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941.
A series of nitrosyl complexes of empirical formula Kn[M(CN)5NO], where M = V, Cr, Mn and Co and n = 3, or M = Mo and n = 4, have been prepared which are notional analogues of the widely used vasodilator sodium nitroprusside. Their reactivity towards common nucleophiles (OH?, NH2R, NHR2, HS? and RS?), acid and photolysis has been investigated to elucidate the desired properties required of new metal nitrosyls which may have some potential as new non-cyanide-based vasodilators. 相似文献
942.
Philippe Quevauviller Rob Ritsema Roberto Morabito Wilfried M. R. Dirkx Salvatore Chiavarini Jos M. Bayona Olivier F. X. Donard 《应用有机金属化学》1994,8(6):541-549
Biogeochemical pathways of tin species in the environment are still controversial, e.g. with regard to methylation and transmethylation phenomena, owing to the fact that the identification of methylated tin-compounds is often difficult. The previous tentative identification of a mixed methylbutyltin compound in sediment and biological samples by GC/AAS after hydride generation gave an illustration of this problem. This compound was previously identified in sediments by other authors and also suspected to occur in a contaminated sediment sample from the Boyardville Marina, France. The retention time obtained by GC/AAS corresponded to the actual retention time of a mixed methylbutyltin calibrant. However, additional checks demonstrated that the compound detected was actually monophenyltin. This evidence was produced by a thorough analysis of a selected sediment sample by alternative techniques such as GC/AAS and GC/AES after pentylation, GC/FPD and GC/MS. The results presented highlight the need for a full identification of compounds to avoid mis-interpretation. 相似文献
943.
944.
A kinetic model is presented to describe the high temperature (1800 K < T < 3000 K) surface oxidation of particulate boron in a hydrocarbon combustion environment. The model includes a homogeneous gas-phase B/O/H/C oxidation mechanism consisting of 19 chemical species and 58 forward and reverse elementary reactions, multi-component gas-phase diffusion, and a heterogeneous surface oxidation mechanism consisting of ‘elementary’ adsorption and desorption reaction steps. Thermochemical and kinetic parameters for the surface reactions are estimated from available experimental data and/or elementary transition state arguments. The kinetic processes are treated using a generalized kinetics code, with embedded sensitivity analysis, for the combustion of a one-dimensional (particle radius), spherical particle. Model results are presented for the oxidation of a 200 μm boron particle in a JP-4/air mixture at ambient temperatures of 1400 K and 2000 K. These results include temperature and gas-phase species profiles as a function of radial distance and particle burning rates. © 1994 John Wiley & Sons, Inc. 相似文献
945.
R. D. Patel 《国际化学动力学杂志》1994,26(4):403-406
Pseudo-first-order rate constants and activation parameters have been measured for the solvolysis of 2-chloroquinoxaline in various aquo-organic mixtures using methanol, ethanol, and isopropanol as the organic solvent. Excellent linear correlations are found between lnk and the mol fraction of cosolvent and ln[H2O]. The medium effect on the rates of solvolysis is assessed by Grunwald–Winstein's mY correlationship. The estimated values of m (0.55–0.72) and the entropy of activation (148–212 J deg?1 mol?1) for the reactions are well in the range for a bimolecular aromatic substitution reactions. © 1994 John Wiley & Sons, Inc. 相似文献
946.
The kinetics of the title reactions were investigated in a discharge flow tube by using laser magnetic resonance detection of HO2. The upper limits for the bimolecular rate constants for the reactions of HO2 with H2S (k1), CH3SH (k2), and CH3SCH3 (k3) are <3 × 10?15, <4 × 10?15, and <5 × 10?15 cm3 molecule?1 s?1, respectively, at 298 K. Our upper limit for k1 is three orders of magnitude lower than the previously reported value. Measurements at higher temperatures also yield similar upper limits. Our results suggest that HO2 is not an important oxidant for these reduced compounds in the atmosphere. © 1994 John Wiley & Sons, Inc. 相似文献
947.
The kinetics of the thermal decomposition reaction of gaseous 3,3,6,6-tetramethyl-1,2,4,5-tetroxane (ACDP) in the presence of n-octane was studied in the 403.2–523.2 K temperature range. This reaction yields acetone as the organic product. Under optimum conditions, first-order kinetics were observed, included when the S/V ratio of the Pyrex reaction vessel was increased by a nearly six-fold factor. In the range 443.2–488.2 K the temperature dependence of the rate constants for the unimolecular reaction in conditioned vessels is given by In k1/(s?1) = (31.8 ± 2.5) ? [(39.0 ± 2.5)/RT]. The value of the energy of activation in kcal/mol correspond to one O? O bond homolysis of the ACDP molecule in a stepwise biradical initiated decomposition mechanism. At the lower reaction temperatures as well in preliminary experiments participation of a surface catalyzed ACDP decomposition process could be detected. © 1994 John Wiley & Sons, Inc. 相似文献
948.
949.
In contrast to stochastic differential equation models used for the calculation of the term structure of interest rates, we
develop an approach based on linear dynamical systems under non-stochastic uncertainty with perturbations. The uncertainty
is described in terms of known feasible sets of varying parameters. Observations are used in order to estimate these parameters
by minimizing the maximum of the absolute value of measurement errors, which leads to a linear or nonlinear semi-infinite
programming problem. A regularized logarithmic barrier method for solving (ill-posed) convex semi-infinite programming problems
is suggested. In this method a multi-step proximal regularization is coupled with an adaptive discretization strategy in the
framework of an interior point approach. A special deleting rule permits one to use only a part of the constraints of the
discretized problems. Convergence of the method and its stability with respect to data perturbations in the cone of convexC
1-functions are studied. On the basis of the solutions of the semi-infinite programming problems a technical trading system
for future contracts of the German DAX is suggested and developed.
Supported by the Stiftung Rheinland/Pfalz für Innovation, No. 8312-386261/307. 相似文献
950.
S. I. Pesotskii R. B. Lyubovskii W. Biberacher M. V. Kartsovnik V. I. Nizhankovskii N. D. Kushch H. Kobayashi A. Kobayashi 《Journal of Experimental and Theoretical Physics》2002,94(2):431-433
Behavior of the de Haas-van Alphen (dHvA) oscillations depending on the angle between the magnetic field direction and the perpendicular to conducting layers in the quasi-two-dimensional organic metal α-(BETS)2 KHg(SCN)4 was studied in detail. The angular dependence of the dHvA oscillation amplitude exhibits a series of minima (at ±43.2°, ±64.6°, and ±72.0°) related to the “zero spin” effect, through which it is possible to estimate the splitting factor. An analysis of this value suggests that many-body interactions in the compound studied are either absent or at least radically weakened. 相似文献