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181.
Ivana Kiov Zdenk To
ík Milo Budínský Ondej imk Radek Liboska Dominik Rejman Ondej Pa
es Ivan Rosenberg 《Tetrahedron letters》2009,50(49):6745-6747
A straightforward procedure leading to the new phosphonylating reagent, methyl 4-toluenesulfonyloxymethylphosphonate, requiring no chromatographic purification is described. This stable reagent works with the same efficiency as dimethyl and other dialkyl esters for the introduction of an O-phosphonomethyl moiety while, in contrast to dimethyl ester, it does not cause any unwanted methylation of sensitive functionalities. Its utility for the alkylation of protected nucleosides in high yield is exemplified. 相似文献
182.
Annekathrin Seifert Dominik Scheid Gerald Linti Prof. Dr. Thomas Zessin 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(44):12114-12120
The gallium(I) derivative [Ga({N(dipp)CMe}2CH)] ( 1 ; dipp=2,6‐diisopropylphenyl) undergoes facile oxidative addition reactions with various element–hydrogen bonds including N? H, P? H, O? H, Sn? H, and H? H bonds. This was demonstrated by its reaction with triphenyltin hydride, ethanol, water, diethylamine, diphenylphosphane, and dihydrogen. All products were characterized by means of single‐crystal X‐ray structure determination, NMR spectroscopy, IR spectroscopy, and mass spectrometry. 相似文献
183.
Andrea Schuy Theo Woike Dominik Schaniel 《Journal of Sol-Gel Science and Technology》2009,50(3):403-408
Photoswitchable hybrid materials are successfully prepared by embedding guanidinium nitroprussides (GuNP, (CN3H6)2[Fe(CN)5NO]) into mesopores of transparent xerogel monoliths. The such prepared hybrid materials exhibit a higher photostability than
the corresponding GuNP solutions, whereby the chemical stability of the [Fe(CN)5NO]2−-anion in titania gel is nearly infinite. By irradiation with light in the blue-green spectral range one nitrosyl isomer is
formed by a 180° rotation of the NO ligand changing the Fe–NO into a Fe–ON coordination (SI), which is detected by the shift
of the ν(NO) stretching vibration from 1945 cm−1 (Fe–NO) to 1820 cm−1 (Fe–ON). Consequently there is enough space around the NO-ligand for such movement in xerogel mesopores. The embedding in
silica xerogels increases the achievable population of the isomeric nitrosyl configuration to about 15% with respect to a
single crystalline powder where only 9% are reached. 相似文献
184.
Natalya Hessenauer‐Ilicheva Alicja Franke Dr. Dominik Meyer Wolf‐D. Woggon Prof. Dr. Rudi van Eldik Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(12):2941-2959
Two new models for cytochrome P450 in which the thiolate axial ligand is replaced by an RSO3? group, form oxo‐iron(IV) porphyrin π‐cation radicals as sole oxidation products in “peroxo shunt” reactions (see scheme) independent of the nature of the employed solvent (polar or non‐polar) and electronic nature of the porphyrin rings.
185.
Dominik Nied Wim Klopper Prof. Dr. Frank Breher Prof. Dr. 《Angewandte Chemie (International ed. in English)》2009,48(8):1411-1416
Ge, whiz! A detailed study of the synthesis, structure, redox chemistry, and bonding properties of pentagerma[1.1.1]propellane ( 1 , see picture) examines fundamental aspects of the interactions between the bridgehead germanium atoms. DFT and CASSCF calculations unravel the biradicaloid characteristics of 1 , and preliminary reactivity studies indicate that 1 features some radical‐type behavior.
186.
The applicability of different concentration detection methods for online quantification of liposomes upon asymmetric flow field‐flow fractionation was investigated. Filter‐extruded egg phosphatidylcholine liposomes of different size were used. Online quantification using a differential refractive index (dRI) detector was found feasible for relatively high sample loads in the magnitude of 100 μg lipid (under the chosen fractionation conditions). UV–Vis detection of the turbidity of liposomes was ruled out as online detection method because turbidity increases with particle size and the signal is not only concentration but also particle‐size dependent. Staining of liposomes by Rhodamine phosphatidylethanolamine or Sudan Red and subsequent online UV–Vis detection at the absorption maximum of the dye enabled quantification with much higher sensitivity than dRI detection. Furthermore analyte loss and carry‐over phenomena upon repeated injection of varying liposome sample loads were studied using regenerated cellulose (RC) membranes as accumulation wall. It could be shown that RC membranes are prone to adsorption in case of very small sample loads (0.5 μg). This effect may be overcome by pre‐saturation of the membrane with sample loads of at least 2 μg. For higher sample loads adsorptive losses play a minor role. Recovery from pre‐saturated membranes reached approximately 100% and carry‐over was found negligible. 相似文献
187.
The Finite Cell Method (FCM) combines the fictitious domain approach with high-order finite elements and adaptive integration. For linear elastic problems with smooth solution, FCM has been shown to achieve exponential rates of convergence in energy norm, while its structured cell grid guarantees simple mesh generation irrespective of the geometric complexity involved. In this contribution, the FCM idea is combined with standard finite element technology for the solution of geometrically nonlinear problems. In particular, a modified FCM formulation is introduced, which resets the deformed configuration of the fictitious domain to the deformation-free reference configuration after each Newton iteration. Numerical experiments show that this intervention allows for stable nonlinear FCM analysis with very small values of the penalty parameter, while the accuracy of the geometrically nonlinear solution within the physical domain remains unaffected. (© 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
188.
Dominik Kortschak Hansjörg Albrecher 《Methodology and Computing in Applied Probability》2009,11(3):279-306
In this paper we extend some results about the probability that the sum of n dependent subexponential random variables exceeds a given threshold u. In particular, the case of non-identically distributed and not necessarily positive random variables is investigated. Furthermore
we establish criteria how far the tail of the marginal distribution of an individual summand may deviate from the others so
that it still influences the asymptotic behavior of the sum. Finally we explicitly construct a dependence structure for which,
even for regularly varying marginal distributions, no asymptotic limit of the tail of the sum exists. Some explicit calculations
for diagonal copulas and t-copulas are given.
Dominik Kortschak was supported by the Austrian Science Fund Project P18392. 相似文献
189.
The (-)-sparteine-coordinated lithiosilanes (Lis)-4 and 5 crystallize as monomers with coordination numbers of 4 and 3 on lithium and represent the first structurally characterized enantiopure lithiosilanes. Both systems are also monomeric in solution with Si-Li contacts detected by 29Si-7Li couplings in the 29Si NMR spectrum (for 5 even at room temperature). 相似文献
190.
Craig L. Bull Tetsuya Kawashima Paul F. McMillan Denis Machon Dominik Daisenberger E. Takayama-Muromachi 《Journal of solid state chemistry》2006,179(6):1762-1767
We prepared samples of cubic γ-MoNx (x∼0.5) by high-pressure-high-temperature synthesis. N atom site occupancies within the defect rock salt structure were determined from time-of-flight neutron diffraction and powder X-ray diffraction data by Rietveld analysis. The results show that N atoms occupy only octahedral sites within the structure. The semi-metallic compound is a superconductor, with determined by SQUID magnetometry. The compressibility of the material was determined by synchrotron X-ray diffraction measurements at high pressure in the diamond anvil cell. The vibrational density of states was studied by Raman scattering spectroscopy. 相似文献