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Summary The aquation kinetics of [Co(Py)4Cl2]X salts (X=Cl–, NO
3
–
, IO
4
–
, ClO
4
–
, SCN– and N
3
–
) in EtOH/H2O have been widely investigated over a range of solvent compositions. Similarly, the aquation rate constants were determined in aqueous solution (11 v/v) containing other organic solvents. The study reveals the existence of specine solvation of the activated complex and that the rate constant associated with the rate-determining step of the reaction depends to some extent on the ionizing power of the medium. The influence of the counter ions on the aquation rate is also discussed. Basicity, the capacity of the nucleophiles to abstract the exchangeable proton from a titanium selenite inorganic exchanger was found to follow the order: SCN–3
–
–4
–
4
–
3
–
. 相似文献
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Ian Drake Gregoire Cardoen Andrew Hughes Kebede Beshah Kenneth L. Kearns Tianlan Zhang John Reffner Casey Wolf Ralph Even 《Journal of polymer science. Part A, Polymer chemistry》2019,57(13):1373-1388
A polyurea macromer (PUM) was synthesized and dispersed in basic conditions to form self‐assembled nanoparticles (<20 nm dispersions, up to 30 wt % aq. soln.). These nanoparticles enabled surfactant‐free emulsion polymerization to form hybrid polyurea‐acrylic particles despite the absence of a measureable water‐soluble fraction. The Tg of the starting PUM material was a strong function of the PUM's extent of neutralization and hydration (varying between 100 °C and >175 °C) due to changes in hydrogen and ionic bonding. Two separate hybrid polyurea‐acrylic emulsion systems were prepared: one by direct polymerization of (meth)acrylic monomers in the presence of the nanodispersion and a second by a physical blend of PUM nanodispersion with an acrylic latex control. The direct polymerization method resulted in a hybrid emulsion particle size that developed by a mechanism resembling conventional emulsion polymerization and was unlike that described for seeded polyurethane dispersion systems. Film hardness was shown to increase with increasing coating thickness for the hybrid film prepared by direct polymerization. The resulting mechanical properties could be explained by applying mechanical models for a composite foam structure. These results were unprecedented for normal elastomer films. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019, 57, 1373–1388 相似文献
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Srinivasan A Kebede N Saavedra JE Nikolaitchik AV Brady DA Yourd E Davies KM Keefer LK Toscano JP 《Journal of the American Chemical Society》2001,123(23):5465-5472
We have found O(2)-substituted diazeniumdiolates, compounds of structure R(2)N-N(O)=NOR' that are under development for various possible pharmaceutical uses, to be rather photosensitive. With R = ethyl and R' = methyl, benzyl, or 2-nitrobenzyl, the observed product distributions suggest that two primary pathways are operative. A minor pathway involves the extrusion of nitrous oxide (N(2)O) with simultaneous generation of R(2)N(*) and R'O(*), which may then form amines, aldehydes, and alcohols. The major reaction pathway is an interesting photochemical cleavage of the N=N bond to form a nitrosamine (R(2)NN=O) and an oxygen-substituted nitrene (R'ON). The intermediacy of the O-nitrene was inferred from the production of abundant oxime, via rearrangement of the O-nitrene to a C-nitroso compound (R'ON --> O=NR'), and subsequent tautomerization to the more stable oxime. Involvement of the O-nitrene was confirmed by trapping with 2,3-dimethyl-2-butene to form the aziridine and with oxygen to generate the nitrate ester. 2-Nitro substitution on the benzyl derivative had surprisingly little effect on the reaction course. For each compound examined, minor amounts of nitric oxide (NO), presumably produced by secondary photolysis of the nitrosamine, were observed. Time-resolved infrared experiments provided additional support for the above reaction pathways and confirmed that the nitrosamine is a primary photoproduct. We have also found that the relative contributions of the reaction pathways can be altered in certain derivatives. For example, when R' = 2,4-dinitrophenyl, the contribution of the nitrosamine/O-nitrene-forming pathway was diminished. Pharmacological implications of these results are discussed. 相似文献
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Kebede Beshah James E. Mark Jerome L. Ackerman Alan Himstedt 《Journal of Polymer Science.Polymer Physics》1986,24(6):1207-1225
