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131.
Taking into account softening effects in connection with conventional inelastic material models can cause ill-posed boundary value problems. These problems can be established by obtaining no unique solution for the resulting algebraic system or by having a strong mesh dependence of the numerical results. This is the consequence of losing ellipticity of the governing field equations. A possible approach to solve these problems is to introduce a non-local field function in the model which includes an internal material length scale. For this purpose a gradient-enhanced free energy function is used for the current continuum damage model from which two variational equations are resulting. Calculations with less effort can be achieved due to the enhancement of the free energy function in comparison to other approaches. The mentioned model is applied to a material with locally varying damage properties (yield limits). Furthermore, the model is able to describe crack propagation in cases of completely damaged material. Therewith, a matrix material including precipitates, such as carbides, is modeled. This allows to investigate ship screws, which usually exhibit the mentioned composition, with regard to the influence of cavitation. Cavitation describes the implosion of risen vapor bubbles, whereby the impact on screws causes heavy damages which can lead to a complete destruction. (© 2014 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
132.
Andreas Fischer 《Annals of Pure and Applied Logic》2009,157(2-3):130-138
We study the Hardy field associated with an o-minimal expansion of the real numbers. If the set of analytic germs is dense in the Hardy field, then we can definably analytically separate sets in , and we can definably analytically approximate definable continuous unary functions. A similar statement holds for definable smooth functions. 相似文献
133.
Jochen Münchenberg Jens R. Goerlich Axel K. Fischer Peter G. Jones Reinhard Schmutzler 《无机化学与普通化学杂志》1996,622(2):348-354
Synthesis, Structure, and some Reactions of N-(N′,N′,N″,N″-tetramethyl)guanidinyl-substituted Phosphoryl Compounds The tetramethylguanidinyl-substituted phosphoryl compounds 1 – 10 were prepared in the reaction of the appropriate chlorophosphoryl compounds with either N′,N′,N″,N″-tetramethylguanidine (HTMG) or N-trimethylsilyl-(N′,N′,N″,N″-tetramethyl)guanidine (TMSTMG). With methyl iodide 1 reacted with N-alkylation to give the ammonium salt 11. 1 reacted with BF3 · Et2O at both imino nitrogen atoms with formation of the bis-BF3-adduct 12 . The X-ray structure determination of phenylphosphonic acid-bis(N′,N′,N″,N″-tetramethylguanidinide) 3 shows shortened PN-bonds and widened PNC-angles, consistent with the partial double bond character of the PN-bond. 相似文献
134.
The three molybdenum-N2 complexes [Mo(N2)(dpepp)(depe)] (1), [Mo(N2)(dpepp)(dppe)] (2), and [Mo(N2)(dpepp)(1,2-dppp)] (3), all of which contain a combination of a bi- and a tridentate phosphine ligand, were prepared and investigated by vibrational and (31)P NMR spectroscopy. As a tridentate ligand bis(2-diphenylphosphinoethyl)phenylphosphine (dpepp) has been employed. The three different bidentate ligands are 1,2-bis(diethylphosphino)ethane (depe), 1,2-bis(diphenylphosphino)ethane (dppe), and R-(+)-1,2-bis(diphenylphosphino)propane (1,2-dppp). N-N as well as metal-N vibrations of 1-3 are identified and interpreted in terms of the geometric and electronic structures of the complexes. (31)P NMR spectra are recorded and fully analyzed. Moreover, correlation spectroscopy (COSY)-45 measurements are performed to determine the relative signs of coupling constants. Special attention is directed to a detection of different isomers and their (31)P NMR, as well as vibrational spectroscopic properties. The implications of the results for the area of synthetic nitrogen fixation with phosphine complexes are discussed. 相似文献
135.
Jan-Niklas Dienemann Shu-Yu Chen Manuel Hitzenberger Montana L. Sievert Stephan M. Hacker Sean T. Prigge Martin Zacharias Michael Groll Stephan A. Sieber 《Angewandte Chemie (International ed. in English)》2023,62(31):e202304533
The development of novel anti-infectives requires unprecedented strategies targeting pathways which are solely present in pathogens but absent in humans. Following this principle, we developed inhibitors of lipoic acid ( LA ) salvage, a crucial pathway for the survival of LA auxotrophic bacteria and parasites but non-essential in human cells. An LA -based probe was selectively transferred onto substrate proteins via lipoate protein ligase (LPL) in intact cells, and their binding sites were determined by mass spectrometry. Probe labeling served as a proxy of LPL activity, enabling in situ screenings for cell-permeable LPL inhibitors. Profiling a focused compound library revealed two substrate analogs ( LAMe and C3 ) as inhibitors, which were further validated by binding studies and co-crystallography. Importantly, LAMe exhibited low toxicity in human cells and achieved killing of Plasmodium falciparum in erythrocytes with an EC50 value of 15 μM, making it the most effective LPL inhibitor reported to date. 相似文献
136.
