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811.
812.
Micro-machining processes on metalic microstructures are influenced by the crystal structure, i. e. the grain orientation. Furthermore, the chip formation underlies large deformations. To perform finite element simulations of micro-cutting processes, a large deformation material model is necessary in order to model the hyperelastic and finite plastic material behaviour. In the case of cp-titanium material with hcp-crystal structure the anisotropic behaviour must be considered by an appropriate set of slip planes and slip directions. In the present work the impact of the grain orientation on the plastic deformation is demonstrated by means of finite element simulations of a finite deformation single slip crystal plasticity model. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
813.
Felix Diewald Charlotte Kuhn Ricardo Blauwhoff Michaela Heier Stefan Becker Stephan Werth Martin Horsch Hans Hasse Ralf Müller 《PAMM》2016,16(1):519-520
In the proposed phase field model a continuous order parameter indicates the phase distribution (liquid/gas). An energy density functional which is dependent on the surface tensions and defined by three contributions yields the total energy of the system. An equilibrium state is then computed by minimizing this energy of the system using an evolution equation. Details of the algorithmic implementation are discussed by illustrative examples. (© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim) 相似文献
814.
Gong X Moghaddam MJ Sagnella SM Conn CE Danon SJ Waddington LJ Drummond CJ 《Colloids and surfaces. B, Biointerfaces》2011,85(2):2137-359
An amphiphile prodrug, 5′-deoxy-5-fluoro-N4-(palmityloxycarbonyl) cytidine or 5′-deoxy-5-fluoro-N4-(hexadecanaloxycarbonyl) cytidine (5-FCPal), consisting of the same head group as the commercially available chemotherapeutic agent Capecitabine, linked to a palmityl hydrocarbon chain via a carbamate bond is reported. Thermal analysis of this prodrug indicates that it melts at ∼115 °C followed quickly by degradation beginning at ∼120 °C. The neat solid 5-FCPal amphiphile acquires a lamellar crystalline arrangement with a d-spacing of 28.6 ± 0.3 Å, indicating interdigitation of the hydrocarbon chains. Under aqueous conditions, solid 5-FCPal is non-swelling and no lyotropic liquid crystalline phase formation is observed. In order to assess the in vitro toxicity and in vivo efficacy in colloidal form, solid lipid nanoparticles (SLNs) with an average size of ∼700 nm were produced via high pressure homogenization. The in vitro toxicity of the 5-FCPal SLNs against several different cancer and normal cell types was assessed over a 48 h period, and IC50 values were comparable to those observed for Capecitabine. The in vivo efficacy of the 5-FCPal SLNs was then assessed against the highly aggressive mouse 4T1 breast cancer model. To do so, the prodrug SLNs were administered orally at 3 different dosages (0.1, 0.25, 0.5 mmol/mouse/day) and compared to Capecitabine delivered at the same dosages. After 21 days of receiving the treatments, the 0.5 mmol dose of 5-FCPal exhibited the smallest average tumour volume. Since 5-FCPal is activated in a similar manner to Capecitabine via a 3 step enzymatic pathway with the final step occurring preferentially at the tumour site, formulation of the prodrug into SLNs combines the advantage of selective, localized activation with the sustained release properties of nanostructured amphiphile self-assembly and multiple payload materials thereby potentially creating a more effective anticancer agent. 相似文献
815.
Charlotte M. Griffiths-Jones David W. Knight 《Tetrahedron》2011,67(44):8515-8528
The indole alkaloid α-cyclopiazonic acid 1 has been synthesised by a route, which features at its core an acid-catalysed cationic cascade cyclisation terminated by a sulfonamide group. 相似文献
816.
Fiona M. Deane Charlotte M. Miller Anita R. Maguire Florence O. McCarthy 《Journal of heterocyclic chemistry》2011,48(4):814-823
An improved method for the preparation of 3‐formyl‐1,4‐dimethylcarbazole, a key intermediate in the synthesis of ellipticine, is presented. Conditions of the Vilsmeier‐Haack reaction have been modified to facilitate the production of 3‐formyl‐1,4‐dimethylcarbazole as a major product leading to an overall improvement in yield of ellipticine from 3% to 14%. This approach was also applied to the synthesis of 6‐methylellipticine and 9‐methoxyellipticine. J. Heterocyclic Chem., (2011). 相似文献
817.