The application of 29Si solution and solid-state cross-polarization/magic-angle spinning (CP/MAS) nuclear magnetic resonance (NMR) techniques to the study of structural features in polydimethylsiloxane (PDMS) model endlinked elastomeric networks is explored. The relationship between the topological (network) functionality of a structural moiety, which determines network mechanical properties, and its chemical (spectral) functionality, which is reported by the NMR, is discussed. The second-order spectral shifts corresponding to topographical functionality variation within a chemical functionality class are usually sufficiently well resolved in these networks to allow positive identification of a variety of structural features. The basic PDMS repeat unit, ? OSi(CH3)2? , is found to possess an axially symmetric chemical shift tensor with σ∥ = ?56.8 ppm downfield from TMS, and σ⊥ = ?4.4 ppm. This axial symmetry does not result from rapid reorientation about the chain axis. The NMR spectrum reveals defects in model endlinked networks. In the case of vinyl-endlinked systems, the defects are ascribed to the formation of elastically ineffective loops. Hydroxyl-endlinked systems contain either loops or else trifunctional junctions (hydrolyzed before chain coupling could take place) and dangling chain ends. The CP/MAS technique provides an order-of-magnitude reduction over standard solution techniques in the time to acquire a spectrum from a network not containing paramagnetic doping. 13C spectra of PDMS systems are not as informative as 29Si spectra. 相似文献
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Europium-doped barium aluminate (BaAl x O y :Eu2+) phosphors were obtained at low temperatures (500°C) using the solution — combustion of corresponding metal nitrate-urea solution mixtures. The particle size and morphology and the structural and luminescent properties of the synthesized phosphors were examined by means of scanning electron microscopy (SEM), X-ray diffraction (XRD), Electron diffraction spectroscopy (EDS) and photoluminescence (PL). It was found that the change in Ba: Al molar ratios showed greatly influence not only on the particle size and morphology, but also on their PL spectra and crystalline structure. The structure of BaAl x O y nanophosphors changes from a hexagonal Ba2Al10O17 phase for samples with 6:100 molar ratios to a hexagonal BaAl2O4 one with an increase in Ba content. The peak of the emission band occurs at a longer wavelength (around 615 nm) with a decrease in Ba concentration but displays a broad blue-green emission band composed from two emissions with the maximum at 495 and 530nm coming from Eu2+ in two sites for increasing Ba content. The blue-green emission is probably due to the influence of 5d electron states of Eu2+ in the crystal field because of atomic size variation causing crystal defects while the red emission is due to f - f transitions. These findings clearly demonstrate the possibility of fine tuning the colour emission. 相似文献
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A large and robust selectivity improvement of ion-selective electrodes is presented for the measurement of abundant ions. An improvement in selectivity by more than two orders of magnitude has been attained for the hydrophilic chloride ions measured in a dilute background of the lipophilic ions perchlorate and salicylate in a pulsed chronopotentiometric measurement mode. This is attributed to a robust kinetic discrimination of the dilute lipophilic ions in this measuring mode, which is not possible to achieve in classical potentiometry. Maximum tolerable concentrations of the interfering ions are found to be on the order of 30 μM before causing substantial changes in potential. As an example of practical relevance, the robust detection of chloride in 72 μM salicylate (reflecting 1:10 diluted blood) with a detection limit of 0.5 mM chloride is demonstrated. Corresponding potentiometric sensors did not give a useful chloride response under these conditions. 相似文献
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Hyoun Woo Kim Mesfin Abayneh Kebede Hyo Sung Kim Myung Ho Kong Chongmu Lee 《Journal of luminescence》2009,129(12):1619-793
We reported the preparation and annealing effects of Zinc oxide ZnO/SiOx core-shell nanowires, in which ZnO shell layers were deposited by sputtering. Based on scanning electron microscopy, transmission electron microscopy, X-ray diffraction, and photoluminescence (PL) investigations, we monitored structural and optical changes with respect to the post-annealing process. The samples were mostly amorphous with some crystalline ZnO structure, whereas annealing at 900-1000 °C reduced the amount of Zn elements. Thermal annealing induced change in the shape of the PL emission spectra. 相似文献