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51.
S. S. Krishnan M. T. Bayley A. J. W. Hitchman S. C. Lin K. G. McNeill J. E. Harrison 《Journal of Radioanalytical and Nuclear Chemistry》1987,114(1):173-180
This work describes an in vivo neutron activation analysis facility for small samples, such as rats or human hand, using two 100 g252Cf neutron sources. The irradiation area is a cylindrical space, of 12 cm diameter and about 15 cm length, with fairly uniform neutron flux distribution. Experimental data on the reproducibility, effects of volume and other conditions for in vivo measurements are given. Comparative atomic absorption data on calcium measurements on rats are reported. The facility is now used for animal experiments as well as human hand irradiations in clinical investigations involving calcium metabolism and bone diseases. 相似文献
52.
Bernard Gordon Jacqueline S. Butler Ian R. Harrison 《Journal of polymer science. Part A, Polymer chemistry》1987,25(8):2139-2142
Catalysts bound to polymers in the form of crosslinked beads have been demonstrated to have a number of advantages over homogeneous catalysts. However, there are several problems that exist due to the polymer support being in the form of a bead. The rate of reaction depends on the presence of solvents that adequately swell the bead in order to allow access to the catalytic sites. Differences in polarity and reactant size can inhibit diffusion into the bead. Recently a new system has been developed whereby tris(triphenyl phosphine) chlororhodium (I) (Wilkinson's catalyst) is bound to the surface of polyethylene single crystals. Polyethylene single crystals have a very high surface to volume ratio allowing for greater ease of reaction compared to a bead system. In a previous paper we showed that there is a dramatic increase in catalytic activity and that the reaction rate increased as the polarity of solvent was increased, even in ethanol where the homogeneous catalyst is not soluble and the polystyrene bead support would not swell. In this letter we are describing the activity of hydrogenation of olefins contained in both large and/or polar molecules. The results demonstrate the advantages of supported catalysts on polyethylene single crystals rather than on polymer beads. 相似文献
53.
The hydrothermal syntheses of a family of new alkali-metal/ammonium vanadium(V) methylphosphonates, M(VO(2))(3)(PO(3)CH(3))(2) (M = K, NH(4), Rb, Tl), are described. The crystal structures of K(VO(2))(3)(PO(3)CH(3))(2) and NH(4)(VO(2))(3)(PO(3)CH(3))(2) have been determined from single-crystal X-ray data. Crystal data: K(VO(2))(3)(PO(3)CH(3))(2), M(r) = 475.93, trigonal, R32 (No. 155), a = 7.139(3) ?, c = 19.109(5) ?, Z = 3; NH(4)(VO(2))(3)(PO(3)CH(3))(2), M(r) = 454.87, trigonal, R32 (No. 155), a = 7.150(3) ?, c = 19.459(5) ?, Z = 3. These isostructural, noncentrosymmetric phases are built up from hexagonal tungsten oxide (HTO) like sheets of vertex-sharing VO(6) octahedra, capped on both sides of the V/O sheets by PCH(3) entities (as [PO(3)CH(3)](2-) methylphosphonate groups). In both phases, the vanadium octahedra display a distinctive two short + two intermediate + two long V-O bond distance distribution within the VO(6) unit. Interlayer potassium or ammonium cations provide charge balance for the anionic (VO(2))(3)(PO(3)CH(3))(2) sheets. Powder X-ray, TGA, IR, and Raman data for these phases are reported and discussed. The structures of K(VO(2))(3)(PO(3)CH(3))(2) and NH(4)(VO(2))(3)(PO(3)CH(3))(2) are compared and contrasted with related layered phases based on the HTO motif. 相似文献
54.
Harrison JF 《The journal of physical chemistry. A》2005,109(24):5492-5497
The magnitude and algebraic sign of the molecular quadrupole moments of the homonuclear diatomic molecules N2, O2, F2, P2, S2 and Cl2 are analyzed by expressing them as a sum of the quadrupole moments of the free atoms and an induced molecular quadrupole due to bond formation. This induced molecular quadrupole is further analyzed in terms of in situ atomic dipole and quadrupole moments constructed following the electron partitioning method suggested by Hirshfeld. These in situ moments are interpreted in terms of the sigma and pi character of the chemical bonds and are compared with those predicted by the DMA method of Stone (The Theory of Intermolecular Forces; Clarendon: Oxford, 1996). 相似文献
55.
