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251.
Several instrumental neutron activation analysis techniques (parametric, comparative, and ko-standardization) are evaluated using three reference materials. Each technique is applied to National Institute of Standards and Technology standard reference materials, SRM 1577a (Bovine Liver) and SRM 2704 (Buffalo River Sediment), and the United States Geological Survey standard BHVO-1 (Hawaiian Basalt Rock). Identical (but not optimum) irradiation, decay, and counting schemes are employed with each technique to provide a basis for comparison and to determine sensitivities in a routine irradiation scheme. Fifty-one elements are used in this comparison; however, several elements are not detected in the reference materials due to rigid analytical conditions (e.g., insufficient length of irradiation or activity for radioisotope of interest decaying below the lower limit of detection before counting interval). Most elements are normally distributed around certified or consensus values with a standard deviation of 10%. For some elements, discrepancies are observed and discussed. The accuracy, precision, and sensitivity of each technique are discussed by comparing the analytical results to consensus values for the Hawaiian Basalt Rock to demonstrate the diversity of multielement applications. 相似文献
252.
K. I. Pashkevich V. I. Filyakova V. G. Ratner O. G. Khomutov 《Russian Chemical Bulletin》1998,47(7):1239-1247
Efficient procedures for the regioselective synthesis of fluoroalkyl-containing threefive-, six-, and seven-membered heterocycles
as well as of related fused compounds, namely, α,β-epoxyketones, α,β-aziridinylketones, pyrazoles, pyrazolines, isoxazolines,
1,2-dithiolenes, amino- and mercaptopyrimidines, Δ3,5-2-thioxo-1,3,2-thiazaphosphorines, Δ3,5-2-thioxo-1,3,2-oxazaphosphorines, 2,3-dihydro-1,4-diazepines, azirino[1,2-a]quinoxalines, benzo[b]-and naphtho[2,3-b]-1,4-diazepines, and triazolopyridazines, which have been developed by the authors and coworkers, are summarized. The α-
and β-functionalized fluoroalkylcontaining carbonyl compounds (β-diketones, β-ketoesters, their salts, regioisomeric β-aminovinyl
ketones, β-aminovinylthiones, β-hydroxyketones, α,β-enones, and their halogen derivatives) were used as synthons in the processes
of formation of the above-mentioned heterocycles.
Dedicated to the memory of Academician I. Ya. Postovskii on his 100th birthday.
Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1279–1286, July, 1998. 相似文献
253.
A Hubbard model-based expression for the magnetic exchange interaction, 2J, between the spins of a radical ion pair is derived for a generic donor-bridge-acceptor (D-B(n)-A) system in terms of the superexchange coupling, t, between molecular orbitals of the donor, bridge, and acceptor and the energies, epsilon, and same-site Coulomb repulsions, U, of these orbitals. The formulation is used to predict 2J for the photophysically well-characterized series phenothiazine-p-(phenylene)n-perylene diimide, n = 2,3,4,5, where the superexchange coupling is calculated with multipathway, second- and third-order perturbation theory coupled with the extended Huckel formalism. U and epsilon are estimated through experimentally determined electrochemical potentials. Due to multiple interactions arising from the large distance between magnetic centers in these donor-bridge-acceptor systems, agreement with experiment was substantially improved when third-order corrections were included in the calculation of t and 2J. 相似文献
254.
The geometric and electronic structural properties of symmetric and asymmetric metal cluster-molecule-cluster' complexes have been explored. The metals include Au, Ag, Pd, and Al, and both benzenedithiol and the three isometric forms of dicyanobenzene are included as bridging molecules. Calculated properties such as cluster-molecule interface geometry, electronic state, degree of metal --> molecule charge transfer, metal-molecule mixing in the highest occupied molecular orbital-lowest unoccupied molecular orbital (HOMO-LUMO) energy region, the HOMO-LUMO gap, cluster --> cluster' charge transfer as a function of external field strength and direction, and the form of the potential profile across such complexes have been examined. Attempts are made to correlate charge transport with the characteristics of the cluster-complex systems. Indications of rectification in complexes that are asymmetric in the molecule, clusters, and molecule-cluster interfaces are discussed. The results obtained here are only suggestive because of the limitations of the cluster-complex model as it relates to charge transport. 相似文献
255.
The phosphorescence of tetrabutylammonium tetrahalomanganate salts has been investigated, both in the crystal and in the fused salt. The lifetime behavior of the 4T1 → 6A transition in these tetrahedral systems is extremely unusual: The phosphorescence remains in the low viscosity melt; the bromide lifetime is ten times smaller than the chloride at room temperature, but about twenty times larger at 130°C; there is highly specific structure in the lifetime data of the solid which correlates with thermal phase transitions. Dilution experiments demonstrate that cooperative effects and electronic charge transfer processes are not important in these species. An explanation is suggested in terms of both low Franck—Condon factors and of frequency or Stokes shift of accepting modes for vibronically-induced radiative decay by the steric packing effects of the neighboring organic ion. Experiments for distinguishing the effects of these two mechanisms are suggested. 相似文献
256.
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259.
A statistical-dynamic model for calculating product state distributions for reactive collisions is presented. For the vibrational-translational coupling Franck-Condon type approximations are adopted which lead to very good agreement with exact quantum calculations in the limit of the collinear arrangement. The rotational degrees of freedom are treated statistically. The energy distribution among vibrational translational and rotational degrees of freedom is discussed as a function of the masses and the attractive part of the potential. Extension from triatomic to polyatomic exchange reactions are considered. A detailed comparison with other simple models is made. 相似文献
260.
Gabriel P. Lpez Buddy D. Ratner 《Journal of polymer science. Part A, Polymer chemistry》1992,30(11):2415-2425
The influence of substrate temperature during plasma deposition on the chemistry of the organic films formed was examined. Plasma ionization of precursor gases that are polymerizable by conventional mechanisms was studied. Film chemistry was analyzed by x-ray photoelectron spectroscopy (XPS). Monomers that polymerize by a free radical mechanism [2-hydroxyethyl methacrylate (HEMA) and hexafluorobutadiene (HFB)] form more regular polymers (i.e. with less molecular rearrangement) by plasma deposition at low substrate temperatures than monomers that polymerize by ionic mechanisms [ethylene oxide (EO) and tetrahydrofuran (THF)]. In all cases, lowering the substrate temperature during deposition produces films with elemental composition virtually identical to that of the precursor gas. Comparison of high-resolution XPS spectra of the deposited films with those for model polymers suggests that functional groups in the monomers used to generate the plasma are incorporated to a greater extent at low substrate temperatures. The effect of plasma power on the degree of precursor structure retention obtained when reduced substrate temperatures are employed was also examined. Plasma deposition of HEMA at low substrate temperatures and low plasma power produces thin films which are, by core level XPS, indistinguishable from HEMA polymerized by conventional methods. EO and THF films coated at low substrate temperatures on glass, polyethylene, or polytetrafluoroethylene varied widely in surface chemistry due to differences in film uniformity. Film quality (uniformity) is enhanced for these low reactivity precursors by pretreating substrates with an argon plasma. © 1992 John Wiley & Sons, Inc. 相似文献