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211.
212.
Kalina Kostova Annalaura Lorenzi-Riatsch Yoshihiko Nakashita Manfred Hesse 《Helvetica chimica acta》1982,65(1):249-251
Synthesis of Macrocyclic Lactones by Ring Enlargement Reaction Treatment of 3-(1-nitro-2-oxocyclohexyl)propanal ( 1 ) prepared by Michael addition of 2-nitrocyclohexanon and acrylaldehyde with methyltri (2-propoxy)tita-nium yielded a mixture of 2 and 3 which was converted into 6-nitro-9-decanolide ( 4 ). 相似文献
213.
(Z)-2-Butenyl-dimethoxyborane adds smoothly to propanal and benzaldehyde to afford the homoallyl alcohols (R*,R*)- 1 and (R*,R*)- 2 , In contrast (E)-2-butenyl-dimethoxyborane leads to adducts having the (R*,S*)-configuration. Dimethoxy-(Z)-2-pentenylborane, dimethoxy-(Z)-(2-methyl-2-butenyl)borane and (2Z,4E)-or (2E,4Z)hexadienyl-dimethoxyborane, treated with propanal, give (R*,R*)- 3 , (R*,R*)- 4 , (E),(R*,S*)- 5 and (Z),(R*, R*)- 5 , respectively. A transition state model implying a pericyclic electron motion is in perfect agreement with the regio- and stereoselective outcome of these borane reactions. 相似文献
214.
In the past few years millimeter and submillimeter wave spectroscopy has been the backbone for modern molecular line astronomy. The detection of unstable and high-temperature molecular species in the interstellar environment has stimulated the development of methods of detecting molecular ions, radicals and unstable molecules in the laboratory by means of millimeter wave technology. Some of the recent experimental advances as well as the developments which have occurred in the analysis of high resolution rotational and vibrational spectra with regard to understanding molecular dynamics will be discussed. 相似文献
215.
Andrea Schfer Berthold Fischer Henning Paul Ren Bosshard Manfred Hesse Max Viscontinif 《Helvetica chimica acta》1992,75(6):1955-1964
This paper marks the first reported detection of radical cations by Electrospray-Ionization Mass Spectrometry (ESI-MS). Electron Spin Resonance (ESR) measurements have proven that the detected radical cation existed already in solution and has not been generated by the electrospray ionization technique. However, we observed that the radical cation can be generated by changes in the ionization conditions. A molar mixture of 2-amino-5,6,7,8-tetrahydro-5-methylpterin-4(4H)-one dihydrochloride ( = 5,6,7,8-tetrahydro-N(5)-methylpterin-2 HCl, N(5)-MTHP-2 HCl), and tris(pentane-2,4-dionato)iron(III) in MeCN at pH 2–3 leads to the formation of a [bis(pentane-2,4-dionato)(2-amino-5,6,7,8-tetrahydro-5-methylpteridin-4 (4H)-one)]iron complex ( = [bis(pentane-2,4-dionato) (5,6,7,8-tetrahydro-N(5)-methylpteridin)]iron complex) which can be detected by ESI-MS. The results suggest that this complex might be an FeII radical cation, which could possibly be a suitable model complex for the active center of the phenylalanine hydroxylase. In the same solution, the stable radical cation of N(5)-MTHP is identified by ESI-MS and ESR. 相似文献
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A scaling of a nonnegative matrixA is a matrixXAY ?1, whereX andY are nonsingular, nonnegative diagonal matrices. Some condition may be imposed on the scaling, for example, whenA is square,X=Y or detX=detY. We characterize matrices for which there exists a scaling that satisfies predetermined upper and lower bound. Our principal tools are a piecewise linear theorem of the alternative and a theorem decomposing a solution of a system of equations as a sum of minimal support solutions which conform with the given solutions. 相似文献
219.
In this paper a two-dimensional discrete element method with rigid, polygonal particles is used to model material failure of granular as well as quasi-brittle materials. Different models for soft contact as well as cohesion between the particles are presented. The capabilities of the method are demonstrated simulating simplistic granular model materials as well as complex concrete specimens with an artificial microstructure. (© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
220.
Manfred H. Ulz 《PAMM》2014,14(1):571-572
Hierarchical two-scale methods are computationally very powerful as there is no direct coupling between the macro- and microscale. Such schemes develop first a microscale model under macroscopic constraints, then the macroscopic constitutive laws are found by averaging over the microscale. The heterogeneous multiscale method (HMM) is a general top-down approach for the design of multiscale algorithms. While this method is mainly used for concurrent coupling schemes in the literature, the proposed methodology also applies to a hierarchical coupling. This contribution discusses a hierarchical two-scale setting based on the heterogeneous multi-scale method for quasi-static problems: the macroscale is treated by continuum mechanics and the finite element method and the microscale is treated by statistical mechanics and molecular dynamics. Our investigation focuses on an optimised coupling of solvers on the macro- and microscale which yields a significant decrease in computational time with no associated loss in accuracy. In particular, the number of time steps used for the molecular dynamics simulation is adjusted at each iteration of the macroscopic solver. A numerical example demonstrates the performance of the model. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献