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101.
102.
Optimization of separations of alkyl-substituted phenolate anions by capillary zone electrophoresis 总被引:1,自引:0,他引:1
Anions of alkylphenols have very similar electrophoretic mobilities in CZE owing to their very small differences in size and the narrow range of their pKa values. By studying electrophoretic mobility as a function both of pH and of the amount of acetonitrile in the electrolyte solution, optimum separation conditions were determined. It was possible to separate a group of methyl-substituted phenols, including several positional isomers. Mixtures containing n-propyl and isopropyl phenols and 1°, 2°, and 3° butylphenols could be resolved. 相似文献
103.
This paper presents a network model with discrete requirements for a nuclear power plant. The model determines the batch size and timing for nuclear unit refueling and how much energy should be produced by nuclear and non-nuclear units for each time period to satisfy forecasted demand with minimum total operating costs over the planning horizon. Efficient modeling and solution strategies are developed which constitute a merger of operations research and artificial intelligence. A branch-and-bound solution approach is combined with a pattern recognition component, involving non-parametric discrimination analyses, to select branching variables and directions. By coupling this approach with network optimization techniques to exploit the underlying network structure of the problem, substantial improvements are obtained both in solution quality and solution efficiency.This research was supported in part by the Center for Business Decision Analysis, the Hugh Roy Cullen Centennial Chair in Business Administration, and the Office of Naval Research under contract N00014-87-K-0190. Reproduction in whole or in part is permitted for any purpose of the U.S. Government. CENTER FOR BUSINESS DECISION ANALYSIS Darwin Klingman, Director The University of Texas at Austin Austin, TX 78712, U.S.A. 相似文献
104.
Selective reagent ionisation‐time of flight‐mass spectrometry: a rapid technology for the novel analysis of blends of new psychoactive substances
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Matteo Lanza W. Joe Acton Philipp Sulzer Kostiantyn Breiev Simone Jürschik Alfons Jordan Eugen Hartungen Gernot Hanel Lukas Märk Tilmann D. Märk Chris A. Mayhew 《Journal of mass spectrometry : JMS》2015,50(2):427-431
In this study we demonstrate the potential of selective reagent ionisation‐time of flight‐mass spectrometry for the rapid and selective identification of a popular new psychoactive substance blend called ‘synthacaine’, a mixture that is supposed to imitate the sensory and intoxicating effects of cocaine. Reactions with H3O+ result in protonated parent molecules which can be tentatively assigned to benzocaine and methiopropamine. However, by comparing the product ion branching ratios obtained at two reduced electric field values (90 and 170 Td) for two reagent ions (H3O+ and NO+) to those of the pure chemicals, we show that identification is possible with a much higher level of confidence then when relying solely on the m/z of protonated parent molecules. A rapid and highly selective analytical identification of the constituents of a recreational drug is particularly crucial to medical personnel for the prompt medical treatment of overdoses, toxic effects or allergic reactions. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
105.
Alexander Stephenson-Brown Aaron L. Acton Jon A. Preece John S. Fossey Paula M. Mendes 《Chemical science》2015,6(9):5114-5119
Many glycoproteins are intimately linked to the onset and progression of numerous heritable or acquired diseases of humans, including cancer. Indeed the recognition of specific glycoproteins remains a significant challenge in analytical method and diagnostic development. Herein, a hierarchical bottom-up route exploiting reversible covalent interactions with boronic acids and so-called click chemistry for the fabrication of glycoprotein selective surfaces that surmount current antibody constraints is described. The self-assembled and imprinted surfaces, containing specific glycoprotein molecular recognition nanocavities, confer high binding affinities, nanomolar sensitivity, exceptional glycoprotein specificity and selectivity with as high as 30 fold selectivity for prostate specific antigen (PSA) over other glycoproteins. This synthetic, robust and highly selective recognition platform can be used in complex biological media and be recycled multiple times with no performance decrement. 相似文献
106.
107.