Alex. G. Harrison R. Krishna Mohan Rao Kallury 《Journal of mass spectrometry : JMS》1980,15(6):284-288
The H2 and CH4 chemical ionization mass spectra of a selection of substituted nitrobenzenes have been determined. It is shown that reduction of the nitro group to the amine is favoured by high source temperatures and the presence of water in the ion source. The H2 chemical ionization mass spectra are much more useful for distinguishing between isomeric compounds than the CH4 CI mass spectra because of the more extensive fragmentation. For ortho substituents bearing a labile hydrogen abundant [MH ? H2O]+ fragments are observed. When the substituent is electron-releasing both ortho and para substituted nitrobenzenes show abundant [MH? OH]+ fragment ions while meta substituted compounds show abundant loss of NO and NO2 from [MH]+. The latter fragmentation is interpreted in terms of protonation para to the substituent or ortho to the vitro function, while the first two fragmentation routes arise from protonation at the nitro group. When the substituent is electron-attracting the chemical ionization mass spectra of isomers are very similar except for the H2O loss reaction for ortho compounds. 相似文献
56.
In a previous study we reported an efficient, accurate multiresolution solver for the Kohn-Sham self-consisitent field (KS-SCF) method for general polyatomic molecules. This study presents an efficient numerical algorithm to evalute Hartree-Fock (HF) exchange in the multiresolution SCF method to solve the HF equations. The algorithm employs fast integral convolution with the Poission kernel in the nonstandard form, screening the sparse multiwavelet representation to compute results of the integral operator only where required by the nonlocal exchange operator. Localized molecular obitals are used to attain near linear scaling. Results for atoms and molecules demonstrate reliable precision and speed. Calculations for small water clusters demonstrate a total cost to compute the HF exchange potential for all n(occ) occpuied MOs scaling as O(n(occ) (1.5)). 相似文献
57.
The O?˙ chemical ionization mass spectrri of the C8H10 alkylbenzenes, o-, m-. andp -xylene and ethylbenzene, show formation of [M ? H + O]?, [M ? H]?, [M ? H2]?˙ and, for the xylenes, [M ? CH3 + O]? as primary reaction products; the relative importance of these products depends on the isomer. However, [OH]? is a primary product from reaction of O?˙ with both the C8H10 isomers and hydrogen-containing impurities; [OH]? reacts further with the alkylbenzenes to produce [M ? H]? with the result that the chemical ionization mass spectra depend on experimental conditions such as sample size and the presence of impurities. The collision-induced charge inversion mass spectra of the [M ? H + O]? and [M ? H]? products allow only distinction of ethylbenzene from the xylenes. However, the collision-induced charge inversion mass spectra of the [M ? H2]?˙ ions show differences which allow identification of each isomer. 相似文献
58.
The charge exchange mass spectra of a selection of C5-C7 ketones have been measured using [CS2]+˙, [COS]+˙ and [N2O]+. as reagent ions. The low energy charge exchange with [CS2]+˙ or [COS]+˙ provides simple primary ion mass spectra, which readily permit structure elucidation in contrast to metastable ion spectra. In several cases, isomer distinction is easier from the charge exchange mass spectra than from the electron impact mass spectra. The energy transfer from [N2O]+˙ is sufficiently high for complex spectra resembling electron impact mass spectra to be obtained. 相似文献
59.
Using specifically labelled compounds we have made a detailed study of the source of the hydrogen transferred in the elimination of C3H6 from the molecular ion of phenyln-propyl ether following electron impact ionization and from the protonated (and ethylated) molecule following chemical ionization. The migrating hydrogen originates from all three positions of the npropyl group but not in the ratio expected for randomization of the alkyl hydrogens prior to transfer. The source of the migrating hydrogen is similar for both electron impact ionization and chemical ionization, indicating that the factors governing the rearrangement are the same for both modes of ionization. From a comparison of the results for labelled 2,6-dimethyl phenyl n-propyl ethers with the results for the unsubstituted ether it is concluded that hydrogen transfer occurs only to the ether oxygen and not to the phenyl ring. A two-step mechanism involving a set of competing reversible hydrogen transfer reactions followed by C? O bond cleavage is proposed to explain the results. 相似文献
60.
E. R. Bauminger P. M. Harrison D. Hechel I. Nowik A. Treffry 《Journal of Radioanalytical and Nuclear Chemistry》1995,190(2):237-241
Iron(III) monomers, dimers and clusters have been identified by Mössbauer spectroscopy during the initial stages of iron incorporation into ferritins, following Fe(II) oxidation. Iron(III) monomers seem to arise from dimer dissociation. Some of the monomers are transferred from iron poor to iron rich ferritin molecules, where they join the iron core clusters. Horse spleen ferritin, several variants of human H chain ferritin andEscherichia coli ferritin (Ec-FTN) can all accept the iron from human H chain ferritin. The small iron cores of Ec-FTN are different from those of mammalian ferritins, which indicates that the structure of the iron core depends on the protein shell. 相似文献