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901.
Christopher Bonet Andrew Pratt Mohamed M El-Gomati Jim A D Matthew Steven P Tear 《Microscopy and microanalysis》2008,14(5):439-450
Experimental low-loss electron (LLE) yields were measured as a function of loss energy for a range of elemental standards using a high-vacuum scanning electron microscope operating at 5 keV primary beam energy with losses from 0 to 1 keV. The resulting LLE yield curves were compared with Monte Carlo simulations of the LLE yield in the particular beam/sample/detector geometry employed in the experiment to investigate the possibility of modeling the LLE yield for a series of elements. Monte Carlo simulations were performed using both the Joy and Luo [Joy, D.C. & Luo, S., Scanning 11(4), 176988 (2005)] to assess the influence of the more recent stopping power data on the simulation results. Further simulations have been conducted to explore the influence of sample/detector geometry on the LLE signal in the case of layered samples consisting of a thin C overlayer on an elemental substrate. Experimental LLE data were collected from a range of elemental samples coated with a thin C overlayer, and comparisons with Monte Carlo simulations were used to establish the overlayer thickness. 相似文献
902.
CE and hydrogen-deuterium (H/D) exchange MS are useful tools in the analysis and characterisation of peptides. This study reports the facile coupling of these tools in the H/D exchange CE-MS analysis of model and pharmaceutically important peptides, using a sheath flow interface. The peptides varied in mass from 556 (leucine enkephalin) to 1620 Da (bombesin), and in charge state from 0.33 (leucine enkephalin) to 3.0 (substance P). The application of a BGE composed of ammonium formate buffer (25 mM, pD 3.5 in D(2)O (>98% D atom)), a sheath liquid composed of formic acid (0.25% v/v in D(2)O) and ACN (30:70 v/v), and dissolving the samples in a mixture of ACN/D(2)O (50:50 v/v) facilitates complete H/D exchange. Because of complete H/D exchange the ESI mass spectra produced are easy to interpret and comparable to those obtained from LC-MS analysis. The CE-H/D-MS approach has the advantage of requiring lower volumes of deuterated solvents. The b- and y-series fragments produced by using in-source decomposition correspond to those predicted. With the peptides studied, the complete exchange H/D exchange observed with both the molecular and fragment ions helps to confirm both amino acid composition and sequence. 相似文献
903.
Jonathan A. Dennis Nick W. Johnson Thomas W. Thorpe Stephen Wallace 《Angewandte Chemie (International ed. in English)》2023,62(38):e202306347
Small molecule organocatalysts are abundant in all living organisms. However, their use as organocatalysts in cells has been underexplored. Herein, we report that organocatalytic aldol chemistry can be interfaced with living Escherichia coli to enable the α-methylenation of cellular aldehydes using biogenic amines such as L-Pro or phosphate. The biocompatible reaction is mild and can be interfaced with butyraldehyde generated from D-glucose via engineered metabolism to enable the production of 2-methylenebutanal (2-MB) and 2-methylbutanal (2-MBA) by anaerobic fermentation, and 2-methylbutanol (2-MBO) by whole-cell catalysis. Overall, this study demonstrates the combination of non-enzymatic organocatalytic and metabolic reactions in vivo for the sustainable synthesis of valuable non-natural chemicals that cannot be accessed using enzymatic chemistry alone. 相似文献
904.
Bing Lin Minsheng Huang Liguo Zhao Anish Roy Vadim Silberschmidt Nick Barnard 《哲学杂志》2018,98(17):1550-1575
Strain-controlled cyclic deformation of a nickel-based single crystal superalloy has been modelled using three-dimensional (3D) discrete dislocation dynamics (DDD) for both [0?0?1] and [1?1?1] orientations. The work focused on the interaction between dislocations and precipitates during cyclic plastic deformation at elevated temperature, which has not been well studied yet. A representative volume element with cubic γ′-precipitates was chosen to represent the material, with enforced periodical boundary conditions. In particular, cutting of superdislocations into precipitates was simulated by a back-force method. The global cyclic stress–strain responses were captured well by the DDD model when compared to experimental data, particularly the effects of crystallographic orientation. Dislocation evolution showed that considerably high density of dislocations was produced for [1?1?1] orientation when compared to [0?0?1] orientation. Cutting of dislocations into the precipitates had a significant effect on the plastic deformation, leading to material softening. Contour plots of in-plane shear strain proved the development of heterogeneous strain field, resulting in the formation of shear-band embryos. 相似文献
905.