The rate constant of the comparably slow bimolecular NCN radical reaction NCN + O2 has been measured for the first time under combustion relevant conditions using the shock tube method. The thermal decomposition of cyanogen azide (NCN3) served as a clean high‐temperature source of NCN radicals. NCN concentration–time profiles have been detected by narrow‐bandwidth laser absorption at cm?1. The experiments behind incident shock waves have been performed with up to 17% O2 in the reaction gas mixture. At such high O2 mole fractions, it was necessary to take O2 relaxation into account that caused a gradual decrease of the temperature during the experiment. Moreover, following fast decomposition of NCN3 and collision‐induced intersystem crossing of the initially formed singlet NCN to its triplet ground state, an unexpected and slow additional formation of triplet NCN has been observed on a 100‐μs timescale. This delayed NCN formation was attributed to a fast recombination of 1NCN with O2 forming a 3NCNOO adduct acting as a reservoir species for NCN. Rate constant data for the reaction NCN + O2 have been measured at temperatures between 1674 and 2308 K. They are best represented by the Arrhenius expression . No pressure dependence has been observed at pressures between 216 and 706 mbar. 相似文献
108.
Highly trans‐Selective Arylation of Achmatowicz Rearrangement Products by Reductive γ‐Deoxygenation and Heck–Matsuda Reaction: Asymmetric Total Synthesis of (−)‐Musellarins A–C and Their Analogues
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Zhilong Li Dr. Fanny C. F. Ip Prof. Dr. Nancy Y. Ip Prof. Dr. Rongbiao Tong 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(31):11152-11157
Fully functionalized pyranuloses derived from Achmatowicz rearrangement (AR) are versatile building blocks in organic synthesis. However, access to trans‐2,6‐dihydropyrans from pyranuloses remains underexplored. Herein, we report a new two‐step trans arylation of AR products to access 2,6‐trans‐dihydropyranones. This new trans‐arylation method built on numerous plausible, but unsuccessful, direct arylation reactions, including Ferrier‐type and Tsuji–Trost‐type reactions, was finally enabled by an unprecedented, highly regioselective γ‐deoxygenation of AR products by using Zn/HOAc and a diastereoselective Heck–Matsuda coupling. The synthetic utility of the reaction was demonstrated in the first asymmetric total synthesis of (?)‐musellarins A–C and 12 analogues in 11–12 steps. The brevity and efficiency of our synthetic route permitted preparation of enantiomerically pure musellarins and analogues (>20 mg) for preliminary cytotoxicity evaluation, which led us to identify two analogues with three‐to‐six times greater potency than the musellarins as promising new leads. 相似文献
109.
Wooyong Lee Priscilla E. Greenwood Nancy Heckman Wolfgang Wefelmeyer 《Statistical Inference for Stochastic Processes》2017,20(2):237-252
We consider estimation of the drift function of a stationary diffusion process when we observe high-frequency data with microstructure noise over a long time interval. We propose to estimate the drift function at a point by a Nadaraya–Watson estimator that uses observations that have been pre-averaged to reduce the noise. We give conditions under which our estimator is consistent and asympotically normal. Its rate and asymptotic bias and variance are the same as those without microstructure noise. To use our method in data analysis, we propose a data-based cross-validation method to determine the bandwidth in the Nadaraya–Watson estimator. Via simulation, we study several methods of bandwidth choices, and compare our estimator to several existing estimators. In terms of mean squared error, our new estimator outperforms existing estimators. 相似文献
110.
We report parametric studies of elastic wave generation by a pulsed laser and associated spalling of thin surface films by
the corresponding high stresses. Two different substrate materials, single crystal Si (100) and fused silica, are considered.
Spallation behavior of Al thin films is investigated as a function of substrate thickness, film thickness, laser energy, and
various parameters governing the source. Surface displacement due to the stress wave is measured by Michaelson interferometry
and used to infer the stresses on the film interface. Consistent with previous studies, the maximum stress in the substrate
and at the film/substrate interface increases with increasing laser fluence. For many of the conditions tested, the substrate
stress is large enough to damage the Si. Moreover, the maximum interface stress is found to increase with increasing film
thickness, but decrease with increasing substrate thickness due to geometric attenuation. Of particular significance is the
development of a decompression shock in the fused sillica substrates, which results in very high tensile stresses at the interface.
This shock enhances the failure of thin film interfaces, especially in thicker samples. 相似文献