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1.
Bunyard WC Kadla JF DeYoung J DeSimone JM 《Journal of the American Chemical Society》2001,123(30):7199-7206
The thermal decomposition of the free-radical initiator bis(perfluoro-2-N-propoxyprionyl) peroxide (BPPP) was studied in dense carbon dioxide and a series of fluorinated solvents. For the fluorinated solvents, the observed first-order decomposition rate constants, k(obs), increased with decreasing solvent viscosity, suggesting a single-bond decomposition mechanism. The k(obs) values are comparatively larger in dense carbon dioxide and similar to the "zero-viscosity" rate constants extrapolated from the decomposition kinetics in the fluorinated solvents. The decomposition activation parameters demonstrate a compensation behavior of the activation enthalpy with the activation entropy upon change in solvent viscosity. Comparison of the change in activation parameter values upon change in solvent viscosity for BPPP with two additional initiators, acetyl peroxide (AP) and trifluoroacetyl peroxide (TFAP), further suggests that carbon dioxide exerts a very minimal influence on the decomposition mechanism of these initiators through solvent-cage effects. 相似文献
2.
Glassy carbon electrodes modified with (5-amino-1,10-phenanthroline)bis(bipyridine)ruthium(II) chloride hydrate, [(bpy)2Ru(5-phenNH2)]Cl2·H2O, are shown to oxidize hydrazine with excellent sensitivity. The presence of an amine group on the ruthenium complex facilitates electropolymerization onto the electrode surface. Using cyclic voltammetry, a large catalytic current is observed upon oxidation of hydrazine in phosphate buffer (pH 5.0), compared to the current obtained from the ruthenium-modified electrode with no hydrazine present. The sensitivity of cyclic voltammetry is sufficient for obtaining a linear calibration curve for hydrazine over the range of 10−5 to 10−2 M. Hydrodynamic amperometry was used to determine the working potential for flow injection analysis. The limit of detection for hydrazine was determined to be 8.5 μM using FIA. The thickness of these films was shown to increase linearly with the number of electropolymerization cycles, in the range of 1000-2500 nm for 5-20 cycles, respectively, using Rutherford backscattering spectrometry (RBS). RBS analysis also suggests that the film is multilayered with the outermost layers containing a high ruthenium concentration, followed by layers where the concentration of ruthenium decreases linearly and approaches zero at the electrode surface. 相似文献
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4.
Wijkens P Jastrzebski JT van Der Schaaf PA Kolly R Hafner A van Koten G 《Organic letters》2000,2(11):1621-1624
A general method for the functionalization of Si-Cl terminated carbosilane dendritic molecules via organolithium or organomagnesium reagents is described. Quantitative exchange of the bromine atoms of 4-bromophenyl-functionalized dendrimers affords polylithiated species that are valuable starting materials for further functionalization, e.g., into pyridyl alcohols. The latter were successfully applied as catalyst precursors in a ruthenium-mediated ring-closure metathesis reaction. 相似文献
5.
Stephen K. Taylor Dawn DeYoung Lloyd J. Simons James R. Vyvyan ‡ Mary A. Wemple Noelle K. Wood 《合成通讯》2013,43(9):1691-1701
The nucleophilic opening of epoxides by nitrile enolates using an efficient, convenient protocol is described. The diastereoselectivity of this reaction was explored and found to give syn:anti ratios ranging from 1.1:1.0 to 4.8:1.0. 相似文献
6.
Gordeev SN Zhukov AA de Groot PA Jansen AG Gagnon R Taillefer L 《Physical review letters》2000,85(21):4594-4597
We report on transport measurements of YBa 2Cu 3O (7-delta) single crystals with different oxygen contents in the geometry B, J ||ab (J perpendicularB). Our data show that the vortices become confined between the Cu-O planes below a well-defined temperature at which the effective size 2xi of the vortex core is approximately equal to the period of the Cu-O layers. This confinement strongly increases the vortex liquid freezing temperature. A new melting line is found separating a vortex liquid and a smectic phase, which shows an oscillatory field dependence reflecting differences between commensurate and incommensurate smectic states. 相似文献
7.
Sun R Colin E Ajitanand NN Alexander JM Barton MA DeYoung PA Drake KL Elmaani A Gelderloos CJ Gualtieri EE Guinet D Hannuschke S Jaasma JA Kowalski L Lacey RA Lauret J Norbeck E Pak R Peaslee GF Stern M Stone NT Sundbeck SD Vander Molen AM Westfall GD Yang LB Yee J 《Physical review letters》2000,84(1):43-46
For central collisions of (17-115)A MeV 40Ar+Cu, Ag, Au, an overall balance is determined for the average mass, energy, and longitudinal momentum. Light charged particles and fragments are separated into forward-focused and isotropic components in the frame of the heaviest fragment. Energy removal by the isotropic component reaches 1-2 GeV. For such high deposition energies, statistical multifragmentation models predict much more extensive nuclear disassembly than is observed. 相似文献
8.
Ming Xia LI Yan Ming WANG Ru Ru CHEN* Research Institute of Elemento-Organic Chemistry Nankai University Tianjin Pittsburgh University Medical Center Pittsburgh PA U. S. A 《中国化学快报》2001,(6)
The chiral diols ((,(,((,((-Tetraaryl-1,3-dioxolane-4,5-dimethanols) have been used for the formation of cyclic titanates and similar derivatives of Mg, Al and Zr. These complexes of oxophilic metal centers were employed in catalytic and stiochiometric enantioselective reactions such as enantioselective addition reactions of carbon-centered nucleophiles to aldehydes1, [2+2] cycloadditions2, and Diels-Alder reactions3. So far, the two hydrogen atoms of all this type of diols are in trans form… 相似文献
9.
We consider diffraction by a semi-infinite crack located alonga fusion interface between two differing elastic media. Twotypes of crack, namely open and partially closed cracks, areinvestigated. An open crack is modelled by a stress-free contactboundary condition and a partially closed crack is modelledby a spring contact boundary condition. For the latter, thejump in the stress across the crack is assumed to be proportionalto the jump in the displacement across the crack. This situationarises in, for example, a K-weld where the fine grain of theparent material (for example, ferritic or forged austeniticsteel) is in stark contrast with the coarse-grained weld metal(for example, austenitic weld metal). In the metal weld thedirection of the grain axis varies through the metal. However,diffraction is a local phenomenon and so the austenitic steelis assumed to have a zonal axis so that it may be modelled bya transversely isotropic composite. The ferritic or forged austeniticsteel will be modelled as an isotropic material. 相似文献
10.
C.R. Hoffman T. Baumann D. Bazin J. Brown G. Christian D.H. Denby P.A. DeYoung J.E. Finck N. Frank J. Hinnefeld S. Mosby W.A. Peters W.F. Rogers A. Schiller A. Spyrou M.J. Scott S.L. Tabor M. Thoennessen P. Voss 《Physics letters. [Part B]》2009
The decay energy spectrum for neutron unbound states in 24O (Z=8, N=16) has been observed for the first time. The resonance energy of the lowest lying state, interpreted as the 2+ level, has been observed at a decay energy above 600 keV. The resulting excitation energy of the 2+ level above 4.7 MeV, supplies strong evidence that 24O is a doubly magic nucleus. The data is also consistent with the presence of a second excited state around 5.33 MeV which can be interpreted as the 1+ level. 相似文献