Reaction of alkaline benzenearsonous and 2,3‐dihydroxypropylarsonous acids with rac‐glycidol affords the corresponding arsinic acids, which after reduction with thiophenol are acylated with either fatty‐acid chlorides/pyridine or fatty acids/dicyclohexylcarbodiimide/4‐dimethylaminopyridine and oxidized with hydrogen peroxide to give the arsinolipids (rac‐2,3‐diacyloxypropyl)phenylarsinic and bis‐(rac‐2,3‐diacyloxypropyl)arsinic acids. The latter is a non‐isosteric analogue of bisphosphatidic acid. Copyright © 2000 John Wiley & Sons, Ltd. 相似文献
906.
907.
Heidi M. Muchall Nick H. Werstiuk Jean Lessard 《Journal of Molecular Structure》1999,469(1-3):135-142
Restricted open and unrestricted Becke3LYP/6-31+G(d) calculations on Π and Σ states as well as equilibrium geometries of the formamidyl radical (1) and four of its dialkyl substituted derivatives 2–5 have been carried out. While all radicals studied are significantly twisted about the RN–C(O) bond and show a Π-type total spin density, the calculations confirm the special status of N-tert-butyl acetamidyl (4) that was found with EPR spectroscopy. Each of the torsional double-minimum potentials of N-methyl and N-isopropyl radicals 2, 3, and 5 shows a low barrier to interconversion for two equivalent conformers whereas 4 is situated in a steeper well with a larger twist angle which explains reported EPR 13C hyperfine splittings. 相似文献
908.
Design and Modeling for Chatter Control 总被引:1,自引:0,他引:1
Boring bars for single-point turning on a lathe are particularly susceptible to chatter and have been the subject of numerous studies. Chatter is, in general, caused by instability. Clearly, the cutting process can be limited to regions of known stable operation. However, this severely constrains the machine-tool operation and causes a decrease in productivity. The more aggressive approach is to attack the stability problem directly through application of vibration control. Here, we demonstrate a new biaxial vibration control system (VPI Smart Tool) for boring bars. We present the experimentally determined modal properties of the VPI Smart Tool and demonstrate how these properties may be used to develop models suitable for chatter stability analysis, simulation, and development of feedback compensation. A phenomenological chatter model that captures much of the rich dynamic character observed during experiments is presented. We introduce the notion that the mean cutting force changes direction as the width of cut increases due to the finite nose radius of the tool. This phenomenon is used to explain the progression from chatter that is dominated by motions normal to the machined surface at small widths of cut to chatter that is dominated by motions tangential to the machined surface at large widths of cut. We show experimental evidence to support our assertion that a biaxial actuation scheme is necessary to combat the tendency of the tool to chatter in both directions. We then present some preliminary theoretical results concerning the persistence of subcritical instability as we expand consideration to high-speed machining. 相似文献
909.
Stanley A. Bajue Shellie Gumbs Lauren Jones Fitzgerald B. Bramwell Brian O. Patrick John P. Selegue Carolyn Pratt Brock 《Acta Crystallographica. Section C, Structural Chemistry》2003,59(1):m10-m12
Reaction of the potentially hexadentate ligand 1,9‐bis(2‐hydroxy‐1‐naphthalenemethylimino)‐3,7‐dithianonane with dimethyltin chloride gave the title 1:1 adduct, in which the long ligand wraps around the SnCl2Me2 unit and in which the stereochemistry is fully trans. This compound crystallizes from acetonitrile as the 1:1 solvate [Sn(CH3)2(C29H30N2O2S2)Cl2]·C2H3N. During the reaction, the hydroxyl protons move to the N atoms. Most of the chemically equivalent bond lengths agree to within experimental uncertainty, but the Sn—Cl bond that is inside the ligand pocket is substantially longer than the Sn—Cl bond that points away from the long ligand [2.668 (1) versus 2.528 (1) Å]. The O—Sn—O angle is 166.0 (1)°. Comparison of the Sn—O, C—O and aryl C—C bond lengths with those of related compounds shows that the most important resonance forms for the Schiff base aryloxide ligand are double zwitterions, but that the uncharged resonance forms having carbonyl groups also contribute significantly. 相似文献
910.
Grey Ballard Christian Ikenmeyer J.M. Landsberg Nick Ryder 《Journal of Pure and Applied Algebra》2019,223(8):3205-3224
This is the second in a series of papers on rank decompositions of the matrix multiplication tensor. We present new rank 23 decompositions for the matrix multiplication tensor . All our decompositions have symmetry groups that include the standard cyclic permutation of factors but otherwise exhibit a range of behavior. One of them has 11 cubes as summands and admits an unexpected symmetry group of order 12.We establish basic information regarding symmetry groups of decompositions and outline two approaches for finding new rank decompositions of for larger n. 相似文献