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排序方式: 共有302条查询结果,搜索用时 921 毫秒
1.
M. R. McEwen J. P. Sephton P. H. G. Sharpe D. R. Shipley 《Radiation Physics and Chemistry》2003,68(6):1017-1022
A phantom composed of alanine dosimeter material has been constructed and depth–dose measurements made in a 10 MeV electron beam. The results have demonstrated the feasibility of using relative depth–dose measurements to determine stopping power ratios in materials of dosimetric interest. Experimental stopping power ratios for alanine dosimeter material and water agreed with the data of ICRU Report 37 within the uncertainty of the experiment (±1.2% at a 95% confidence level). 相似文献
2.
Gary H. Posner Timothy P. Kogan Stephen R. Haines Leah L. Frye 《Tetrahedron letters》1984,25(25):2627-2630
A short, reliable, and practical synthesis of ()-(+)-2-(-tolylsulfinyl)-2-buten-4-olide has been developed, and the utility of this Michael acceptor for highly enantiocontrolled synthesis of 3-substituted 4-butanolides has been demonstrated. 相似文献
3.
LacTek tests are competitive enzyme-linked immunosorbent assays intended for rapid detection of antimicrobial residues in bovine milk. In this study, the LacTek test protocol was modified for use with extracts of bovine tissue to detect beta-lactam, tetracycline, and sulfamethazine residues. Test performance characteristics--precision, accuracy, ruggedness, practicability, and analytical specificity and sensitivity--were investigated. Results suggest that LacTek tests can be easily adapted to detect antimicrobial residues in extracts of lean ground beef. However, positive samples may not contain residues at violative concentrations (i.e., Canadian maximum residue limits), and therefore, additional analysis would be required for final confirmation and quantitation (e.g., chromatography). 相似文献
4.
Appelhans LN Zuccaccia D Kovacevic A Chianese AR Miecznikowski JR Macchioni A Clot E Eisenstein O Crabtree RH 《Journal of the American Chemical Society》2005,127(46):16299-16311
Changing the counteranion along the series Br, BF4, PF6, SbF6 in their ion-paired 2-pyridylmethyl imidazolium salts causes the kinetic reaction products with IrH5(PPh3)2 to switch from chelating N-heterocyclic carbenes (NHCs) having normal C2 (N path) to abnormal C5 binding (AN path). Computational work (DFT) suggests that the AN path involves C-H oxidative addition to Ir(III) to give Ir(V) with little anion dependence. The N path, in contrast, goes by heterolytic C-H activation with proton transfer to the adjacent hydride. The proton that is transferred is accompanied by the counteranion in an anion-coupled proton transfer, leading to an anion dependence of the N path, and therefore of the N/AN selectivity. The N path goes via Ir(III), not Ir(V), because the normal NHC is a much less strong donor ligand than the abnormal NHC. PGSE NMR experiments support the formation of ion-pair in both the reactants and the products. 19F,1H-HOESY NMR experiments indicate an ion-pair structure for the products that is consistent with the computational prediction (ONIOM(B3PW91/UFF)). 相似文献
5.
Vera A. Vil' Yana A. Barsegyan Leah Kuhn Maria V. Ekimova Egor A. Semenov Alexander A. Korlyukov Alexander O. Terent'ev Igor V. Alabugin 《Chemical science》2020,11(20):5313
How far can we push the limits in removing stereoelectronic protection from an unstable intermediate? We address this question by exploring the interplay between the primary and secondary stereoelectronic effects in the Baeyer–Villiger (BV) rearrangement by experimental and computational studies of γ-OR-substituted γ-peroxylactones, the previously elusive non-strained Criegee intermediates (CI). These new cyclic peroxides were synthesized by the peroxidation of γ-ketoesters followed by in situ cyclization using a BF3·Et2O/H2O2 system. Although the primary effect (alignment of the migrating C–Rm bond with the breaking O–O bond) is active in the 6-membered ring, weakening of the secondary effect (donation from the OR lone pair to the breaking C–Rm bond) provides sufficient kinetic stabilization to allow the formation and isolation of stable γ-hydroperoxy-γ-peroxylactones with a methyl-substituent in the C6-position. Furthermore, supplementary protection is also provided by reactant stabilization originating from two new stereoelectronic factors, both identified and quantified for the first time in the present work. First, an unexpected boat preference in the γ-hydroperoxy-γ-peroxylactones weakens the primary stereoelectronic effects and introduces a ∼2 kcal mol−1 Curtin–Hammett penalty for reacquiring the more reactive chair conformation. Second, activation of the secondary stereoelectronic effect in the TS comes with a ∼2–3 kcal mol−1 penalty for giving up the exo-anomeric stabilization in the 6-membered Criegee intermediate. Together, the three new stereoelectronic factors (inverse α-effect, misalignment of reacting bonds in the boat conformation, and the exo-anomeric effect) illustrate the richness of stereoelectronic patterns in peroxide chemistry and provide experimentally significant kinetic stabilization to this new class of bisperoxides. Furthermore, mild reduction of γ-hydroperoxy-γ-peroxylactone with Ph3P produced an isolable γ-hydroxy-γ-peroxylactone, the first example of a structurally unencumbered CI where neither the primary nor the secondary stereoelectronic effect are impeded. Although this compound is relatively unstable, it does not undergo the BV reaction and instead follows a new mode of reactivity for the CI – a ring-opening process.Protecting stereoelectronic effects prevent Baeyer–Villiger rearrangement and stabilize γ-OX-γ-peroxylactones (X = H, OH), the previously elusive non-strained Criegee intermediates. 相似文献
6.
Lake DA Johnson MV McEwen CN Larsen BS 《Rapid communications in mass spectrometry : RCM》2000,14(11):1008-1013
An automated sample preparation for high throughput accurate mass determinations by matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOFMS) has been developed. Sample preparation was performed with an automated workstation and automated mass analyses were performed with a commercial MALDI-TOF mass spectrometer. The method was tested with a 41-sample library. MALDI-TOFMS was found to give the needed sensitivity, accurate mass measurement, and soft ionization necessary for structure confirmation, even of mixtures. A mass accuracy of 5 ppm or less was obtained in over 80% of known compound measurements. A mass accuracy better than 10 ppm was obtained for all measurements of known compounds. Analyses of parallel synthesis products resulted in 77% of the measurements with a mass accuracy of 5 ppm or better. 相似文献
7.
A conventional ion-exchange amino acid analyser kit has been simply and economically constructed for use with existing high-performance liquid chromatography (HPLC) apparatus. Sequential elution conditions are fully programmable by virtue of a 32K BBC microcomputer interfaced with an elution buffer selection valve and a thermostatically controlled column. Post-column derivatization with o-phthaladehyde-2-mercaptoethanol reagent enables fluorimetric detection at the picomole level. The system enables sensitive amino acid analysis of complex mixtures to be carried out by clinical and research laboratories who already possess HPLC apparatus but whose sample turnover does not merit purchase of a dedicated fully automated analyser. 相似文献
8.
9.
Verena Bögelein Frank Duzaar Leah Schätzler Christoph Scheven 《Journal of Differential Equations》2019,266(11):7709-7748
We establish that solutions to the Cauchy–Dirichlet problem for functionals of linear growth can be obtained as limits of solutions to flows with p-growth in the limit . The result can be interpreted on the one hand as a stability result. On the other hand it provides an existence result for general flows with linear growth. 相似文献
10.