Stevens CJ Dallanegra R Chaplin AB Weller AS Macgregor SA Ward B McKay D Alcaraz G Sabo-Etienne S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(10):3011-3020
The IrIII fragment {Ir(PCy3)2(H)2}+ has been used to probe the role of the metal centre in the catalytic dehydrocoupling of H3B?NMe2H ( A ) to ultimately give dimeric aminoborane [H2BNMe2]2 ( D ). Addition of A to [Ir(PCy3)2(H)2(H2)2][BArF4] ( 1 ; ArF=(C6H3(CF3)2), gives the amine‐borane complex [Ir(PCy3)2(H)2(H3B?NMe2H)][BArF4] ( 2 a ), which slowly dehydrogenates to afford the aminoborane complex [Ir(PCy3)2(H)2(H2B? NMe2)][BArF4] ( 3 ). DFT calculations have been used to probe the mechanism of dehydrogenation and show a pathway featuring sequential BH activation/H2 loss/NH activation. Addition of D to 1 results in retrodimerisation of D to afford 3 . DFT calculations indicate that this involves metal trapping of the monomer–dimer equilibrium, 2 H2BNMe2 ? [H2BNMe2]2. Ruthenium and rhodium analogues also promote this reaction. Addition of MeCN to 3 affords [Ir(PCy3)2(H)2(NCMe)2][BArF4] ( 6 ) liberating H2B? NMe2 ( B ), which then dimerises to give D . This is shown to be a second‐order process. It also allows on‐ and off‐metal coupling processes to be probed. Addition of MeCN to 3 followed by A gives D with no amine‐borane intermediates observed. Addition of A to 3 results in the formation of significant amounts of oligomeric H3B?NMe2BH2?NMe2H ( C ), which ultimately was converted to D . These results indicate that the metal is involved in both the dehydrogenation of A , to give B , and the oligomerisation reaction to afford C . A mechanism is suggested for this latter process. The reactivity of oligomer C with the Ir complexes is also reported. Addition of excess C to 1 promotes its transformation into D , with 3 observed as the final organometallic product, suggesting a B? N bond cleavage mechanism. Complex 6 does not react with C , but in combination with B oligomer C is consumed to eventually give D , suggesting an additional role for free aminoborane in the formation of D from C . 相似文献
818.
Lee CY Bae YS Jeong NC Farha OK Sarjeant AA Stern CL Nickias P Snurr RQ Hupp JT Nguyen ST 《Journal of the American Chemical Society》2011,133(14):5228-5231
A series of isostructural, noncatenated, zinc-pillared-paddlewheel metal-organic framework materials has been synthesized from 1,2,4,5-tetrakis(carboxyphenyl)benzene and trans-1,2-dipyridylethene struts. Substantial kinetic selectivity in the adsorption of propene over propane can be observed, depending on the pore apertures and the rectangular-plate morphology of the crystals. 相似文献
819.
Harvey DJ Sobott F Crispin M Wrobel A Bonomelli C Vasiljevic S Scanlan CN Scarff CA Thalassinos K Scrivens JH 《Journal of the American Society for Mass Spectrometry》2011,22(3):568-581
The analysis of glycosylation from native biological sources is often frustrated by the low abundances of available material.
Here, ion mobility combined with electrospray ionization mass spectrometry have been used to extract the spectra of N-glycans released with PNGase F from a serial titration of recombinantly expressed envelope glycoprotein, gp120, from the
human immunodeficiency virus (HIV). Analysis was also performed on gp120 expressed in the α-mannosidase inhibitor, and in
a matched mammalian cell line deficient in GlcNAc transferase I. Without ion mobility separation, ESI spectra frequently contained
no observable ions from the glycans whereas ions from other compounds such as detergents and residual buffer salts were abundant.
After ion mobility separation on a Waters T-wave ion mobility mass spectrometer, the N-glycans fell into a unique region of the ion mobility/m/z plot allowing their profiles to be extracted with good signal:noise ratios. This method allowed N-glycan profiles to be extracted from crude incubation mixtures with no clean-up even in the presence of surfactants such
as NP40. Furthermore, this technique allowed clear profiles to be obtained from sub-microgram amounts of glycoprotein. Glycan
profiles were similar to those generated by MALDI-TOF MS although they were more susceptible to double charging and fragmentation.
Structural analysis could be accomplished by MS/MS experiments in either positive or negative ion mode but negative ion mode
gave the most informative spectra and provided a reliable approach to the analysis of glycans from small amounts of glycoprotein. 相似文献
820.
G. Peter Matthews Charlotte L. Levy Giuliano M. Laudone Katie L. Jones Cathy J. Ridgway Ingrid L. Hallin S. Andrea Gazze Lewis Francis W. Richard Whalley Joachim Schoelkopf Patrick A. C. Gane 《Transport in Porous Media》2018,124(2):631-653
This work addresses two continuing fallacies in the interpretation of percolation characteristics of porous solids. The first is that the first derivative (slope) of the intrusion characteristic of the non-wetting fluid or drainage characteristic of the wetting fluid corresponds to the void size distribution, and the second is that the sizes of all voids can be measured. The fallacies are illustrated with the aid of the PoreXpert® inverse modelling package. A new void analysis method is then described, which is an add-on to the inverse modelling package and addresses the second fallacy. It is applied to three widely contrasting and challenging porous media. The first comprises two fine-grain graphites for use in the next-generation nuclear reactors. Their larger void sizes were measured by mercury intrusion, and the smallest by using a grand canonical Monte Carlo interpretation of surface area measurement down to nanometre scale. The second application is to the mercury intrusion of a series of mixtures of ground calcium carbonate with powdered microporous calcium carbonate known as functionalised calcium carbonate (FCC). The third is the water retention/drainage characteristic of a soil sample which undergoes naturally occurring hydrophilic/hydrophobic transitions. The first-derivative approximation is shown to be reasonable in the interpretation of the mercury intrusion porosimetry of the two graphites, which differ only at low mercury intrusion pressures, but false for FCC and the transiently hydrophobic soil. The findings are supported by other experimental characterisations, in particular electron and atomic force microscopy. 相似文献