Hyehwang Kim Dr. Zheng-wang Qu Prof. Dr. Stefan Grimme Nahil Al-Zuhaika Prof. Dr. Douglas W. Stephan 《Angewandte Chemie (International ed. in English)》2023,62(43):e202312587
The phosphino-phosphonium cations of the form [R3PPR′2]+ are labile and provide access to the constituent Lewis acidic and Lewis basic fragments. This permits frustrated Lewis pair-type addition reactions to alkynes, affording unprecedented phosphino-phosphination reactions and giving cations of the form [cis-R3PCHC(R′′)PR′2]+. This reactivity is further adapted to prepare several examples of a rare class of dissymmetric cis-olefin-linked bidentate phosphines. 相似文献
137.
Men Y Rieger J Roth SV Gehrke R Kong X 《Langmuir : the ACS journal of surfaces and colloids》2006,22(20):8285-8288
A polymer dispersion consisting of soft latex spheres with a diameter of 135 nm was used to produce a crystalline film with face-centered cubic (fcc) packing of the spheres. Different from conventional small-molecule and hard-sphere colloidal crystals, the crystalline latex film in the present case is soft (i.e., easily deformable). The structural evolution of this soft colloidal latex film under stretching was investigated by in-situ synchrotron ultra-small-angle X-ray scattering. The film exhibits polycrystalline scattering behavior corresponding to fcc structure. Stretching results not only in a large deformation of the crystallographic structure but also in considerable nonaffine deformation at high draw ratios. The unexpected nonaffine deformation was attributed to slippage between rows of particles and crystalline grain boundaries. The crystalline structure remains intact even at high deformation, suggesting that directional anisotropic colloidal crystallites can be easily produced. 相似文献
138.
PLD-assisted VLS growth of aligned ferrite nanorods, nanowires, and nanobelts-synthesis, and properties 总被引:4,自引:0,他引:4
Morber JR Ding Y Haluska MS Li Y Liu JP Wang ZL Snyder RL 《The journal of physical chemistry. B》2006,110(43):21672-21679
We report here a systematic synthesis and characterization of aligned alpha-Fe2O3 (hematite), epsilon-Fe2O3, and Fe3O4 (magnetite) nanorods, nanobelts, and nanowires on alumina substrates using a pulsed laser deposition (PLD) method. The presence of spherical gold catalyst particles at the tips of the nanostructures indicates selective growth via the vapor-liquid-solid (VLS) mechanism. Through a series of experiments, we have produced a primitive "phase diagram" for growing these structures based on several designed pressure and temperature parameters. Transmission electron microscopy (TEM) analysis has shown that the rods, wires, and belts are single-crystalline and grow along <111>m or <110>h directions. X-ray diffraction (XRD) measurements confirm phase and structural analysis. Superconducting quantum interference device (SQUID) measurements show that the iron oxide structures exhibit interesting magnetic behavior, particularly at room temperature. This work is the first known report of magnetite 1D nanostructure growth via the vapor-liquid-solid (VLS) mechanism without using a template, as well as the first known synthesis of long epsilon-Fe2O3 nanobelts and nanowires. 相似文献
139.
Raman Maksimenka Markus Margraf Juliane Khler Alexander Heckmann Christoph Lambert Ingo Fischer 《Chemical physics》2008,347(1-3):436-445
In this article we report a femtosecond time-resolved transient absorption study of a neutral organic mixed-valence (MV) compound with the aim to gain insight into its charge-transfer dynamics upon optical excitation. The back-electron transfer was investigated in five different solvents, toluene, dibutyl ether, methyl-tert-butyl ether (MTBE), benzonitrile and n-hexane. In the pump step, the molecule was excited at 760 nm and 850 nm into the intervalence charge-transfer band. The resulting transients can be described by two time constant. We assign one time constant to the rearrangement of solvent molecules in the charge-transfer state and the second time constant to back-electron transfer to the electronic ground state. Back-electron transfer rates range from 1.5 × 1012 s−1 in benzonitrile through 8.3 × 1011 s−1 in MTBE, around 1.6 × 1011 s−1 in dibutylether and toluene and to 3.8 × 109 s−1 in n-hexane. 相似文献
140.
Mohamed GG Szesni N Fischer H 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2008,71(1):161-168
The fragmentation pathways of allenylidene and carbene complexes have been studied using FAB mass spectrometry in comparison with thermal analyses (TGA, DrTG and DTA). Both the decomposition modes are investigated and the possible fragmentation pathways are suggested. The use of mass and thermal analyses (TGA and DTA) in the analyses of allenylidene and carbene complexes allowed the characterization of the fragmentation pathways in MS. The major pathway includes successive loss of carbon monoxide followed by fragmentation of the organic part of the allenylidene or carbene molecules. This is also confirmed by thermogravimetric analysis (TGA) where the first step involves the loss of carbon monoxide followed by the organic ligand. The nature of each step; exothermic or endothermic, is also studied using DTA technique. The kinetic parameters of the thermal decomposition are also studied using the Coates-Redfern method. 相似文献