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21.
The chemical aspects of isotopic fractionation in a multiple filament thermal ionization source were investigated. Samples
of uranium were loaded as nitrates, chlorides and sulphates. The dependence of measured isotopic ratios on the filament material
and the chemical form of the loading solution was studied. The dependence of the formation of uranium and its oxide ions on
various chemical and instrumental conditions were investigated using tungsten and rhenium filaments. 相似文献
22.
T. Korhonen A. Settels N. Papanikolaou R. Zeller P. H. Dederichs 《Hyperfine Interactions》2001,133(1-4):235-238
We present first-principles calculations of hyperfine fields of heavy impurities in bcc Fe. In particular, the effect of lattice relaxations on the calculated hyperfine fields are studied. The calculations are based on a full-potential Korringa–Kohn–Rostoker Green's-function method for defects and employ the local spin-density approximation for the exchange and correlation effects. The calculated lattice relaxations around the 5sp and 6sp impurities in Fe are found to be relatively small, for the first and second nearest neighbor shells less than 6% of the nearest neighbor distance. Also the estimated relative volume changes induced by the sp impurities are found to be around 60–95% of the elementary volume of Fe, surprisingly small in view of the large atomic volumes of the impurities. The calculated hyperfine fields of 5sp and 6sp elements are compared with available experimental data and it is shown that the inclusion of lattice relaxations in the calculation improves the agreement with experiments. 相似文献
23.
Terhi HirvikorpiMika Vähä-Nissi Ali HarlinMikko Salomäki Sami ArevaJuuso T. Korhonen Maarit Karppinen 《Applied Surface Science》2011,257(22):9451-9454
Commercial polylactide (PLA) films are coated with a thin (20 nm) non-toxic polyelectrolyte multilayer (PEM) film made from sodium alginate and chitosan and additionally with a 25-nm thick atomic layer deposited (ALD) Al2O3 layer. The double-coating of PEM + Al2O3 is found to significantly enhance the water vapor barrier properties of the PLA film. The improvement is essentially larger compared with the case the PLA film being just coated with an ALD-grown Al2O3 layer. The enhanced water vapor barrier characteristics of the PEM + Al2O3 double-coated PLA films are attributed to the increased hydrophobicity of the surface of these films. 相似文献
24.
Let w(z) be an admissible finite-order meromorphic solutionof the second-order difference equation
where R(z, w(z)) is rational in w(z) withcoefficients that are meromorphic in z. Then either w(z) satisfiesa difference linear or Riccati equation or else the above equationcan be transformed to one of a list of canonical differenceequations. This list consists of all known difference Painlevéequations of the above form, together with their autonomousversions. This suggests that the existence of finite-order meromorphicsolutions is a good detector of integrable difference equations. 相似文献
25.
Korhonen H Mikkola S Williams NH 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(2):659-670
The cleavage and isomerisation of uridine 3'-alkylphosphates was studied in the presence of a dinuclear Zn(2+) complex, 3. The rate acceleration of the cleavage by 1 mM 3 is approximately 10(6)-fold under neutral conditions. Most remarkably, the complex also promotes the isomerisation of phosphodiester bonds, although the rate-enhancement is more modest: under neutral conditions complex 3 (1 mM) catalyses isomerisation by about 500-fold. The observation of this reaction shows that the reactions of these substrates catalysed by 3 proceed through a stepwise mechanism involving an intermediate phosphorane. A β(lg) value of -0.92 was determined for the 3-promoted cleavage reaction, and modest kinetic solvent deuterium isotope effects ranging from 1.5 to 2.8 were observed. Isomerisation was less sensitive to the nature of the esterifying group, with a β value of -0.5, and the kinetic solvent deuterium isotope effects were less than 1.5. Most of these characteristics of the 3-promoted cleavage are very similar to those for the cleavage of nucleoside 3'-phosphotriesters. These data are explained by a mechanism in which the complex primarily acts as an electrophilic catalyst neutralising the charge on the phosphate and stabilising an intermediate phosphorane, with general acid catalysis promoting the cleavage reaction. In contrast to the behaviour of triesters, isomerisation is significantly slower than cleavage; this suggests that the changes in geometry that occur during isomerisation lead to a much less stable complex between 3 and the phosphorane intermediate. 相似文献
26.
