity of sperm incubated in hypo-osmotic media. However, when EGK cauda epididymidal sperm were incubated in isosmotic media, there was a progressive loss of sperm motility with increasing cytochalasin D concentration. The results of this study indicated that the F-actin distribution in cauda epididymidal spermatozoa of the EGK was surprisingly different from that of the Tammar Wallaby (M. eugenii) and that cytochalasin-D does not appear to improve the tolerance of EGK cauda epididymidal sperm to osmotically induced injury. 相似文献