Pekka J. Korhonen Kari Silvennoinen Jyrki Wallenius Anssi Öörni 《Annals of Operations Research》2013,211(1):565-578
We investigate the connection between weights, scales, and the importance of criteria, when a linear value function is assumed to be a suitable representation of a decision maker’s preferences. Our considerations are based on a simple two-criteria experiment, where the participants were asked to indicate which of the criteria was more important, and to pairwise compare a number of alternatives. We use the participants’ pairwise choices to estimate the weights for the criteria in such a way that the linear value function explains the choices to the extent possible. More specifically, we study two research questions: (1) is it possible to find a general scaling principle that makes the rank order of the importance of criteria consistent with the rank order of the magnitudes of the weights, and (2) how good is a simple, direct method of asking the decision maker to “provide” weights for the criteria compared to our estimation procedure. Our results imply that there is reason to question two common beliefs, namely that the values of the weights would reflect the importance of criteria, and that people could reliably “provide” such weights without estimation. 相似文献
27.
In this paper we propose a computer-graphics based Decision Support System for multiple objective linear programming that builds on the VIG system (Visual Interactive Goal programming). The essential part of the VIG system is Pareto Race, a dynamic and visual approach for exploring the efficient frontier of a multiple objective linear programming problem. Our objective is to extend Pareto Race to large-scale multiple objective linear programming. The approach works with any efficient solutions that are in general not extreme point solutions. Interactive use of computer graphics plays a central role. The approach, the underlying theory, and an illustrative example are described. 相似文献
28.
Ilpo O. O. Korhonen 《Journal of mass spectrometry : JMS》1984,19(2):92-95
The mass spectral fragmentation of trihalogenated methyl esters, formed in the reactions of monochlorinated methyl propenoates and 2-butenoates with Cl2, BrCl and Br2, have been investigated. In most cases α-cleavage gives the base peak, [COOCH3]+, the peaks originating from the subsequent losses of one or two halogen atoms also being abundant. The primary loss of a halogen atom is more prominent in the C4 derivatives, Br˙ and Cl˙ being preferentially lost from the 2- and 3-positions, respectively. The McLafferty rearrangement yields in one case the base peak; the 2-halo compounds could in general be distinguished by that fragmentation. Typical for all 2-bromo-substituted methyl butanoates studied is the base peak, [C3H3]+, at m/z 39, and for some 3-halo compounds the peaks at m/z 95, [C2H4ClO2]+ and 139, [C2H4BrO2]+. 相似文献
29.
The fragmentation of chlorinated guaiacols (2-methoxyphenols) on electron impact has been studied. The most common fragmentation processes are interpreted and in some cases the small differences between spectra of positional isomers are explained. In addition to the well-known alkyl-oxygen fission (loss of methyl radical), metastable ion studies and deuterium labelling have indicated several new fragmentation pathways. The most characteristic are the formation of [M? CH3? HCl]+ and [M? CH3? Cl]+· ions. In general, however, the spectra of positional isomers are shown to be very similar. 相似文献
30.
I. O. O. Korhonen 《Chromatographia》1982,15(8):505-508
Summary The gas chromatography of all chlorinated methyl acetates, methyl propanoates and methyl mono- and dichlorobutanoates has been studied on Carbowax 20M and SE-30 glass capillary columns under various running conditions. The order of elution on a non-polar column was largely determined by the boiling point of esters, whereas on a polar column it was much influenced by the structure of compounds. Complete separation of the combined mixture of all 27 compounds could not be achieved, however, methyl 3,3-dichlorobutanoate was the only ester overlapped on both columns in spite of the various column temperatures used. The best separation of the mixture was on Carbowax 20M with a temperature program from 50°C at 8°C/min, isothermal running conditions leading either to poor separation of volatile components or long analysis time and broad peaks of higher chlorinated esters. The relative retention times for compounds at the various column temperatures are given and the retention order on a polar and on a non-polar column discussed. 相似文献